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Supporting Information

Stable Crystalline Annulated Diaminocarbenes: Coordination with Rhodium (I), Iridium (I) and

Catalytic Hydroformylation Studies

Sarim Dastgir,*a Karl S. Coleman,b Andrew R. Cowleya and Malcolm L. H. Green*a

*a Inorganic Chemistry Laboratory, University of Oxford, South Parks Road,

Oxford,OX1 3QR, UK.

E-mail: [email protected] (Professor Malcolm L. H. Green FRS.);

Tel: +44 (0) 1865 272600; Fax: +44 (0) 1865 272690;

E-mail: [email protected] (Dr. Sarim Dastgir; Present Address: Department of Chemistry,

York University, 4700 Keele Street, Toronto, ON, M3J 2Z3, Canada);

Tel: +1 416 736 2100 Ext. 77720; Fax:+1 416 736 5936.

b Department of Chemistry, University of Durham., UK.

Electronic Supplementary Information for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2009

mailto:[email protected]�


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General procedures:

• All manipulations were performed under dinitrogen using standard Schlenk vessel

techniques or in an inert atmosphere glove box.

• Solvents used in the preparation of air and/or moisture sensitive compounds were dried by

passage through an alumina column or by refluxing and then distilling from

potassium/sodium (3:1 w/w) alloy (40-60 petroleum ether, pentane, THF), sodium (DME,

toluene, diethyl ether, 1,4-dioxane), magnesium/iodine (methanol, ethanol, tBuOH) under a

positive pressure of dinitrogen. All the dry solvents were deoxygenated by bubbling dry

dinitrogen through the solvents for twenty minutes before use.

• Deuterated solvents were degassed using three freeze-pump-thaw cycles and were vacuum

distilled from potassium or sodium (d6-benzene, d8-toluene) or CaH2 (CD2Cl2, CDCl3,

CD3CN) and stored in Young’s ampoules under nitrogen.

• NMR spectra were recorded on either a Varian Unity Plus 500 (1H at 500 MHz, 13C at

125.7 MHz) or on a Varian Mercury 300 (1H at 300 MHz, 13C at 75.5 MHz) spectrometer at

room temperature unless otherwise stated. The spectra were referenced internally relative to

the residual protio-solvent (1H) and solvent (13C) resonances and chemical shifts were

reported with respect to δ = 0 for tetramethylsilane.

• Electrospray mass spectra were recorded in acetonitrile (unless otherwise stated) on a

Micromass LC TOF spectrometer.

• Microanalyses were performed by the microanalytical laboratory of the Inorganic

Chemistry Laboratory, University of Oxford.

• Gas Chromatographs were recorded using Perkin Elmer XL 1100 instrument with Perkin

Elmer NCI 900 Network Chromatography Interface using fused silica, non-polar SGE



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column 25QC2/BP1 1.0.

• All reagents were purchased from Aldrich, metal precursors from Johnson-Matthey and

used as received unless otherwise stated. The reagents Ar-BIAN,1, 2 [(BIAN-

SIMes)(H)]BF4,3 [(BIAN-SIPr)(H)]BF4,3 [Rh(COD)Cl]24

and [Ir(COD)Cl]25

were prepared

using published procedures.

• The bases NaOtBu, KOtBu were freshly prepared and KN(SiMe3)2 was supplied by Aldrich.

The bases were triply sublimed and kept in the inert atmosphere glove box.

Typical Hydroformylation Conditions

Hydroformylation reactions were carried out in an autoclave, equipped with a glass liner and a

magnetic stirrer. The Liner was charged with the catalyst (1 μmol unless otherwise stated), 1-octene

(156μL, 1.0 mmol) and 5.0 mL of dry toluene. The gauge block assembly was then rapidly attached

and the reaction chamber flushed with CO/H2 (CO/H2, 33:67). The autoclave was pressurized to the

appropriate pressure (8-55 bar), heated to the appropriate temperature (40 – 100 ˚C), and stirred for 24

hours unless otherwise stated. The autoclave was then cooled to room temperature and the pressure

released. The contents were transferred to a 10 mL round bottom flask and 0.2 mL of cyclohexane as

an internal standard was added. The samples were then analyzed by Gas chromatography using a

Perkin S4 Elmer XL 1100 instrument equipped with fused silica, non-polar SGE column 25QC2/BP1

1.0. and the results reported as an average of two GC runs (Table 5).

References

1. A. Paulovicova, U. El-Ayaan, K. Shibayama, T. Morita and Y. Fukuda, Eur. J. Inorg. Chem., 2001, 10, 2641.

2. P. Preishuber-Pflugl and M. Brookhart, Macromolecules, 2002, 35, 6074. 3. S. Dastgir, K. S. Coleman, A. H. Cowley and M. L. H. Green, Manuscripts in preparation,

2009. 4. J. Chatt and L. M. Venanzi, J. Chem. Soc., 1986, 4735. 5. R. H. Crabtree and G. E. Morris, J. Organomet. Chem., 1977, 135, 395.



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Inorganic Chemistry Crystallography Service

Department of Chemistry, University of Oxford Chemistry Research Laboratory

Mansfield Road, Oxford OX1 3TA.



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A. Single-crystal X-ray diffraction report for CCDC_719732_4b

Crystals of the N-(acenaphthylene-1-yl)-N-N-bis(2,6-diisopropylphenyl)formamidine,

4b suitable for X-ray diffraction study were grown from a saturated solution of diethyl ether at

-78oC. A single crystal having dimensions approximately 0.18 x 0.36 x 0.36 mm was mounted

on a glass fibre using perfluoropolyether oil and cooled rapidly to 150K in a stream of cold N2

using an Oxford Cryosystems CRYOSTREAM unit. Diffraction data were measured using an

Enraf-Nonius KappaCCD diffractometer (graphite-monochromated MoKα radiation, λ =

0.71073 Å). Intensity data were processed using the DENZO-SMN package1.

Examination of the systematic absences of the intensity data showed the space group

to be either P 21 or P 21/m. The structure could not be solved in the latter space group but

was solved in the space group P 21 using the direct-methods program SIR922, which located

all non-hydrogen atoms. Subsequent full-matrix least-squares refinement was carried out

using the CRYSTALS program suite3. Coordinates and anisotropic thermal parameters of all

non-hydrogen atoms were refined. One of the isopropyl C atoms (C(70)) was seen to have

abnormally large and anisotropic thermal parameters, indicative of disorder, but attempt to

model this led to no improvement in the agreement with the X-ray data and were abandoned.

Hydrogen atoms were positioned geometrically after each cycle of refinement. A 3-term

Chebychev polynomial weighting scheme was applied. Refinement converged satisfactorily

to give R = 0.0419, wR = 0.0507.

Attached is a thermal ellipsoid plot (ORTEP-34) at 40% probability. A summary of

crystallographic data is given below, as are full lists of atomic coordinates, anisotropic

thermal parameters and those bond lengths and angles not concerning H atoms.

Comment: The two crystallographically-distinct molecules differ in their conformations about the

bond between the tertiary N and the imine C. In both cases the atoms of the phenanthrene,

amine N and imine groups are all approximately coplanar with the two isopropyl groups

apprtoximately perpendicular to these planes.

References: 1 Z. Otwinowski and W. Minor, Processing of X-ray Diffraction Data Collected in

Oscillation Mode, Methods Enzymol., 1997, 276, Eds C. W. Carter and R. M. Sweet,

Academic Press.



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2 A. Altomare, G. Cascarano, G. Giacovazzo, A. Guagliardi ,M. C. Burla, G. Polidori and

M. Camalli, J. Appl. Cryst. 1994, 27, 435.

3 CRYSTALS Issue 12, P. W. Betteridge, J. R. Cooper, R. I. Cooper, K. Prout and D. J.

Watkin, J. Appl. Cryst., 2003, 36, 1487

4 ORTEP-3 v. 1.0.2, C. K. Johnson and M. K. Burnett, 1998.



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Views of the two crystallographically-distinct molecules.



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Table 1: Crystal data and refinement details

Crystal identification CCDC_719732_4b Chemical formula C37H42N2 Formula weight 514.75 Temperature (K) 150 Wavelength (Å) 0.71073 Crystal system Monoclinic Space group P 21 a (Å) 11.8694(2) b (Å) 21.1724(4) c (Å) 12.4791(2) α (°) 90 β (°) 107.5287(9) γ (°) 90 Cell volume (Å3) 2990.43(9) Z 4 Calculated density (Mg/m3) 1.143 Absorption coefficient (mm-1) 0.066 F000 1112 Crystal size (mm) 0.18 x 0.36 x 0.36 Description of crystal Orange tablet Absorption correction Semi-empirical from equivalent reflections Transmission coefficients (min,max) 0.98, 0.99 θ range for data collection (°) 5.0 ≤ θ ≤ 27.5 Index ranges -15 ≤ h ≤ 14, 0 ≤ k ≤ 27, 0 ≤ l ≤ 16 Reflections measured 30599 Unique reflections 6996 Rint 0.037 Observed reflections (I > 3σ(I)) 5394 Refinement method Full-matrix least-squares on F Parameters refined 703 Weighting scheme Chebychev 3-term polynomial Goodness of fit 1.1213 R 0.0419 wR 0.0507 Residual electron density (min,max) (eÅ-3) -0.29, 0.38



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Table 2: Atomic coordinates and equivalent isotropic thermal parameters (Å2) of non-hydrogen atoms

Atom x y z Uequiv

N(1) -0.02029(17) 0.51298(9) 0.01492(16) 0.0246 C(1) -0.1064(2) 0.49768(11) 0.06389(19) 0.0273 N(2) -0.13238(17) 0.44125(9) 0.07914(16) 0.0276 C(2) 0.0028(2) 0.57646(11) -0.00179(19) 0.0257 C(3) -0.0567(2) 0.62813(12) 0.0206(2) 0.0318 C(4) -0.0021(2) 0.68520(12) -0.0074(2) 0.0328 C(5) -0.0213(3) 0.74936(13) -0.0032(3) 0.0419 C(6) 0.0518(3) 0.79157(13) -0.0387(3) 0.0484 C(7) 0.1416(3) 0.77170(13) -0.0789(2) 0.0426 C(8) 0.1651(2) 0.70570(12) -0.0835(2) 0.0358 C(9) 0.2532(2) 0.67682(14) -0.1208(2) 0.0388 C(10) 0.2631(2) 0.61201(14) -0.1206(2) 0.0400 C(11) 0.1866(2) 0.57134(13) -0.0832(2) 0.0338 C(12) 0.0995(2) 0.59822(12) -0.04699(19) 0.0276 C(13) 0.0907(2) 0.66522(12) -0.04764(19) 0.0288 C(14) 0.04712(19) 0.46337(11) -0.01693(19) 0.0243 C(15) 0.0067(2) 0.43913(12) -0.1268(2) 0.0308 C(16) 0.0796(3) 0.39659(13) -0.1593(2) 0.0392 C(17) 0.1869(3) 0.37780(13) -0.0844(3) 0.0412 C(18) 0.2216(2) 0.39949(13) 0.0251(2) 0.0356 C(19) 0.1520(2) 0.44284(11) 0.06145(19) 0.0274 C(20) -0.1121(2) 0.45814(14) -0.2078(2) 0.0382 C(21) -0.0977(3) 0.50728(19) -0.2918(3) 0.0619 C(22) -0.1800(3) 0.40059(19) -0.2694(3) 0.0584 C(23) 0.1927(2) 0.46682(13) 0.1821(2) 0.0338 C(24) 0.3055(2) 0.50658(16) 0.2051(3) 0.0451 C(25) 0.2112(3) 0.41186(16) 0.2658(2) 0.0500 C(26) -0.2251(2) 0.43184(10) 0.1299(2) 0.0265 C(27) -0.2025(2) 0.43779(12) 0.2464(2) 0.0305 C(28) -0.2946(2) 0.42732(14) 0.2910(2) 0.0383 C(29) -0.4061(2) 0.40986(14) 0.2225(3) 0.0423 C(30) -0.4264(2) 0.40274(14) 0.1080(2) 0.0389 C(31) -0.3364(2) 0.41287(12) 0.0600(2) 0.0318 C(32) -0.0806(2) 0.45473(14) 0.3243(2) 0.0373 C(33) -0.0781(3) 0.52109(17) 0.3731(3) 0.0583 C(34) -0.0396(3) 0.40598(19) 0.4185(3) 0.0593 C(35) -0.3586(2) 0.40586(14) -0.0657(2) 0.0418 C(36) -0.4091(4) 0.46626(19) -0.1268(3) 0.0644 C(37) -0.4341(3) 0.34883(17) -0.1155(3) 0.0591

N(3) 0.50612(17) 0.62808(9) 0.50981(16) 0.0258 C(38) 0.5882(2) 0.65403(12) 0.46307(19) 0.0283 N(4) 0.66543(18) 0.62410(10) 0.43413(16) 0.0297 C(39) 0.4899(2) 0.56331(11) 0.52033(18) 0.0253 C(40) 0.5523(2) 0.51551(11) 0.4898(2) 0.0279 C(41) 0.5036(2) 0.45551(12) 0.51240(19) 0.0294 C(42) 0.5289(3) 0.39267(12) 0.4992(2) 0.0363 C(43) 0.4603(3) 0.34564(13) 0.5326(2) 0.0413



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C(44) 0.3713(3) 0.35962(13) 0.5776(2) 0.0403 C(45) 0.3447(2) 0.42406(12) 0.5933(2) 0.0327 C(46) 0.2567(2) 0.44821(13) 0.6385(2) 0.0364 C(47) 0.2423(2) 0.51158(15) 0.6466(2) 0.0413 C(48) 0.3131(2) 0.55702(12) 0.6106(2) 0.0346 C(49) 0.3984(2) 0.53538(11) 0.56601(19) 0.0275 C(50) 0.4115(2) 0.46899(12) 0.55859(18) 0.0287 C(51) 0.4322(2) 0.67429(10) 0.54203(19) 0.0256 C(52) 0.4750(2) 0.70240(12) 0.6487(2) 0.0320 C(53) 0.4024(3) 0.74655(14) 0.6781(2) 0.0427 C(54) 0.2937(3) 0.76278(14) 0.6050(3) 0.0460 C(55) 0.2559(2) 0.73633(13) 0.4991(3) 0.0430 C(56) 0.3248(2) 0.69136(12) 0.4645(2) 0.0314 C(57) 0.5959(2) 0.68635(14) 0.7288(2) 0.0375 C(58) 0.5913(4) 0.6286(2) 0.7999(3) 0.0718 C(59) 0.6531(3) 0.74150(18) 0.8042(3) 0.0628 C(60) 0.2817(2) 0.66505(14) 0.3463(2) 0.0400 C(61) 0.1690(3) 0.62518(17) 0.3287(3) 0.0544 C(62) 0.2575(4) 0.7187(2) 0.2601(3) 0.0742 C(63) 0.7360(2) 0.66115(12) 0.3832(2) 0.0313 C(64) 0.6997(2) 0.66590(15) 0.2653(2) 0.0411 C(65) 0.7713(3) 0.70061(18) 0.2162(2) 0.0517 C(66) 0.8723(3) 0.72979(18) 0.2795(3) 0.0580 C(67) 0.9059(3) 0.72459(16) 0.3956(3) 0.0501 C(68) 0.8401(2) 0.68910(13) 0.4492(2) 0.0378 C(69) 0.5866(3) 0.6331(2) 0.1945(2) 0.0535 C(70) 0.4935(5) 0.6792(3) 0.1380(5) 0.1224 C(71) 0.6065(4) 0.5855(2) 0.1110(4) 0.0741 C(72) 0.8831(2) 0.68029(15) 0.5766(2) 0.0428 C(73) 0.8681(4) 0.7401(2) 0.6369(3) 0.0685 C(74) 1.0103(3) 0.65717(19) 0.6173(3) 0.0577



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Table 3: Atomic coordinates and isotropic thermal parameters (Å2) of hydrogen atoms

Atom x y z Uiso

H(11) -0.1500 0.5326 0.0882 0.0323 H(31) -0.1256 0.6269 0.0510 0.0385 H(51) -0.0864 0.7656 0.0248 0.0481 H(61) 0.0378 0.8379 -0.0344 0.0544 H(71) 0.1904 0.8033 -0.1048 0.0480 H(91) 0.3090 0.7035 -0.1475 0.0462 H(101) 0.3263 0.5927 -0.1478 0.0494 H(111) 0.1963 0.5244 -0.0835 0.0408 H(161) 0.0545 0.3793 -0.2375 0.0498 H(171) 0.2394 0.3483 -0.1101 0.0546 H(181) 0.2972 0.3840 0.0789 0.0445 H(201) -0.1592 0.4775 -0.1620 0.0449 H(211) -0.1771 0.5188 -0.3437 0.0699 H(212) -0.0588 0.5458 -0.2505 0.0699 H(213) -0.0476 0.4895 -0.3362 0.0699 H(221) -0.2575 0.4146 -0.3219 0.0683 H(222) -0.1326 0.3794 -0.3131 0.0683 H(223) -0.1942 0.3703 -0.2134 0.0683 H(231) 0.1287 0.4946 0.1926 0.0392 H(241) 0.3297 0.5215 0.2848 0.0514 H(242) 0.2901 0.5438 0.1535 0.0514 H(243) 0.3701 0.4803 0.1921 0.0514 H(251) 0.2378 0.4288 0.3442 0.0586 H(252) 0.2727 0.3826 0.2543 0.0586 H(253) 0.1352 0.3884 0.2534 0.0586 H(281) -0.2808 0.4324 0.3736 0.0479 H(291) -0.4715 0.4024 0.2561 0.0532 H(301) -0.5067 0.3902 0.0593 0.0461 H(321) -0.0246 0.4543 0.2783 0.0449 H(331) 0.0031 0.5305 0.4237 0.0685 H(332) -0.1358 0.5236 0.4171 0.0685 H(333) -0.0999 0.5526 0.3106 0.0685 H(341) 0.0405 0.4179 0.4687 0.0667 H(342) -0.0967 0.4048 0.4632 0.0667 H(343) -0.0357 0.3634 0.3853 0.0667 H(351) -0.2799 0.3979 -0.0769 0.0480 H(361) -0.4230 0.4605 -0.2093 0.0726 H(362) -0.4856 0.4764 -0.1125 0.0726 H(363) -0.3520 0.5017 -0.0990 0.0726 H(371) -0.4454 0.3469 -0.1982 0.0671 H(372) -0.5128 0.3526 -0.1021 0.0671 H(373) -0.3938 0.3095 -0.0790 0.0671

H(381) 0.5853 0.7008 0.4515 0.0335 H(401) 0.6195 0.5209 0.4578 0.0331 H(421) 0.5936 0.3806 0.4672 0.0431 H(431) 0.4780 0.3002 0.5226 0.0491 H(441) 0.3254 0.3249 0.5994 0.0465



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H(461) 0.2052 0.4184 0.6646 0.0435 H(471) 0.1798 0.5271 0.6788 0.0524 H(481) 0.3007 0.6033 0.6179 0.0422 H(531) 0.4296 0.7669 0.7538 0.0556 H(541) 0.2424 0.7938 0.6288 0.0587 H(551) 0.1780 0.7494 0.4461 0.0520 H(571) 0.6466 0.6765 0.6799 0.0447 H(581) 0.6722 0.6195 0.8514 0.0774 H(582) 0.5364 0.6369 0.8453 0.0774 H(583) 0.5624 0.5914 0.7497 0.0774 H(591) 0.7321 0.7282 0.8549 0.0721 H(592) 0.6633 0.7778 0.7567 0.0721 H(593) 0.6015 0.7546 0.8506 0.0721 H(601) 0.3454 0.6371 0.3355 0.0452 H(611) 0.1428 0.6085 0.2500 0.0614 H(612) 0.1051 0.6521 0.3417 0.0614 H(613) 0.1859 0.5891 0.3829 0.0614 H(621) 0.2292 0.7006 0.1825 0.0825 H(622) 0.3319 0.7431 0.2689 0.0825 H(623) 0.1957 0.7474 0.2724 0.0825 H(651) 0.7482 0.7042 0.1324 0.0651 H(661) 0.9216 0.7547 0.2423 0.0751 H(671) 0.9788 0.7468 0.4417 0.0617 H(691) 0.5583 0.6082 0.2496 0.0627 H(701) 0.4214 0.6560 0.0929 0.1237 H(702) 0.5230 0.7068 0.0873 0.1237 H(703) 0.4734 0.7058 0.1959 0.1237 H(711) 0.5293 0.5661 0.0681 0.0879 H(712) 0.6418 0.6073 0.0576 0.0879 H(713) 0.6616 0.5517 0.1522 0.0879 H(721) 0.8326 0.6468 0.5952 0.0507 H(731) 0.8969 0.7329 0.7199 0.0837 H(732) 0.9148 0.7749 0.6164 0.0837 H(733) 0.7827 0.7521 0.6141 0.0837 H(741) 1.0350 0.6520 0.7009 0.0670 H(742) 1.0629 0.6887 0.5965 0.0670 H(743) 1.0165 0.6156 0.5814 0.0670



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Table 4: Anisotropic thermal parameters (Å2)

Atom U11 U22 U33 U23 U13 U12

N(1) 0.0267(9) 0.0179(9) 0.0288(9) 0.0009(7) 0.0078(8) -0.0015(7) C(1) 0.0249(11) 0.0252(11) 0.0307(11) 0.0001(9) 0.0069(9) 0.0013(9) N(2) 0.0291(9) 0.0247(9) 0.0313(9) -0.0003(8) 0.0126(8) -0.0023(8) C(2) 0.0260(11) 0.0225(11) 0.0267(10) 0.0001(9) 0.0048(9) -0.0049(9) C(3) 0.0326(12) 0.0264(12) 0.0372(12) 0.0003(10) 0.0120(10) 0.0015(10) C(4) 0.0347(12) 0.0280(13) 0.0314(12) 0.0010(10) 0.0035(10) -0.0015(10) C(5) 0.0493(16) 0.0250(13) 0.0458(15) -0.0049(11) 0.0062(13) 0.0008(12) C(6) 0.064(2) 0.0191(12) 0.0526(17) 0.0002(12) 0.0037(15) -0.0054(12) C(7) 0.0539(17) 0.0259(13) 0.0401(14) 0.0067(11) 0.0025(13) -0.0134(12) C(8) 0.0401(14) 0.0299(13) 0.0307(12) 0.0039(10) 0.0008(11) -0.0123(11) C(9) 0.0398(14) 0.0432(15) 0.0325(12) 0.0038(11) 0.0093(11) -0.0171(12) C(10) 0.0360(13) 0.0475(16) 0.0400(14) 0.0003(12) 0.0168(11) -0.0091(11) C(11) 0.0347(13) 0.0329(13) 0.0344(12) 0.0002(10) 0.0111(10) -0.0066(10) C(12) 0.0284(11) 0.0266(12) 0.0254(11) 0.0016(9) 0.0046(9) -0.0052(9) C(13) 0.0314(12) 0.0250(12) 0.0256(11) 0.0022(9) 0.0020(9) -0.0062(9) C(14) 0.0256(10) 0.0209(10) 0.0280(10) -0.0011(8) 0.0102(9) -0.0037(8) C(15) 0.0374(12) 0.0271(11) 0.0311(11) 0.0000(9) 0.0149(10) -0.0086(10) C(16) 0.0475(15) 0.0375(14) 0.0395(13) -0.0097(11) 0.0237(12) -0.0123(12) C(17) 0.0480(16) 0.0305(13) 0.0580(17) -0.0072(12) 0.0356(14) -0.0025(11) C(18) 0.0315(12) 0.0308(13) 0.0490(14) -0.0005(11) 0.0189(11) 0.0019(10) C(19) 0.0267(10) 0.0239(11) 0.0338(11) 0.0004(9) 0.0124(9) -0.0014(9) C(20) 0.0391(13) 0.0444(15) 0.0288(11) -0.0044(11) 0.0067(10) -0.0118(12) C(21) 0.070(2) 0.064(2) 0.0405(16) 0.0131(16) 0.0001(15) -0.0193(18) C(22) 0.0518(18) 0.070(2) 0.0494(17) -0.0176(16) 0.0086(15) -0.0246(17) C(23) 0.0303(11) 0.0347(13) 0.0330(12) -0.0021(10) 0.0044(10) 0.0052(10) C(24) 0.0317(13) 0.0491(17) 0.0478(15) -0.0076(13) 0.0018(11) -0.0031(12) C(25) 0.0589(18) 0.0519(18) 0.0356(14) 0.0095(13) 0.0087(13) 0.0103(15) C(26) 0.0268(10) 0.0205(10) 0.0344(11) 0.0021(9) 0.0126(9) 0.0012(8) C(27) 0.0310(11) 0.0292(12) 0.0329(11) 0.0017(9) 0.0122(10) 0.0046(10) C(28) 0.0380(13) 0.0419(15) 0.0397(14) 0.0082(11) 0.0190(11) 0.0059(11) C(29) 0.0318(13) 0.0431(15) 0.0581(17) 0.0125(13) 0.0230(12) 0.0017(11) C(30) 0.0252(11) 0.0382(14) 0.0519(15) 0.0081(12) 0.0094(11) -0.0024(10) C(31) 0.0305(12) 0.0253(11) 0.0387(13) 0.0030(9) 0.0092(10) 0.0013(9) C(32) 0.0335(12) 0.0479(15) 0.0309(12) -0.0038(11) 0.0103(10) -0.0034(11) C(33) 0.0546(19) 0.0506(19) 0.066(2) -0.0102(16) 0.0127(16) -0.0153(15) C(34) 0.0478(17) 0.068(2) 0.0507(18) 0.0099(16) -0.0021(14) -0.0025(16) C(35) 0.0380(14) 0.0415(15) 0.0405(14) -0.0021(12) 0.0036(11) -0.0048(12) C(36) 0.079(2) 0.058(2) 0.0453(17) 0.0037(15) 0.0009(17) 0.0045(19) C(37) 0.061(2) 0.053(2) 0.0530(18) -0.0126(15) 0.0028(16) -0.0100(16)

N(3) 0.0276(9) 0.0213(9) 0.0289(9) -0.0004(7) 0.0090(8) 0.0008(8) C(38) 0.0265(11) 0.0300(12) 0.0274(11) 0.0000(9) 0.0067(9) -0.0007(9) N(4) 0.0287(9) 0.0284(10) 0.0312(9) 0.0006(8) 0.0080(8) -0.0004(8) C(39) 0.0270(11) 0.0226(11) 0.0239(10) 0.0015(8) 0.0040(9) -0.0014(9) C(40) 0.0290(11) 0.0233(11) 0.0305(11) 0.0016(9) 0.0075(9) 0.0032(9) C(41) 0.0319(11) 0.0268(12) 0.0278(11) 0.0014(9) 0.0066(9) -0.0030(9) C(42) 0.0470(15) 0.0251(12) 0.0356(13) 0.0012(10) 0.0107(12) 0.0051(11) C(43) 0.0556(17) 0.0264(13) 0.0407(14) 0.0006(11) 0.0128(13) 0.0011(12) C(44) 0.0494(16) 0.0309(13) 0.0360(13) 0.0015(11) 0.0058(12) -0.0093(12)



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C(45) 0.0354(12) 0.0320(13) 0.0280(11) 0.0021(9) 0.0055(10) -0.0069(10) C(46) 0.0357(13) 0.0399(15) 0.0333(12) 0.0007(11) 0.0100(11) -0.0126(11) C(47) 0.0382(14) 0.0463(16) 0.0466(15) -0.0037(13) 0.0235(12) -0.0070(12) C(48) 0.0318(12) 0.0306(13) 0.0430(14) -0.0031(10) 0.0138(11) -0.0023(10) C(49) 0.0281(11) 0.0267(11) 0.0264(11) -0.0015(9) 0.0062(9) -0.0040(9) C(50) 0.0291(11) 0.0306(12) 0.0240(10) -0.0026(9) 0.0044(9) -0.0033(10) C(51) 0.0281(11) 0.0186(10) 0.0331(11) -0.0010(9) 0.0139(9) -0.0027(9) C(52) 0.0367(13) 0.0264(12) 0.0368(12) -0.0031(10) 0.0170(11) -0.0095(10) C(53) 0.0542(17) 0.0322(14) 0.0525(16) -0.0122(12) 0.0326(14) -0.0101(12) C(54) 0.0454(16) 0.0304(14) 0.071(2) -0.0097(13) 0.0307(15) 0.0018(12) C(55) 0.0333(13) 0.0297(13) 0.0669(18) 0.0011(13) 0.0164(13) 0.0054(11) C(56) 0.0264(11) 0.0249(11) 0.0429(13) 0.0015(10) 0.0105(10) -0.0015(9) C(57) 0.0395(14) 0.0412(15) 0.0312(12) -0.0077(11) 0.0096(11) -0.0080(11) C(58) 0.075(2) 0.065(2) 0.0535(19) 0.0191(19) -0.0136(18) -0.022(2) C(59) 0.060(2) 0.057(2) 0.064(2) -0.0180(17) 0.0065(17) -0.0223(17) C(60) 0.0339(13) 0.0382(15) 0.0410(14) -0.0006(11) 0.0006(11) 0.0012(11) C(61) 0.0339(14) 0.0502(18) 0.069(2) -0.0180(16) 0.0007(14) -0.0040(13) C(62) 0.091(3) 0.065(3) 0.050(2) 0.0100(17) -0.0036(19) -0.007(2) C(63) 0.0323(12) 0.0284(12) 0.0348(12) 0.0040(9) 0.0128(10) 0.0023(9) C(64) 0.0359(13) 0.0566(17) 0.0330(12) 0.0096(12) 0.0139(11) 0.0156(13) C(65) 0.0507(17) 0.072(2) 0.0402(15) 0.0226(15) 0.0252(14) 0.0238(16) C(66) 0.0551(19) 0.063(2) 0.069(2) 0.0327(18) 0.0392(17) 0.0115(16) C(67) 0.0378(15) 0.0481(17) 0.068(2) 0.0150(15) 0.0219(14) -0.0029(13) C(68) 0.0360(13) 0.0374(14) 0.0420(13) 0.0073(11) 0.0149(11) -0.0032(11) C(69) 0.0450(16) 0.082(2) 0.0295(12) -0.0010(14) 0.0057(12) 0.0120(16) C(70) 0.090(3) 0.083(3) 0.136(4) -0.056(3) -0.054(3) 0.044(3) C(71) 0.080(3) 0.054(2) 0.085(3) -0.0068(19) 0.021(2) 0.010(2) C(72) 0.0376(14) 0.0483(16) 0.0407(13) -0.0005(12) 0.0093(11) -0.0133(12) C(73) 0.075(2) 0.068(2) 0.067(2) -0.0090(19) 0.027(2) -0.006(2) C(74) 0.0453(17) 0.071(2) 0.0506(17) 0.0059(16) 0.0057(14) -0.0036(16)



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Table 5: Bond lengths (Å)

N(1) - C(1) 1.379(3) N(3) - C(38) 1.390(3) N(1) - C(2) 1.400(3) N(3) - C(39) 1.396(3) N(1) - C(14) 1.447(3) N(3) - C(51) 1.450(3) C(1) - N(2) 1.263(3) C(38) - N(4) 1.254(3) N(2) - C(26) 1.440(3) N(4) - C(63) 1.429(3) C(2) - C(3) 1.376(3) C(39) - C(40) 1.374(3) C(2) - C(12) 1.495(3) C(39) - C(49) 1.492(3) C(3) - C(4) 1.462(4) C(40) - C(41) 1.458(3) C(4) - C(5) 1.381(4) C(41) - C(42) 1.385(4) C(4) - C(13) 1.406(4) C(41) - C(50) 1.410(3) C(5) - C(6) 1.406(4) C(42) - C(43) 1.426(4) C(6) - C(7) 1.374(5) C(43) - C(44) 1.370(4) C(7) - C(8) 1.429(4) C(44) - C(45) 1.427(4) C(8) - C(9) 1.406(4) C(45) - C(46) 1.423(4) C(8) - C(13) 1.397(3) C(45) - C(50) 1.388(3) C(9) - C(10) 1.377(4) C(46) - C(47) 1.360(4)

C(10) - C(11) 1.428(4) C(47) - C(48) 1.436(4) C(11) - C(12) 1.371(4) C(48) - C(49) 1.373(4) C(12) - C(13) 1.422(3) C(49) - C(50) 1.420(4) C(14) - C(15) 1.406(3) C(51) - C(52) 1.406(3) C(14) - C(19) 1.401(3) C(51) - C(56) 1.396(3) C(15) - C(16) 1.391(4) C(52) - C(53) 1.393(4) C(15) - C(20) 1.521(4) C(52) - C(57) 1.520(4) C(16) - C(17) 1.392(4) C(53) - C(54) 1.380(5) C(17) - C(18) 1.381(4) C(54) - C(55) 1.379(4) C(18) - C(19) 1.399(3) C(55) - C(56) 1.405(4) C(19) - C(23) 1.523(3) C(56) - C(60) 1.514(4) C(20) - C(21) 1.522(4) C(57) - C(58) 1.521(5) C(20) - C(22) 1.534(4) C(57) - C(59) 1.525(4) C(23) - C(24) 1.534(4) C(60) - C(61) 1.541(4) C(23) - C(25) 1.534(4) C(60) - C(62) 1.531(5) C(26) - C(27) 1.402(3) C(63) - C(64) 1.406(3) C(26) - C(31) 1.405(3) C(63) - C(68) 1.394(4) C(27) - C(28) 1.386(4) C(64) - C(65) 1.397(4) C(27) - C(32) 1.523(3) C(64) - C(69) 1.534(5) C(28) - C(29) 1.391(4) C(65) - C(66) 1.368(5) C(29) - C(30) 1.384(4) C(66) - C(67) 1.386(5) C(30) - C(31) 1.390(4) C(67) - C(68) 1.392(4) C(31) - C(35) 1.518(4) C(68) - C(72) 1.527(4) C(32) - C(33) 1.528(5) C(69) - C(70) 1.484(6) C(32) - C(34) 1.530(4) C(69) - C(71) 1.519(5) C(35) - C(36) 1.517(5) C(72) - C(73) 1.511(5) C(35) - C(37) 1.520(4) C(72) - C(74) 1.521(4)

Note – H atoms have been excluded



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Table 6: Bond angles (°)

C(1) - N(1) - C(2) 119.77(19) C(38) - N(3) - C(39) 124.15(19) C(1) - N(1) - C(14) 119.77(19) C(38) - N(3) - C(51) 114.11(18) C(2) - N(1) - C(14) 120.45(18) C(39) - N(3) - C(51) 121.65(18) N(1) - C(1) - N(2) 122.4(2) N(3) - C(38) - N(4) 125.9(2) C(1) - N(2) - C(26) 116.8(2) C(38) - N(4) - C(63) 115.4(2) N(1) - C(2) - C(3) 126.7(2) N(3) - C(39) - C(40) 126.6(2) N(1) - C(2) - C(12) 124.0(2) N(3) - C(39) - C(49) 124.2(2) C(3) - C(2) - C(12) 109.3(2) C(40) - C(39) - C(49) 109.2(2) C(2) - C(3) - C(4) 108.5(2) C(39) - C(40) - C(41) 108.0(2) C(3) - C(4) - C(5) 135.5(3) C(40) - C(41) - C(42) 134.5(2) C(3) - C(4) - C(13) 106.7(2) C(40) - C(41) - C(50) 107.7(2) C(5) - C(4) - C(13) 117.7(2) C(42) - C(41) - C(50) 117.8(2) C(4) - C(5) - C(6) 119.2(3) C(41) - C(42) - C(43) 118.2(2) C(5) - C(6) - C(7) 122.7(3) C(42) - C(43) - C(44) 123.2(2) C(6) - C(7) - C(8) 119.8(3) C(43) - C(44) - C(45) 119.5(2) C(7) - C(8) - C(9) 127.7(3) C(44) - C(45) - C(46) 128.1(2) C(7) - C(8) - C(13) 115.9(3) C(44) - C(45) - C(50) 116.2(2) C(9) - C(8) - C(13) 116.3(2) C(46) - C(45) - C(50) 115.7(2) C(8) - C(9) - C(10) 120.3(2) C(45) - C(46) - C(47) 120.5(2)

C(9) - C(10) - C(11) 122.6(3) C(46) - C(47) - C(48) 122.6(2) C(10) - C(11) - C(12) 118.3(2) C(47) - C(48) - C(49) 118.4(2) C(2) - C(12) - C(11) 137.5(2) C(39) - C(49) - C(48) 137.1(2) C(2) - C(12) - C(13) 104.3(2) C(39) - C(49) - C(50) 105.1(2) C(11) - C(12) - C(13) 118.2(2) C(48) - C(49) - C(50) 117.7(2)

C(4) - C(13) - C(8) 124.6(2) C(41) - C(50) - C(45) 125.1(2) C(4) - C(13) - C(12) 111.2(2) C(41) - C(50) - C(49) 109.9(2) C(8) - C(13) - C(12) 124.2(2) C(45) - C(50) - C(49) 125.0(2) N(1) - C(14) - C(15) 118.6(2) N(3) - C(51) - C(52) 118.2(2) N(1) - C(14) - C(19) 118.83(19) N(3) - C(51) - C(56) 119.0(2) C(15) - C(14) - C(19) 122.5(2) C(52) - C(51) - C(56) 122.7(2) C(14) - C(15) - C(16) 117.5(2) C(51) - C(52) - C(53) 117.2(2) C(14) - C(15) - C(20) 121.8(2) C(51) - C(52) - C(57) 121.9(2) C(16) - C(15) - C(20) 120.7(2) C(53) - C(52) - C(57) 120.9(2) C(15) - C(16) - C(17) 120.8(2) C(52) - C(53) - C(54) 121.5(3) C(16) - C(17) - C(18) 120.6(2) C(53) - C(54) - C(55) 120.1(3) C(17) - C(18) - C(19) 120.6(2) C(54) - C(55) - C(56) 121.2(3) C(14) - C(19) - C(18) 117.7(2) C(51) - C(56) - C(55) 117.2(2) C(14) - C(19) - C(23) 122.5(2) C(51) - C(56) - C(60) 123.3(2) C(18) - C(19) - C(23) 119.8(2) C(55) - C(56) - C(60) 119.5(2) C(15) - C(20) - C(21) 111.4(2) C(52) - C(57) - C(58) 111.7(2) C(15) - C(20) - C(22) 111.4(3) C(52) - C(57) - C(59) 113.0(3) C(21) - C(20) - C(22) 110.4(2) C(58) - C(57) - C(59) 110.1(3) C(19) - C(23) - C(24) 111.5(2) C(56) - C(60) - C(61) 111.4(2) C(19) - C(23) - C(25) 111.0(2) C(56) - C(60) - C(62) 110.4(3) C(24) - C(23) - C(25) 110.5(2) C(61) - C(60) - C(62) 109.6(3) N(2) - C(26) - C(27) 120.7(2) N(4) - C(63) - C(64) 118.0(2) N(2) - C(26) - C(31) 117.8(2) N(4) - C(63) - C(68) 120.3(2) C(27) - C(26) - C(31) 121.3(2) C(64) - C(63) - C(68) 121.7(2) C(26) - C(27) - C(28) 118.3(2) C(63) - C(64) - C(65) 117.5(3) C(26) - C(27) - C(32) 122.1(2) C(63) - C(64) - C(69) 120.6(2) C(28) - C(27) - C(32) 119.6(2) C(65) - C(64) - C(69) 121.9(3)



S17

C(27) - C(28) - C(29) 121.0(2) C(64) - C(65) - C(66) 121.8(3) C(28) - C(29) - C(30) 120.1(2) C(65) - C(66) - C(67) 119.6(3) C(29) - C(30) - C(31) 120.7(2) C(66) - C(67) - C(68) 121.3(3) C(26) - C(31) - C(30) 118.5(2) C(63) - C(68) - C(67) 118.1(3) C(26) - C(31) - C(35) 120.5(2) C(63) - C(68) - C(72) 121.5(2) C(30) - C(31) - C(35) 120.9(2) C(67) - C(68) - C(72) 120.4(2) C(27) - C(32) - C(33) 111.8(2) C(64) - C(69) - C(70) 111.9(4) C(27) - C(32) - C(34) 110.7(2) C(64) - C(69) - C(71) 114.0(3) C(33) - C(32) - C(34) 110.5(3) C(70) - C(69) - C(71) 111.0(3) C(31) - C(35) - C(36) 110.9(2) C(68) - C(72) - C(73) 111.3(3) C(31) - C(35) - C(37) 113.4(3) C(68) - C(72) - C(74) 111.9(2) C(36) - C(35) - C(37) 111.6(3) C(73) - C(72) - C(74) 110.9(3)




S18

B. Single-crystal X-ray diffraction report for CCDC_719731_5a Single crystals of the BIAN-SIMes 5a suitable for X-ray diffraction study were grown

from a saturated solution of benzene at room temperature. An ORTEP view of the

molecule 5a is depicted in Figure 2.

A single crystal having dimensions approximately 0.16 x 0.24 x 0.40 mm was

mounted on a glass fibre using perfluoropolyether oil and cooled rapidly to 150K in a

stream of cold N2 using an Oxford Cryosystems CRYOSTREAM unit. Diffraction data were

measured using an Enraf-Nonius KappaCCD diffractometer (graphite-monochromated

MoKα radiation, λ = 0.71073 Å). Intensity data were processed using the DENZO-SMN

package1.

Examination of the systematic absences of the intensity data showed the space

group to be either C c or C 2/c. The structure was solved in the space group C 2/c using

the direct-methods program SIR922, which located all non-hydrogen atoms. Subsequent

full-matrix least-squares refinement was carried out using the CRYSTALS program suite3.

Coordinates and anisotropic thermal parameters of all non-hydrogen atoms were refined.

Hydrogen atoms were positioned geometrically after each cycle of refinement. A 3-term

Chebychev polynomial weighting scheme was applied. Refinement converged

satisfactorily to give R = 0.0482, wR = 0.0584.




Comment: The asymmetric unit contains one molecule of the carbene located on a site with no

crystallographic symmetry and a molercule of solvent located on a crystallographic twofold

axis.


Oscillation Mode, Methods Enzymol., 1997, 276, Eds C. W. Carter and R. M. Sweet,

Academic Press.

2 A. Altomare, G. Cascarano, G. Giacovazzo, A. Guagliardi ,M. C. Burla, G. Polidori

and M. Camalli, J. Appl. Cryst. 1994, 27, 435.



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3 CRYSTALS Issue 12, P. W. Betteridge, J. R. Cooper, R. I. Cooper, K. Prout and D.

J. Watkin, J. Appl. Cryst., 2003, 36, 1487


Solvent molecule not shown



S20


Crystal identification CCDC_719731_5a Chemical formula C34H33N2 Formula weight 469.65 Temperature (K) 150 Wavelength (Å) 0.71073 Crystal system Monoclinic Space group C 2/c a (Å) 25.9142(4) b (Å) 11.0550(2) c (Å) 19.0937(3) α (°) 90 β (°) 105.1595(8) γ (°) 90 Cell volume (Å3) 5279.64(15) Z 8 Calculated density (Mg/m3) 1.182 Absorption coefficient (mm-1) 0.068 F000 2008 Crystal size (mm) 0.16 x 0.24 x 0.40 Description of crystal Colourless block Absorption correction Semi-empirical from equivalent reflections Transmission coefficients (min,max) 0.97, 0.99 θ range for data collection (°) 5.0 ≤ θ ≤ 27.5 Index ranges -33 ≤ h ≤ 32, 0 ≤ k ≤ 14, 0 ≤ l ≤ 24 Reflections measured 32188 Unique reflections 6309 Rint 0.051 Observed reflections (I > 3σ(I)) 3638 Refinement method Full-matrix least-squares on F Parameters refined 326 Weighting scheme Chebychev 3-term polynomial Goodness of fit 1.0758 R 0.0482 wR 0.0584 Residual electron density (min,max) (eÅ-3) -0.32, 0.29



S21


Atom x y z Uequiv

C(1) 0.25305(7) 0.46843(16) 0.33541(9) 0.0248 N(1) 0.29348(6) 0.50747(13) 0.39058(7) 0.0231 C(2) 0.28035(7) 0.61036(15) 0.43341(9) 0.0222 C(3) 0.22035(7) 0.63239(15) 0.39442(9) 0.0227 N(2) 0.21112(6) 0.54053(13) 0.33491(8) 0.0241 C(4) 0.28113(7) 0.57772(15) 0.51085(9) 0.0223 C(5) 0.32205(7) 0.55072(17) 0.57054(10) 0.0283 C(6) 0.30900(8) 0.52204(17) 0.63664(9) 0.0311 C(7) 0.25753(8) 0.52266(17) 0.64308(9) 0.0313 C(8) 0.19066(7) 0.60713(15) 0.45162(9) 0.0228 C(9) 0.13761(7) 0.61139(18) 0.45002(11) 0.0306 C(10) 0.12258(8) 0.58426(19) 0.51515(12) 0.0347 C(11) 0.15926(8) 0.55579(18) 0.57914(11) 0.0322 C(12) 0.21452(7) 0.55026(16) 0.58195(10) 0.0261 C(13) 0.22829(7) 0.57645(15) 0.51687(9) 0.0223 C(14) 0.34539(7) 0.45253(16) 0.41103(9) 0.0239 C(15) 0.38808(7) 0.50972(18) 0.39226(10) 0.0296 C(16) 0.43840(8) 0.4556(2) 0.41362(12) 0.0382 C(17) 0.44686(8) 0.3482(2) 0.45282(12) 0.0404 C(18) 0.40348(9) 0.29347(19) 0.46966(11) 0.0382 C(19) 0.35233(8) 0.34285(17) 0.44902(10) 0.0294 C(20) 0.38004(9) 0.6242(2) 0.34846(12) 0.0403 C(21) 0.50169(10) 0.2915(3) 0.47470(16) 0.0578 C(22) 0.30559(9) 0.27684(18) 0.46402(12) 0.0373 C(23) 0.15918(7) 0.52398(16) 0.28599(9) 0.0237 C(24) 0.13673(7) 0.61591(17) 0.23751(9) 0.0267 C(25) 0.08578(8) 0.59851(18) 0.19114(10) 0.0303 C(26) 0.05779(7) 0.4913(2) 0.19066(10) 0.0329 C(27) 0.08153(8) 0.40053(19) 0.23881(11) 0.0343 C(28) 0.13155(8) 0.41512(17) 0.28734(10) 0.0305 C(29) 0.16670(10) 0.7300(2) 0.23118(11) 0.0428 C(30) 0.00326(9) 0.4734(3) 0.13877(13) 0.0495 C(31) 0.15454(10) 0.3145(2) 0.33947(13) 0.0470

C(32) 0.5 0.4281(3) 0.75 0.0581 C(33) 0.45822(10) 0.4898(3) 0.70476(18) 0.0605 C(34) 0.45812(11) 0.6136(3) 0.70530(17) 0.0593 C(35) 0.5 0.6757(3) 0.75 0.0545



S22


Atom x y z Uiso

H(21) 0.3063 0.6782 0.4358 0.0270 H(31) 0.2090 0.7144 0.3740 0.0270 H(51) 0.3601 0.5511 0.5678 0.0332 H(61) 0.3386 0.5006 0.6801 0.0358 H(71) 0.2503 0.5037 0.6908 0.0380 H(91) 0.1100 0.6329 0.4044 0.0363 H(101) 0.0838 0.5861 0.5141 0.0430 H(111) 0.1470 0.5390 0.6237 0.0409 H(161) 0.4692 0.4952 0.4003 0.0458 H(181) 0.4091 0.2159 0.4976 0.0437 H(201) 0.4150 0.6509 0.3407 0.0510 H(202) 0.3658 0.6886 0.3751 0.0510 H(203) 0.3540 0.6092 0.3004 0.0510 H(211) 0.5244 0.3356 0.5175 0.0653 H(212) 0.5186 0.2964 0.4333 0.0653 H(213) 0.4985 0.2048 0.4878 0.0653 H(221) 0.3184 0.2009 0.4916 0.0458 H(222) 0.2879 0.3297 0.4934 0.0458 H(223) 0.2794 0.2560 0.4171 0.0458 H(251) 0.0690 0.6651 0.1574 0.0358 H(271) 0.0621 0.3224 0.2385 0.0407 H(291) 0.1437 0.7838 0.1936 0.0483 H(292) 0.1763 0.7727 0.2790 0.0483 H(293) 0.2001 0.7094 0.2167 0.0483 H(301) -0.0219 0.5360 0.1483 0.0570 H(302) 0.0061 0.4814 0.0877 0.0570 H(303) -0.0104 0.3910 0.1460 0.0570 H(311) 0.1288 0.2454 0.3317 0.0525 H(312) 0.1610 0.3447 0.3904 0.0525 H(313) 0.1891 0.2869 0.3308 0.0525

H(321) 0.5 0.3376 0.75 0.0732 H(331) 0.4281 0.4445 0.6717 0.0722 H(341) 0.4276 0.6590 0.6732 0.0703 H(351) 0.5 0.7661 0.75 0.0671



S23


Atom U11 U22 U33 U23 U13 U12

C(1) 0.0301(9) 0.0253(9) 0.0194(8) 0.0009(7) 0.0071(7) 0.0010(7) N(1) 0.0241(7) 0.0243(7) 0.0216(7) -0.0032(6) 0.0075(6) 0.0017(6) C(2) 0.0246(8) 0.0198(8) 0.0231(8) -0.0032(6) 0.0077(6) 0.0001(6) C(3) 0.0265(9) 0.0213(8) 0.0196(8) -0.0009(6) 0.0045(6) 0.0012(7) N(2) 0.0281(8) 0.0243(7) 0.0186(7) -0.0032(5) 0.0038(6) 0.0018(6) C(4) 0.0244(9) 0.0206(8) 0.0219(8) -0.0038(6) 0.0064(7) 0.0008(6) C(5) 0.0281(9) 0.0295(9) 0.0253(9) -0.0036(7) 0.0032(7) 0.0038(7) C(6) 0.0384(11) 0.0294(10) 0.0218(8) 0.0001(7) 0.0011(7) 0.0059(8) C(7) 0.0461(12) 0.0265(10) 0.0223(9) 0.0024(7) 0.0110(8) 0.0025(8) C(8) 0.0253(9) 0.0198(8) 0.0231(8) -0.0029(6) 0.0063(7) 0.0012(6) C(9) 0.0263(9) 0.0329(10) 0.0316(9) -0.0020(8) 0.0059(7) 0.0023(8) C(10) 0.0256(10) 0.0377(11) 0.0441(11) -0.0021(9) 0.0152(8) -0.0019(8) C(11) 0.0371(10) 0.0309(10) 0.0342(10) 0.0002(8) 0.0194(8) -0.0028(8) C(12) 0.0337(10) 0.0210(8) 0.0261(9) -0.0011(6) 0.0120(7) -0.0005(7) C(13) 0.0262(9) 0.0185(8) 0.0229(8) -0.0017(6) 0.0075(7) 0.0003(6) C(14) 0.0250(8) 0.0241(8) 0.0226(8) -0.0048(7) 0.0060(7) 0.0033(7) C(15) 0.0290(9) 0.0302(10) 0.0313(9) -0.0069(8) 0.0111(7) 0.0005(7) C(16) 0.0265(10) 0.0392(11) 0.0488(12) -0.0131(9) 0.0100(9) -0.0002(8) C(17) 0.0313(11) 0.0409(12) 0.0429(11) -0.0142(9) -0.0014(9) 0.0087(9) C(18) 0.0424(12) 0.0346(11) 0.0324(10) -0.0044(8) 0.0004(9) 0.0113(9) C(19) 0.0357(10) 0.0269(9) 0.0250(9) -0.0032(7) 0.0069(7) 0.0043(8) C(20) 0.0401(12) 0.0385(11) 0.0489(12) 0.0038(10) 0.0236(10) -0.0011(9) C(21) 0.0370(13) 0.0567(15) 0.0696(17) -0.0181(13) -0.0040(12) 0.0170(11) C(22) 0.0495(13) 0.0275(10) 0.0374(11) 0.0045(8) 0.0160(9) 0.0003(9) C(23) 0.0263(9) 0.0257(9) 0.0184(7) -0.0029(6) 0.0044(6) 0.0012(7) C(24) 0.0336(10) 0.0266(9) 0.0198(8) -0.0013(7) 0.0068(7) 0.0028(7) C(25) 0.0309(10) 0.0352(10) 0.0234(9) 0.0020(7) 0.0047(7) 0.0079(8) C(26) 0.0272(10) 0.0444(11) 0.0262(9) -0.0032(8) 0.0055(7) 0.0017(8) C(27) 0.0337(10) 0.0350(11) 0.0329(10) -0.0020(8) 0.0067(8) -0.0073(8) C(28) 0.0351(10) 0.0285(10) 0.0268(9) 0.0016(7) 0.0063(8) -0.0005(8) C(29) 0.0573(14) 0.0336(11) 0.0299(10) 0.0102(8) -0.0020(9) -0.0078(10) C(30) 0.0301(11) 0.0686(16) 0.0440(12) 0.0033(11) -0.0010(9) -0.0046(11) C(31) 0.0542(14) 0.0316(11) 0.0453(12) 0.0119(9) -0.0045(10) -0.0097(10)

C(32) 0.0375(19) 0.0450(19) 0.101(3) 0. 0.034(2) 0. C(33) 0.0355(13) 0.0597(17) 0.085(2) -0.0054(15) 0.0138(13) -0.0064(12) C(34) 0.0434(14) 0.0586(16) 0.0737(19) 0.0098(14) 0.0114(13) 0.0038(12) C(35) 0.047(2) 0.0459(19) 0.075(2) 0. 0.0237(18) 0.



S24


C(1) - N(1) 1.348(2) C(12) - C(13) 1.410(2) C(1) - N(2) 1.346(2) C(14) - C(15) 1.399(3) N(1) - C(2) 1.491(2) C(14) - C(19) 1.400(3) N(1) - C(14) 1.434(2) C(15) - C(16) 1.395(3) C(2) - C(3) 1.558(2) C(15) - C(20) 1.501(3) C(2) - C(4) 1.517(2) C(16) - C(17) 1.390(3) C(3) - N(2) 1.496(2) C(17) - C(18) 1.387(3) C(3) - C(8) 1.517(2) C(17) - C(21) 1.509(3) N(2) - C(23) 1.435(2) C(18) - C(19) 1.392(3) C(4) - C(5) 1.371(3) C(19) - C(22) 1.504(3) C(4) - C(13) 1.404(2) C(23) - C(24) 1.395(2) C(5) - C(6) 1.425(3) C(23) - C(28) 1.404(3) C(6) - C(7) 1.371(3) C(24) - C(25) 1.397(3) C(7) - C(12) 1.420(3) C(24) - C(29) 1.502(3) C(8) - C(9) 1.368(3) C(25) - C(26) 1.389(3) C(8) - C(13) 1.408(2) C(26) - C(27) 1.391(3) C(9) - C(10) 1.429(3) C(26) - C(30) 1.512(3)

C(10) - C(11) 1.374(3) C(27) - C(28) 1.392(3) C(11) - C(12) 1.420(3) C(28) - C(31) 1.507(3)

C(32) - C(33) 1.377(3) C(34) - C(35) 1.376(3) C(33) - C(34) 1.369(4)




S25


N(1) - C(1) - N(2) 106.09(14) C(8) - C(13) - C(12) 123.56(16) C(1) - N(1) - C(2) 115.51(14) N(1) - C(14) - C(15) 119.14(16) C(1) - N(1) - C(14) 124.01(14) N(1) - C(14) - C(19) 119.47(16) C(2) - N(1) - C(14) 120.40(13) C(15) - C(14) - C(19) 121.39(17) N(1) - C(2) - C(3) 101.51(13) C(14) - C(15) - C(16) 118.18(18) N(1) - C(2) - C(4) 113.97(14) C(14) - C(15) - C(20) 121.31(17) C(3) - C(2) - C(4) 105.08(13) C(16) - C(15) - C(20) 120.48(18) C(2) - C(3) - N(2) 101.43(13) C(15) - C(16) - C(17) 121.84(19) C(2) - C(3) - C(8) 104.95(13) C(16) - C(17) - C(18) 118.31(19) N(2) - C(3) - C(8) 114.30(14) C(16) - C(17) - C(21) 120.6(2) C(1) - N(2) - C(3) 115.37(14) C(18) - C(17) - C(21) 121.1(2) C(1) - N(2) - C(23) 123.18(14) C(17) - C(18) - C(19) 122.2(2) C(3) - N(2) - C(23) 121.14(14) C(14) - C(19) - C(18) 118.04(18) C(2) - C(4) - C(5) 132.23(16) C(14) - C(19) - C(22) 121.21(17) C(2) - C(4) - C(13) 108.52(15) C(18) - C(19) - C(22) 120.69(18) C(5) - C(4) - C(13) 119.25(16) N(2) - C(23) - C(24) 119.74(16) C(4) - C(5) - C(6) 118.26(17) N(2) - C(23) - C(28) 119.56(16) C(5) - C(6) - C(7) 122.69(16) C(24) - C(23) - C(28) 120.70(16) C(6) - C(7) - C(12) 120.00(16) C(23) - C(24) - C(25) 118.74(17) C(3) - C(8) - C(9) 132.33(16) C(23) - C(24) - C(29) 122.02(17) C(3) - C(8) - C(13) 108.48(14) C(25) - C(24) - C(29) 119.16(17) C(9) - C(8) - C(13) 119.18(16) C(24) - C(25) - C(26) 121.82(17) C(8) - C(9) - C(10) 118.32(17) C(25) - C(26) - C(27) 118.12(17)


C(4) - C(13) - C(8) 112.95(15) C(27) - C(28) - C(31) 119.52(18) C(4) - C(13) - C(12) 123.47(16)

C(33) - C(32) - C(33)* 120.5(4) C(33) - C(34) - C(35) 120.0(3) C(32) - C(33) - C(34) 119.6(3) C(34) - C(35) - C(34)* 120.2(4)

*related to asymmetric unity by twofold rotation, symmetry operator 1-x, y, 3/2-z




S26

C. Single-crystal X-ray diffraction report for CCDC_719729_6a

A single-crystal X-ray diffraction study was performed on crystals grown from slow

diffusion of pentane into a saturated dichloromethane solution. A prismatic single crystal

was cut to give a fragment having dimensions approximately 0.14 x 0.18 x 0.18 mm. This

was mounted on a glass fibre using perfluoropolyether oil and cooled rapidly to 150K in a

stream of cold N2 using an Oxford Cryosystems CRYOSTREAM unit. Diffraction data were

measured using an Enraf-Nonius KappaCCD diffractometer (graphite-monochromated

MoKα radiation, λ = 0.71073 Å). Intensity data were processed using the DENZO-SMN

package1.


group to be P 21/c. The structure was solved using the direct-methods program SIR922,

which located all non-hydrogen atoms. Subsequent full-matrix least-squares refinement

was carried out using the CRYSTALS program suite3. Coordinates and anisotropic thermal

parameters of all non-hydrogen atoms were refined. The hydrogen atoms of the

coordinated alkene groups were located in a difference Fourier map and their coordinates

and isotropic thermal parameters subsequently refined. Other hydrogen atoms were

positioned geometrically after each cycle of refinement. A 3-term Chebychev polynomial

weighting scheme was applied. Refinement converged satisfactorily to give R = 0.0386,

wR = 0.0415.





Oscillation Mode, Methods Enzymol., 1997, 276, Eds C. W. Carter and R. M.

Sweet, Academic Press.





S27




Hydrogen atoms have been omitted for clarity



S28


Crystal identification CCDC_719729_6a Chemical formula C39H42ClN2Rh Formula weight 677.13 Temperature (K) 150 Wavelength (Å) 0.71073 Crystal system Monoclinic Space group P 21/c a (Å) 9.0034(2) b (Å) 17.0287(5) c (Å) 21.0890(5) α (°) 90 β (°) 93.5968(15) γ (°) 90 Cell volume (Å3) 3226.92(14) Z 4 Calculated density (Mg/m3) 1.394 Absorption coefficient (mm-1) 0.642 F000 1408 Crystal size (mm) 0.14 x 0.18 x 0.18 Description of crystal Yellow fragment Absorption correction Semi-empirical from equivalent reflections Transmission coefficients (min,max) 0.89, 0.91 θ range for data collection (°) 5.0 ≤ θ ≤ 27.5 Index ranges -11 ≤ h ≤ 11, 0 ≤ k ≤ 22, 0 ≤ l ≤ 27 Reflections measured 26281 Unique reflections 7519 Rint 0.064 Observed reflections (I > 3σ(I)) 4293 Refinement method Full-matrix least-squares on F Parameters refined 404 Weighting scheme Chebychev 3-term polynomial Goodness of fit 1.1352 R 0.0386 wR 0.0415 Residual electron density (min,max) (eÅ-3) -0.45, 0.65



S29


Atom x y z Uequiv

Rh(1) 0.18309(3) 0.189114(18) 0.207472(13) 0.0242 Cl(1) -0.06448(11) 0.14052(7) 0.21123(5) 0.0380 C(1) 0.1401(4) 0.2682(2) 0.13590(17) 0.0243 N(1) 0.0852(4) 0.33999(19) 0.14647(14) 0.0263 C(2) 0.0981(4) 0.3959(2) 0.09245(18) 0.0282 C(3) 0.1499(4) 0.3402(2) 0.03974(18) 0.0285 N(2) 0.1827(4) 0.2666(2) 0.07508(15) 0.0291 C(4) -0.0464(5) 0.4299(2) 0.06625(18) 0.0311 C(5) -0.1365(5) 0.4872(2) 0.0886(2) 0.0370 C(6) -0.2702(5) 0.5054(3) 0.0526(2) 0.0418 C(7) -0.3094(5) 0.4682(3) -0.0039(2) 0.0431 C(8) 0.0194(4) 0.3374(2) -0.00953(18) 0.0302 C(9) -0.0050(5) 0.2969(3) -0.06567(19) 0.0359 C(10) -0.1382(5) 0.3129(3) -0.1038(2) 0.0439 C(11) -0.2417(5) 0.3683(3) -0.0864(2) 0.0420 C(12) -0.2184(5) 0.4099(3) -0.0289(2) 0.0356 C(13) -0.0863(4) 0.3922(2) 0.00825(18) 0.0294 C(14) 0.0134(4) 0.3629(2) 0.20258(18) 0.0273 C(15) -0.1365(4) 0.3427(2) 0.20789(18) 0.0296 C(16) -0.2027(5) 0.3643(3) 0.2629(2) 0.0365 C(17) -0.1272(5) 0.4053(3) 0.3118(2) 0.0426 C(18) 0.0192(5) 0.4282(3) 0.3033(2) 0.0379 C(19) 0.0907(4) 0.4084(2) 0.24946(19) 0.0306 C(20) -0.2283(4) 0.3030(3) 0.1554(2) 0.0351 C(21) -0.2021(6) 0.4291(4) 0.3709(2) 0.0631 C(22) 0.2460(5) 0.4402(3) 0.2422(2) 0.0457 C(23) 0.2317(4) 0.2003(2) 0.03966(17) 0.0290 C(24) 0.1302(5) 0.1396(2) 0.02364(19) 0.0326 C(25) 0.1783(5) 0.0791(3) -0.0145(2) 0.0382 C(26) 0.3210(5) 0.0778(3) -0.0373(2) 0.0391 C(27) 0.4154(5) 0.1394(3) -0.02155(19) 0.0401 C(28) 0.3741(4) 0.2014(3) 0.01641(18) 0.0315 C(29) -0.0255(5) 0.1394(3) 0.0449(2) 0.0388 C(30) 0.3700(6) 0.0113(3) -0.0781(2) 0.0526 C(31) 0.4829(5) 0.2679(3) 0.0314(2) 0.0406 C(32) 0.4086(4) 0.1837(3) 0.18733(19) 0.0351 C(33) 0.3896(4) 0.2462(3) 0.22843(19) 0.0330 C(34) 0.4418(6) 0.2442(3) 0.2987(2) 0.0457 C(35) 0.3241(6) 0.2128(3) 0.3397(2) 0.0486 C(36) 0.2178(5) 0.1540(3) 0.30713(18) 0.0350 C(37) 0.2577(5) 0.0912(3) 0.2712(2) 0.0348 C(38) 0.4174(5) 0.0677(3) 0.2627(2) 0.0473 C(39) 0.4765(6) 0.1047(3) 0.2042(2) 0.0487



S30


Atom x y z Uiso

H(1) 0.411(5) 0.197(3) 0.145(2) 0.034(11) H(2) 0.383(5) 0.300(3) 0.208(2) 0.030(11) H(3) 0.107(5) 0.158(3) 0.3199(19) 0.029(11) H(4) 0.186(5) 0.056(3) 0.2624(19) 0.028(11) H(21) 0.1627 0.4413 0.1062 0.0339 H(31) 0.2391 0.3547 0.0163 0.0344 H(51) -0.1086 0.5154 0.1292 0.0446 H(61) -0.3380 0.5464 0.0687 0.0507 H(71) -0.4048 0.4829 -0.0278 0.0517 H(91) 0.0686 0.2573 -0.0794 0.0431 H(101) -0.1578 0.2834 -0.1444 0.0523 H(111) -0.3329 0.3786 -0.1147 0.0501 H(161) -0.3090 0.3496 0.2676 0.0437 H(181) 0.0739 0.4598 0.3372 0.0451 H(201) -0.3313 0.2940 0.1691 0.0418 H(202) -0.2328 0.3370 0.1167 0.0418 H(203) -0.1820 0.2514 0.1455 0.0418 H(211) -0.1295 0.4580 0.4002 0.0762 H(212) -0.2889 0.4639 0.3590 0.0762 H(213) -0.2376 0.3811 0.3928 0.0762 H(221) 0.2792 0.4708 0.2810 0.0547 H(222) 0.2450 0.4753 0.2041 0.0547 H(223) 0.3160 0.3955 0.2366 0.0547 H(251) 0.1084 0.0350 -0.0261 0.0458 H(271) 0.5171 0.1396 -0.0380 0.0482 H(291) -0.0786 0.0913 0.0285 0.0466 H(292) -0.0793 0.1872 0.0281 0.0466 H(293) -0.0225 0.1397 0.0924 0.0466 H(301) 0.2873 -0.0277 -0.0844 0.0629 H(302) 0.3961 0.0323 -0.1203 0.0629 H(303) 0.4591 -0.0149 -0.0567 0.0629 H(311) 0.5775 0.2576 0.0105 0.0488 H(312) 0.4385 0.3185 0.0152 0.0488 H(313) 0.5041 0.2715 0.0784 0.0488 H(341) 0.4683 0.2987 0.3129 0.0544 H(342) 0.5318 0.2098 0.3041 0.0544 H(351) 0.3751 0.1866 0.3775 0.0583 H(352) 0.2643 0.2582 0.3541 0.0583 H(381) 0.4806 0.0850 0.3009 0.0566 H(382) 0.4227 0.0093 0.2586 0.0566 H(391) 0.5865 0.1116 0.2118 0.0587 H(392) 0.4555 0.0683 0.1675 0.0587



S31


Atom U11 U22 U33 U23 U13 U12

Rh(1) 0.02412(14) 0.02597(14) 0.02282(13) 0.00261(15) 0.00288(9) -0.00025(15) Cl(1) 0.0298(5) 0.0409(6) 0.0436(6) 0.0099(5) 0.0038(4) -0.0064(4) C(1) 0.0171(17) 0.030(2) 0.0256(18) 0.0009(15) -0.0020(14) -0.0046(15) N(1) 0.0318(18) 0.0258(16) 0.0212(15) 0.0039(13) 0.0008(13) -0.0030(14) C(2) 0.032(2) 0.0254(19) 0.0269(19) 0.0004(16) 0.0023(16) -0.0028(16) C(3) 0.030(2) 0.0270(19) 0.0288(19) 0.0025(16) 0.0057(16) -0.0046(16) N(2) 0.0333(18) 0.0303(18) 0.0236(16) 0.0076(14) 0.0014(13) -0.0029(14) C(4) 0.037(2) 0.029(2) 0.0274(19) 0.0025(16) 0.0075(16) -0.0007(17) C(5) 0.048(3) 0.027(2) 0.037(2) 0.0023(17) 0.0066(19) 0.0058(19) C(6) 0.045(3) 0.038(2) 0.044(3) 0.011(2) 0.014(2) 0.013(2) C(7) 0.032(2) 0.039(3) 0.058(3) 0.012(2) 0.002(2) 0.0063(19) C(8) 0.032(2) 0.032(2) 0.0268(19) 0.0040(16) 0.0045(16) -0.0010(17) C(9) 0.044(2) 0.038(3) 0.0262(19) -0.0003(17) 0.0037(17) 0.0038(19) C(10) 0.048(3) 0.050(3) 0.032(2) -0.003(2) -0.0048(18) -0.004(3) C(11) 0.040(3) 0.051(3) 0.034(2) 0.005(2) -0.0042(19) -0.004(2) C(12) 0.031(2) 0.040(2) 0.035(2) 0.0103(18) 0.0060(17) -0.0031(18) C(13) 0.032(2) 0.0248(19) 0.032(2) 0.0064(16) 0.0044(16) -0.0010(16) C(14) 0.030(2) 0.0219(18) 0.0292(19) 0.0036(15) -0.0020(16) -0.0003(15) C(15) 0.030(2) 0.0269(19) 0.031(2) 0.0048(16) -0.0008(16) -0.0015(17) C(16) 0.030(2) 0.040(2) 0.040(2) 0.0074(19) 0.0016(18) -0.0032(18) C(17) 0.045(3) 0.049(3) 0.035(2) 0.003(2) 0.006(2) 0.008(2) C(18) 0.041(2) 0.037(2) 0.035(2) -0.0067(19) -0.0041(18) 0.0027(19) C(19) 0.028(2) 0.029(2) 0.034(2) -0.0039(16) -0.0021(16) 0.0021(16) C(20) 0.028(2) 0.035(2) 0.041(2) 0.0039(19) -0.0051(16) -0.0046(18) C(21) 0.061(3) 0.090(5) 0.039(3) -0.008(3) 0.013(2) 0.008(3) C(22) 0.032(2) 0.053(3) 0.051(3) -0.022(2) 0.000(2) -0.007(2) C(23) 0.032(2) 0.032(2) 0.0233(17) 0.0010(16) 0.0017(14) 0.0053(17) C(24) 0.036(2) 0.033(2) 0.029(2) 0.0043(17) 0.0030(17) -0.0006(18) C(25) 0.048(3) 0.034(2) 0.032(2) -0.0031(18) 0.0019(19) 0.000(2) C(26) 0.046(3) 0.044(3) 0.027(2) -0.0002(19) 0.0038(18) 0.011(2) C(27) 0.037(2) 0.055(3) 0.028(2) 0.006(2) 0.0041(18) 0.015(2) C(28) 0.0257(19) 0.041(3) 0.0270(18) 0.0071(17) -0.0005(15) 0.0025(17) C(29) 0.036(2) 0.038(2) 0.042(2) -0.0076(19) 0.0051(19) -0.0105(19) C(30) 0.058(3) 0.059(3) 0.041(3) -0.008(2) 0.000(2) 0.016(3) C(31) 0.032(2) 0.055(3) 0.035(2) 0.004(2) 0.0025(18) -0.004(2) C(32) 0.0265(19) 0.050(3) 0.0285(19) 0.006(2) 0.0028(15) 0.001(2) C(33) 0.029(2) 0.040(2) 0.029(2) 0.0069(18) -0.0027(16) -0.0039(18) C(34) 0.055(3) 0.050(3) 0.031(2) 0.004(2) -0.007(2) -0.013(2) C(35) 0.055(3) 0.062(3) 0.029(2) -0.002(2) 0.001(2) -0.016(2) C(36) 0.041(2) 0.043(2) 0.0215(18) 0.0061(17) 0.0038(17) -0.006(2) C(37) 0.037(2) 0.036(2) 0.031(2) 0.0143(18) -0.0001(18) -0.001(2) C(38) 0.044(3) 0.040(3) 0.058(3) 0.011(2) -0.001(2) 0.008(2) C(39) 0.044(3) 0.057(3) 0.046(3) 0.001(2) 0.008(2) 0.011(2)



S32


Rh(1) - Cl(1) 2.3836(11) C(14) - C(15) 1.404(5) Rh(1) - C(1) 2.042(4) C(14) - C(19) 1.406(5)

Rh(1) - C(32) 2.102(4) C(15) - C(16) 1.387(6) Rh(1) - C(33) 2.120(4) C(15) - C(20) 1.500(6) Rh(1) - C(36) 2.189(4) C(16) - C(17) 1.387(6) Rh(1) - C(37) 2.220(4) C(17) - C(18) 1.396(7)

C(1) - N(1) 1.342(5) C(17) - C(21) 1.511(6) C(1) - N(2) 1.362(5) C(18) - C(19) 1.382(6) N(1) - C(2) 1.495(5) C(19) - C(22) 1.516(6) N(1) - C(14) 1.438(5) C(23) - C(24) 1.407(6) C(2) - C(3) 1.555(5) C(23) - C(28) 1.402(5) C(2) - C(4) 1.498(6) C(24) - C(25) 1.394(6) C(3) - N(2) 1.478(5) C(24) - C(29) 1.498(6) C(3) - C(8) 1.520(6) C(25) - C(26) 1.400(6) N(2) - C(23) 1.438(5) C(26) - C(27) 1.378(7) C(4) - C(5) 1.372(6) C(26) - C(30) 1.505(6) C(4) - C(13) 1.408(6) C(27) - C(28) 1.389(6) C(5) - C(6) 1.417(6) C(28) - C(31) 1.517(6) C(6) - C(7) 1.375(7) C(32) - C(33) 1.390(6) C(7) - C(12) 1.412(6) C(32) - C(39) 1.511(7) C(8) - C(9) 1.376(6) C(33) - C(34) 1.527(6) C(8) - C(13) 1.399(6) C(34) - C(35) 1.507(7) C(9) - C(10) 1.428(6) C(35) - C(36) 1.520(6)

C(10) - C(11) 1.391(7) C(36) - C(37) 1.370(6) C(11) - C(12) 1.409(6) C(37) - C(38) 1.514(6) C(12) - C(13) 1.415(6) C(38) - C(39) 1.510(7)




S33


Cl(1) - Rh(1) - C(1) 96.84(10) C(4) - C(13) - C(12) 122.9(4) Cl(1) - Rh(1) - C(32) 155.29(14) C(8) - C(13) - C(12) 123.7(4) C(1) - Rh(1) - C(32) 91.18(16) N(1) - C(14) - C(15) 118.9(3) Cl(1) - Rh(1) - C(33) 164.16(12) N(1) - C(14) - C(19) 120.0(3) C(1) - Rh(1) - C(33) 88.55(15) C(15) - C(14) - C(19) 121.0(4) C(32) - Rh(1) - C(33) 38.45(17) C(14) - C(15) - C(16) 117.9(4) Cl(1) - Rh(1) - C(36) 87.18(12) C(14) - C(15) - C(20) 122.6(4) C(1) - Rh(1) - C(36) 154.06(16) C(16) - C(15) - C(20) 119.4(4) C(32) - Rh(1) - C(36) 95.76(16) C(15) - C(16) - C(17) 122.6(4) C(33) - Rh(1) - C(36) 81.64(15) C(16) - C(17) - C(18) 117.9(4) Cl(1) - Rh(1) - C(37) 88.12(12) C(16) - C(17) - C(21) 121.7(5) C(1) - Rh(1) - C(37) 168.41(16) C(18) - C(17) - C(21) 120.3(5) C(32) - Rh(1) - C(37) 80.21(17) C(17) - C(18) - C(19) 121.9(4) C(33) - Rh(1) - C(37) 89.43(17) C(14) - C(19) - C(18) 118.5(4) C(36) - Rh(1) - C(37) 36.21(17) C(14) - C(19) - C(22) 123.0(4)

Rh(1) - C(1) - N(1) 122.2(3) C(18) - C(19) - C(22) 118.5(4) Rh(1) - C(1) - N(2) 129.2(3) N(2) - C(23) - C(24) 119.1(3) N(1) - C(1) - N(2) 107.6(3) N(2) - C(23) - C(28) 119.3(4) C(1) - N(1) - C(2) 114.0(3) C(24) - C(23) - C(28) 121.3(4) C(1) - N(1) - C(14) 125.0(3) C(23) - C(24) - C(25) 117.5(4) C(2) - N(1) - C(14) 121.0(3) C(23) - C(24) - C(29) 122.3(4) N(1) - C(2) - C(3) 101.4(3) C(25) - C(24) - C(29) 120.1(4) N(1) - C(2) - C(4) 114.8(3) C(24) - C(25) - C(26) 122.3(4) C(3) - C(2) - C(4) 105.3(3) C(25) - C(26) - C(27) 118.1(4) C(2) - C(3) - N(2) 102.5(3) C(25) - C(26) - C(30) 121.0(4) C(2) - C(3) - C(8) 104.7(3) C(27) - C(26) - C(30) 120.9(4) N(2) - C(3) - C(8) 116.1(3) C(26) - C(27) - C(28) 122.3(4) C(1) - N(2) - C(3) 113.5(3) C(23) - C(28) - C(27) 118.4(4) C(1) - N(2) - C(23) 128.2(3) C(23) - C(28) - C(31) 121.9(4) C(3) - N(2) - C(23) 117.5(3) C(27) - C(28) - C(31) 119.7(4) C(2) - C(4) - C(5) 131.8(4) Rh(1) - C(32) - C(33) 71.5(2) C(2) - C(4) - C(13) 108.2(3) Rh(1) - C(32) - C(39) 111.9(3) C(5) - C(4) - C(13) 119.9(4) C(33) - C(32) - C(39) 126.8(4) C(4) - C(5) - C(6) 118.2(4) Rh(1) - C(33) - C(32) 70.1(2) C(5) - C(6) - C(7) 121.8(4) Rh(1) - C(33) - C(34) 113.8(3) C(6) - C(7) - C(12) 121.6(4) C(32) - C(33) - C(34) 123.0(4) C(3) - C(8) - C(9) 132.7(4) C(33) - C(34) - C(35) 112.4(4) C(3) - C(8) - C(13) 107.8(3) C(34) - C(35) - C(36) 114.8(4) C(9) - C(8) - C(13) 119.4(4) Rh(1) - C(36) - C(35) 107.6(3) C(8) - C(9) - C(10) 118.1(4) Rh(1) - C(36) - C(37) 73.1(2)

C(9) - C(10) - C(11) 122.3(4) C(35) - C(36) - C(37) 125.8(4) C(10) - C(11) - C(12) 120.1(4) Rh(1) - C(37) - C(36) 70.7(2) C(7) - C(12) - C(11) 128.1(4) Rh(1) - C(37) - C(38) 112.3(3) C(7) - C(12) - C(13) 115.5(4) C(36) - C(37) - C(38) 123.7(4) C(11) - C(12) - C(13) 116.4(4) C(37) - C(38) - C(39) 111.9(4)

C(4) - C(13) - C(8) 113.3(4) C(32) - C(39) - C(38) 113.9(4)




S34

D. Single-crystal X-ray diffraction report for CCDC_719730_6b

A single-crystal X-ray diffraction study was performed on crystals grown from slow

diffusion of pentane into a saturated dichloromethane solution. A single crystal having

dimensions approximately 0.08 x 0.12 x 0.14 mm was mounted on a glass fibre using

perfluoropolyether oil and cooled rapidly to 150K in a stream of cold N2 using an

Oxford Cryosystems CRYOSTREAM unit. Diffraction data were measured using an

Enraf-Nonius KappaCCD diffractometer (graphite-monochromated MoKα radiation, λ =

0.71073 Å). Intensity data were processed using the DENZO-SMN package1.


group to be either P 21 or P 21/m. The structure could not be solved in the second spasce

group but was readily solved in P 21 using the direct-methods program SIR922, which

located all non-hydrogen atoms. Examination of the resulting model showed that there

were no additional symmetry elements, confirming the choice of space group. Subsequent

full-matrix least-squares refinement was carried out using the CRYSTALS program suite3.

Coordinates and anisotropic thermal parameters of all non-hydrogen atoms were refined.

The hydrogen atoms of the coordinated alkene groups were located in a difference Fourier

map and their coordinates and isotropic thermal parameters subsequently refined. Othe

hydrogen atoms were positioned geometrically after each cycle of refinement. A 3-term

Chebychev polynomial weighting scheme was applied. Refinement converged

satisfactorily to give R = 0.0385, wR = 0.0385.




Comment: The asymmetric unit contains two molecules, both on sites with no crystallographic

symmetry. These differ slightly in their molecular conformations. In both molecules the

carbene ligands have similar geometries whereas the cycloctadiene of the second

molecule is reflected about the RhClC(carbene) plane with respect to that of the first.



S35

Refinement of the Flack enantipole parameter gives a value of 0.01)2), showing the crystal

to consist of a single enantiomer5 despite the lack of inherent chirality of the complex.









5 H. D. Flack and G. Bernardinelli, J. Appl. Cryst., 2000, 33, 1143



S36

View of one of the two crystallographically-distinct molecules. Hydrogen atoms are not shown



S37


Crystal identification CCDC_719730_6b Chemical formula C45H54ClN2Rh Formula weight 761.29 Temperature (K) 150 Wavelength (Å) 0.71073 Crystal system Monoclinic Space group P 21 a (Å) 12.5115(2) b (Å) 12.2042(2) c (Å) 24.8139(5) α (°) 90 β (°) 90.4245(9) γ (°) 90 Cell volume (Å3) 3788.80(12) Z 4 Calculated density (Mg/m3) 1.335 Absorption coefficient (mm-1) 0.555 F000 1600 Crystal size (mm) 0.08 x 0.12 x 0.14 Description of crystal Yellow block Absorption correction Semi-empirical from equivalent reflections Transmission coefficients (min,max) 0.93, 0.96 θ range for data collection (°) 5.0 ≤ θ ≤ 27.5 Index ranges -16 ≤ h ≤ 16, -15 ≤ k ≤ 13, 0 ≤ l ≤ 32 Reflections measured 46131 Unique reflections 14962 Rint 0.072 Observed reflections (I > 3σ(I)) 10770 Refinement method Full-matrix least-squares on F Parameters refined 916 Weighting scheme Chebychev 3-term polynomial Goodness of fit 1.0788 R 0.0385 wR 0.0385 Residual electron density (min,max) (eÅ-3) -0.49, 0.35



S38


Atom x y z Uequiv

Rh(1) 0.30017(2) 0.20429(5) 0.294046(13) 0.0211 Cl(1) 0.44854(9) 0.32047(10) 0.31343(4) 0.0266 C(1) 0.3054(3) 0.1743(3) 0.37647(17) 0.0184 N(1) 0.2530(2) 0.2380(3) 0.41211(12) 0.0181 C(2) 0.3123(3) 0.2573(4) 0.46347(15) 0.0181 C(3) 0.4068(3) 0.1758(3) 0.45801(16) 0.0211 N(2) 0.3895(3) 0.1286(3) 0.40305(13) 0.0194 C(4) 0.2576(3) 0.2254(3) 0.51535(16) 0.0208 C(5) 0.1774(3) 0.2738(4) 0.54416(17) 0.0284 C(6) 0.1512(3) 0.2276(4) 0.59496(17) 0.0311 C(7) 0.2007(4) 0.1377(4) 0.61606(17) 0.0286 C(8) 0.3981(3) 0.0994(4) 0.50553(17) 0.0225 C(9) 0.4614(3) 0.0146(4) 0.52361(17) 0.0264 C(10) 0.4364(4) -0.0354(4) 0.57290(19) 0.0298 C(11) 0.3512(4) -0.0018(4) 0.60426(18) 0.0304 C(12) 0.2856(4) 0.0857(4) 0.58715(17) 0.0268 C(13) 0.3111(3) 0.1334(4) 0.53678(16) 0.0205 C(14) 0.1494(3) 0.2868(4) 0.40305(17) 0.0218 C(15) 0.1428(3) 0.3965(4) 0.38883(17) 0.0247 C(16) 0.0418(4) 0.4437(4) 0.3816(2) 0.0300 C(17) -0.0487(4) 0.3808(5) 0.3877(2) 0.0416 C(18) -0.0414(3) 0.2733(4) 0.4028(2) 0.0361 C(19) 0.0576(3) 0.2225(4) 0.41222(16) 0.0259 C(20) 0.2433(3) 0.4681(4) 0.38315(17) 0.0235 C(21) 0.2521(4) 0.5499(4) 0.4296(2) 0.0323 C(22) 0.2441(4) 0.5273(4) 0.3286(2) 0.0363 C(23) 0.0608(3) 0.1044(4) 0.43112(18) 0.0272 C(24) -0.0020(4) 0.0895(5) 0.4847(2) 0.0401 C(25) 0.0137(4) 0.0251(4) 0.3897(2) 0.0352 C(26) 0.4516(3) 0.0329(3) 0.38871(16) 0.0208 C(27) 0.5634(3) 0.0452(4) 0.38381(16) 0.0231 C(28) 0.6244(3) -0.0510(4) 0.37972(19) 0.0286 C(29) 0.5791(4) -0.1534(4) 0.3812(2) 0.0338 C(30) 0.4692(4) -0.1622(4) 0.38571(19) 0.0279 C(31) 0.4025(3) -0.0705(4) 0.38892(16) 0.0231 C(32) 0.6196(3) 0.1546(4) 0.38419(17) 0.0252 C(33) 0.6864(3) 0.1676(4) 0.43599(18) 0.0284 C(34) 0.6889(3) 0.1710(4) 0.3339(2) 0.0360 C(35) 0.2826(4) -0.0887(4) 0.39394(19) 0.0278 C(36) 0.2522(4) -0.1289(4) 0.4500(2) 0.0350 C(37) 0.2416(4) -0.1705(4) 0.3515(2) 0.0338 C(38) 0.2046(4) 0.0728(4) 0.2704(2) 0.0295 C(39) 0.1411(4) 0.1633(4) 0.2746(2) 0.0307 C(40) 0.0945(4) 0.2237(4) 0.2263(2) 0.0400 C(41) 0.1655(4) 0.3183(5) 0.2076(2) 0.0438 C(42) 0.2831(4) 0.2978(5) 0.21918(19) 0.0334 C(43) 0.3389(4) 0.2041(5) 0.20797(17) 0.0341 C(44) 0.2902(4) 0.1063(5) 0.1789(2) 0.0407



S39

C(45) 0.2432(4) 0.0209(5) 0.2175(2) 0.0399

Rh(2) 0.13243(3) 0.25044(5) -0.162671(14) 0.0274 Cl(2) 0.10366(11) 0.29854(13) -0.07105(5) 0.0412 C(46) 0.2673(4) 0.1770(3) -0.13224(17) 0.0236 N(3) 0.2682(3) 0.0878(3) -0.09951(14) 0.0253 C(47) 0.3582(4) 0.0863(4) -0.06071(18) 0.0286 C(48) 0.4157(3) 0.1961(4) -0.07292(15) 0.0258 N(4) 0.3592(3) 0.2326(3) -0.12290(13) 0.0247 C(49) 0.4427(4) -0.0010(4) -0.0666(2) 0.0373 C(50) 0.4404(5) -0.1128(5) -0.0593(3) 0.0518 C(51) 0.5393(6) -0.1716(5) -0.0636(3) 0.0569 C(52) 0.6335(6) -0.1217(6) -0.0721(3) 0.0611 C(53) 0.5328(4) 0.1656(4) -0.07764(19) 0.0337 C(54) 0.6246(4) 0.2276(4) -0.07911(19) 0.0398 C(55) 0.7247(4) 0.1731(6) -0.0800(2) 0.0532 C(56) 0.7331(4) 0.0618(7) -0.0803(3) 0.0584 C(57) 0.6392(4) -0.0058(5) -0.0778(2) 0.0455 C(58) 0.5406(4) 0.0519(4) -0.07584(18) 0.0348 C(59) 0.1941(3) -0.0049(4) -0.10104(17) 0.0232 C(60) 0.1291(4) -0.0258(4) -0.05588(19) 0.0303 C(61) 0.0675(4) -0.1200(5) -0.0563(2) 0.0401 C(62) 0.0686(5) -0.1915(5) -0.0995(2) 0.0440 C(63) 0.1318(5) -0.1692(5) -0.1429(2) 0.0428 C(64) 0.1963(4) -0.0766(4) -0.14527(18) 0.0288 C(65) 0.1226(5) 0.0480(4) -0.0076(2) 0.0418 C(66) 0.1696(7) -0.0087(6) 0.0421(2) 0.0740 C(67) 0.0042(6) 0.0800(6) 0.0015(3) 0.0765 C(68) 0.2652(4) -0.0620(4) -0.19545(19) 0.0333 C(69) 0.3662(5) -0.1341(5) -0.1934(2) 0.0475 C(70) 0.2026(5) -0.0898(5) -0.2468(2) 0.0442 C(71) 0.4008(3) 0.3142(4) -0.15923(17) 0.0253 C(72) 0.3834(3) 0.4261(4) -0.14896(18) 0.0272 C(73) 0.4204(4) 0.5022(4) -0.1863(2) 0.0339 C(74) 0.4746(4) 0.4693(4) -0.23239(19) 0.0337 C(75) 0.4948(4) 0.3595(4) -0.23995(19) 0.0331 C(76) 0.4604(3) 0.2800(4) -0.20379(18) 0.0265 C(77) 0.3295(4) 0.4679(4) -0.0985(2) 0.0384 C(78) 0.4143(6) 0.5244(6) -0.0624(3) 0.0600 C(79) 0.2387(5) 0.5479(5) -0.1107(3) 0.0601 C(80) 0.4859(4) 0.1598(4) -0.21574(19) 0.0324 C(81) 0.6073(4) 0.1419(5) -0.2166(2) 0.0409 C(82) 0.4376(4) 0.1207(5) -0.2694(2) 0.0366 C(83) 0.1843(4) 0.2822(4) -0.24172(19) 0.0313 C(84) 0.1262(4) 0.1858(5) -0.24176(19) 0.0341 C(85) 0.0125(4) 0.1747(5) -0.2642(2) 0.0494 C(86) -0.0723(4) 0.1947(7) -0.2209(2) 0.0568 C(87) -0.0363(4) 0.2724(6) -0.1779(2) 0.0464 C(88) 0.0115(5) 0.3726(6) -0.1858(3) 0.0461 C(89) 0.0337(5) 0.4214(5) -0.2412(2) 0.0511 C(90) 0.1452(4) 0.3934(5) -0.2608(2) 0.0401



S40


Atom x y z Uiso

H(1) 0.203(4) 0.026(4) 0.296(2) 0.026(13) H(2) 0.103(4) 0.172(4) 0.304(2) 0.027(13) H(3) 0.312(4) 0.369(5) 0.228(2) 0.043(15) H(4) 0.417(4) 0.202(4) 0.2092(17) 0.026(11) H(21) 0.3263 0.3377 0.4669 0.0217 H(31) 0.4818 0.2042 0.4597 0.0253 H(51) 0.1386 0.3395 0.5299 0.0341 H(61) 0.0933 0.2630 0.6164 0.0373 H(71) 0.1778 0.1080 0.6517 0.0343 H(91) 0.5240 -0.0108 0.5021 0.0317 H(101) 0.4817 -0.0977 0.5859 0.0357 H(111) 0.3362 -0.0397 0.6391 0.0365 H(161) 0.0353 0.5230 0.3720 0.0360 H(171) -0.1206 0.4141 0.3811 0.0499 H(181) -0.1084 0.2297 0.4072 0.0433 H(201) 0.3072 0.4189 0.3847 0.0282 H(211) 0.3179 0.5954 0.4250 0.0387 H(212) 0.2565 0.5092 0.4645 0.0387 H(213) 0.1877 0.5984 0.4295 0.0387 H(221) 0.3101 0.5731 0.3259 0.0436 H(222) 0.1796 0.5752 0.3254 0.0436 H(223) 0.2433 0.4719 0.2989 0.0436 H(231) 0.1382 0.0870 0.4367 0.0327 H(241) 0.0014 0.0110 0.4962 0.0482 H(242) 0.0306 0.1367 0.5134 0.0482 H(243) -0.0783 0.1112 0.4790 0.0482 H(251) 0.0177 -0.0514 0.4041 0.0423 H(252) -0.0626 0.0447 0.3824 0.0423 H(253) 0.0553 0.0299 0.3555 0.0423 H(281) 0.7036 -0.0447 0.3756 0.0343 H(291) 0.6247 -0.2205 0.3790 0.0406 H(301) 0.4364 -0.2369 0.3867 0.0335 H(321) 0.5635 0.2129 0.3834 0.0303 H(331) 0.7231 0.2403 0.4357 0.0341 H(332) 0.7410 0.1079 0.4380 0.0341 H(333) 0.6385 0.1630 0.4680 0.0341 H(341) 0.7245 0.2443 0.3357 0.0433 H(342) 0.7444 0.1122 0.3323 0.0433 H(343) 0.6427 0.1673 0.3008 0.0433 H(351) 0.2481 -0.0159 0.3877 0.0334 H(361) 0.1731 -0.1398 0.4516 0.0420 H(362) 0.2744 -0.0733 0.4775 0.0420 H(363) 0.2891 -0.2000 0.4576 0.0420 H(371) 0.1628 -0.1807 0.3558 0.0406 H(372) 0.2786 -0.2424 0.3565 0.0406 H(373) 0.2566 -0.1415 0.3146 0.0406 H(401) 0.0231 0.2539 0.2363 0.0480 H(402) 0.0857 0.1706 0.1959 0.0480



S41

H(411) 0.1432 0.3867 0.2266 0.0525 H(412) 0.1555 0.3281 0.1678 0.0525 H(441) 0.3471 0.0703 0.1570 0.0489 H(442) 0.2319 0.1331 0.1545 0.0489 H(451) 0.2994 -0.0348 0.2261 0.0479 H(452) 0.1813 -0.0159 0.1993 0.0479

H(5) 0.265(4) 0.278(4) -0.2394(19) 0.031(13) H(6) 0.169(3) 0.115(4) -0.2411(16) 0.010(10) H(7) -0.065(4) 0.247(5) -0.146(2) 0.044(15) H(8) 0.015(4) 0.418(5) -0.161(2) 0.035(16)

H(471) 0.3274 0.0730 -0.0242 0.0343 H(481) 0.4136 0.2576 -0.0463 0.0310 H(501) 0.3721 -0.1518 -0.0512 0.0620 H(511) 0.5381 -0.2533 -0.0602 0.0681 H(521) 0.7003 -0.1664 -0.0746 0.0732 H(541) 0.6209 0.3094 -0.0796 0.0477 H(551) 0.7915 0.2181 -0.0804 0.0639 H(561) 0.8053 0.0268 -0.0823 0.0701 H(611) 0.0211 -0.1367 -0.0247 0.0482 H(621) 0.0234 -0.2591 -0.0990 0.0529 H(631) 0.1317 -0.2214 -0.1739 0.0513 H(651) 0.1652 0.1160 -0.0140 0.0503 H(661) 0.1646 0.0414 0.0739 0.0888 H(662) 0.2462 -0.0273 0.0355 0.0888 H(663) 0.1286 -0.0774 0.0495 0.0888 H(671) -0.0009 0.1292 0.0336 0.0921 H(672) -0.0239 0.1190 -0.0311 0.0921 H(673) -0.0390 0.0123 0.0078 0.0921 H(681) 0.2868 0.0169 -0.1960 0.0400 H(691) 0.4089 -0.1222 -0.2268 0.0571 H(692) 0.3449 -0.2129 -0.1910 0.0571 H(693) 0.4102 -0.1140 -0.1611 0.0571 H(701) 0.2496 -0.0795 -0.2788 0.0531 H(702) 0.1781 -0.1678 -0.2451 0.0531 H(703) 0.1391 -0.0404 -0.2499 0.0531 H(731) 0.4077 0.5821 -0.1799 0.0408 H(741) 0.4984 0.5246 -0.2595 0.0405 H(751) 0.5356 0.3361 -0.2725 0.0397 H(771) 0.2970 0.4036 -0.0798 0.0461 H(781) 0.3796 0.5524 -0.0290 0.0721 H(782) 0.4469 0.5870 -0.0825 0.0721 H(783) 0.4712 0.4704 -0.0525 0.0721 H(791) 0.2060 0.5728 -0.0761 0.0723 H(792) 0.2674 0.6126 -0.1306 0.0723 H(793) 0.1831 0.5106 -0.1333 0.0723 H(801) 0.4529 0.1157 -0.1862 0.0390 H(811) 0.6229 0.0631 -0.2244 0.0491 H(812) 0.6396 0.1889 -0.2451 0.0491 H(813) 0.6385 0.1620 -0.1807 0.0491 H(821) 0.4565 0.0420 -0.2753 0.0439 H(822) 0.4668 0.1659 -0.2995 0.0439 H(823) 0.3581 0.1286 -0.2684 0.0439



S42

H(851) 0.0022 0.2294 -0.2938 0.0592 H(852) 0.0030 0.0991 -0.2789 0.0592 H(861) -0.1377 0.2255 -0.2387 0.0681 H(862) -0.0902 0.1230 -0.2037 0.0681 H(891) 0.0266 0.5029 -0.2390 0.0613 H(892) -0.0199 0.3919 -0.2675 0.0613 H(901) 0.1446 0.3939 -0.3011 0.0481 H(902) 0.1960 0.4505 -0.2472 0.0481



S43


Atom U11 U22 U33 U23 U13 U12

Rh(1) 0.02126(15) 0.02140(17) 0.02052(15) 0.00058(16) -0.00129(11) -0.00199(15) Cl(1) 0.0255(5) 0.0277(6) 0.0265(5) 0.0024(5) -0.0005(4) -0.0068(4) C(1) 0.0158(18) 0.017(2) 0.022(2) 0.0028(16) 0.0019(15) -0.0022(15) N(1) 0.0179(15) 0.0172(19) 0.0192(15) 0.0009(14) -0.0012(12) 0.0014(13) C(2) 0.0191(18) 0.015(2) 0.0198(18) -0.0017(18) -0.0061(14) 0.0017(18) C(3) 0.021(2) 0.021(3) 0.021(2) -0.0011(16) -0.0024(15) 0.0014(15) N(2) 0.0220(17) 0.0182(19) 0.0179(16) -0.0010(14) 0.0004(13) 0.0008(13) C(4) 0.0186(18) 0.021(3) 0.0232(19) 0.0000(16) 0.0021(14) -0.0028(15) C(5) 0.026(2) 0.030(3) 0.030(2) -0.0052(19) 0.0008(17) 0.0042(18) C(6) 0.026(2) 0.042(4) 0.026(2) -0.0051(19) 0.0086(16) -0.0041(18) C(7) 0.032(2) 0.031(3) 0.023(2) 0.000(2) 0.0093(18) -0.008(2) C(8) 0.020(2) 0.023(2) 0.024(2) 0.0031(18) 0.0010(16) -0.0029(16) C(9) 0.031(2) 0.024(3) 0.025(2) 0.0043(19) -0.0032(18) 0.0057(18) C(10) 0.035(2) 0.023(3) 0.032(2) 0.007(2) -0.0108(19) -0.0005(19) C(11) 0.039(3) 0.025(3) 0.027(2) 0.007(2) -0.003(2) -0.006(2) C(12) 0.036(2) 0.021(2) 0.024(2) -0.0003(18) -0.0007(18) -0.0123(19) C(13) 0.0152(18) 0.022(2) 0.024(2) -0.0021(17) 0.0006(15) -0.0016(16) C(14) 0.017(2) 0.024(2) 0.024(2) -0.0009(18) 0.0011(16) 0.0056(16) C(15) 0.022(2) 0.025(2) 0.028(2) -0.0001(19) -0.0019(17) 0.0017(17) C(16) 0.029(2) 0.021(3) 0.040(3) 0.005(2) -0.003(2) 0.0066(18) C(17) 0.026(3) 0.042(3) 0.057(3) -0.003(3) -0.004(2) 0.005(2) C(18) 0.017(2) 0.037(3) 0.054(3) -0.004(2) 0.0010(19) 0.0001(19) C(19) 0.0227(19) 0.029(3) 0.0256(19) -0.0026(17) 0.0018(15) -0.0045(17) C(20) 0.027(2) 0.019(2) 0.024(2) 0.0029(18) 0.0043(17) 0.0007(18) C(21) 0.037(3) 0.026(3) 0.034(3) -0.003(2) 0.001(2) -0.002(2) C(22) 0.049(3) 0.027(3) 0.033(3) 0.005(2) 0.002(2) -0.003(2) C(23) 0.021(2) 0.029(3) 0.031(2) 0.006(2) 0.0029(17) -0.0037(18) C(24) 0.035(3) 0.047(3) 0.039(3) 0.009(2) 0.005(2) -0.013(2) C(25) 0.042(3) 0.025(3) 0.039(3) -0.001(2) 0.005(2) -0.009(2) C(26) 0.025(2) 0.021(2) 0.017(2) 0.0005(17) 0.0021(16) 0.0054(17) C(27) 0.026(2) 0.023(2) 0.020(2) -0.0003(17) 0.0024(16) 0.0030(17) C(28) 0.022(2) 0.033(3) 0.031(2) 0.003(2) 0.0047(18) 0.0054(18) C(29) 0.041(3) 0.025(3) 0.036(3) -0.005(2) 0.002(2) 0.011(2) C(30) 0.034(2) 0.013(2) 0.036(2) 0.0002(19) 0.0018(19) 0.0081(17) C(31) 0.028(2) 0.019(2) 0.022(2) 0.0009(17) 0.0005(17) 0.0009(17) C(32) 0.018(2) 0.028(2) 0.030(2) 0.0009(18) -0.0007(17) -0.0023(17) C(33) 0.020(2) 0.031(3) 0.034(2) 0.0012(19) 0.0019(17) 0.0022(16) C(34) 0.022(2) 0.044(3) 0.042(3) 0.000(2) 0.0070(19) -0.0033(18) C(35) 0.026(2) 0.023(3) 0.034(3) 0.000(2) 0.0012(19) 0.0024(18) C(36) 0.037(3) 0.032(3) 0.036(3) 0.001(2) 0.002(2) -0.010(2) C(37) 0.039(3) 0.028(3) 0.035(3) -0.003(2) -0.004(2) 0.000(2) C(38) 0.031(3) 0.025(3) 0.032(3) -0.001(2) -0.001(2) -0.007(2) C(39) 0.019(2) 0.044(3) 0.029(2) -0.003(2) -0.0041(19) -0.0022(19) C(40) 0.035(2) 0.041(4) 0.044(3) 0.003(2) -0.013(2) 0.006(2) C(41) 0.046(3) 0.046(4) 0.040(3) 0.011(3) -0.016(2) -0.007(2) C(42) 0.043(3) 0.032(3) 0.025(2) 0.004(2) -0.007(2) -0.010(2) C(43) 0.036(2) 0.042(3) 0.024(2) -0.005(3) 0.0025(17) -0.006(3) C(44) 0.046(3) 0.048(4) 0.029(3) -0.010(2) -0.001(2) -0.003(2) C(45) 0.035(3) 0.038(3) 0.047(3) -0.012(2) 0.002(2) -0.005(2)



S44

Rh(2) 0.02454(17) 0.0320(2) 0.02581(18) 0.00086(17) 0.00270(13) 0.00307(16) Cl(2) 0.0440(7) 0.0477(8) 0.0321(6) -0.0026(6) 0.0102(5) 0.0085(6) C(46) 0.029(2) 0.017(3) 0.025(2) -0.0038(17) 0.0054(17) -0.0016(17) N(3) 0.0265(19) 0.031(2) 0.0188(17) 0.0016(16) -0.0012(14) -0.0024(15) C(47) 0.029(2) 0.029(3) 0.028(2) 0.0066(19) -0.0053(18) -0.0063(19) C(48) 0.030(2) 0.027(2) 0.0209(18) 0.000(2) -0.0038(15) -0.002(2) N(4) 0.0250(17) 0.025(3) 0.0244(16) 0.0004(15) -0.0016(13) 0.0018(14) C(49) 0.050(3) 0.028(3) 0.034(3) 0.006(2) -0.015(2) 0.000(2) C(50) 0.063(4) 0.043(4) 0.049(3) 0.000(3) -0.026(3) -0.001(3) C(51) 0.077(5) 0.032(3) 0.062(4) 0.003(3) -0.028(3) 0.013(3) C(52) 0.073(5) 0.056(4) 0.054(4) -0.006(3) -0.019(3) 0.028(4) C(53) 0.031(2) 0.041(3) 0.029(2) 0.004(2) -0.0045(19) 0.003(2) C(54) 0.033(2) 0.050(4) 0.036(2) 0.004(2) -0.0038(18) -0.007(2) C(55) 0.036(3) 0.078(6) 0.046(3) 0.005(3) 0.000(2) -0.008(3) C(56) 0.031(3) 0.095(6) 0.049(4) 0.002(4) 0.001(3) 0.015(3) C(57) 0.043(3) 0.057(4) 0.037(3) -0.001(3) -0.005(2) 0.013(3) C(58) 0.037(3) 0.042(3) 0.025(2) 0.005(2) -0.0084(19) 0.006(2) C(59) 0.024(2) 0.022(2) 0.023(2) 0.0027(18) 0.0005(16) 0.0005(17) C(60) 0.035(3) 0.025(3) 0.031(2) 0.002(2) -0.0019(19) -0.003(2) C(61) 0.049(3) 0.040(3) 0.032(3) 0.004(2) 0.008(2) -0.012(2) C(62) 0.053(3) 0.037(3) 0.042(3) -0.004(2) 0.004(2) -0.023(3) C(63) 0.060(3) 0.035(3) 0.033(3) 0.000(2) 0.003(2) -0.009(2) C(64) 0.030(2) 0.029(3) 0.027(2) 0.0013(19) 0.0012(18) -0.0018(19) C(65) 0.060(3) 0.032(3) 0.034(3) -0.007(2) 0.020(2) -0.012(2) C(66) 0.132(7) 0.064(5) 0.026(3) 0.001(3) -0.002(3) -0.046(5) C(67) 0.077(5) 0.043(4) 0.110(6) -0.025(4) 0.058(4) -0.012(3) C(68) 0.040(3) 0.032(3) 0.028(2) -0.008(2) 0.007(2) -0.003(2) C(69) 0.053(4) 0.045(4) 0.045(3) -0.004(3) 0.015(3) 0.020(3) C(70) 0.061(4) 0.044(4) 0.027(3) -0.001(2) 0.006(2) -0.008(3) C(71) 0.024(2) 0.027(3) 0.025(2) 0.0056(18) 0.0005(16) -0.0049(18) C(72) 0.024(2) 0.028(3) 0.030(2) -0.002(2) 0.0017(18) 0.0010(18) C(73) 0.037(3) 0.027(3) 0.037(3) 0.006(2) 0.006(2) -0.004(2) C(74) 0.037(3) 0.033(3) 0.032(2) 0.003(2) 0.006(2) -0.011(2) C(75) 0.030(2) 0.036(3) 0.032(3) -0.003(2) 0.0023(19) -0.006(2) C(76) 0.025(2) 0.027(3) 0.027(2) -0.0021(18) 0.0036(17) -0.0036(17) C(77) 0.047(3) 0.033(3) 0.036(3) -0.005(2) 0.011(2) -0.001(2) C(78) 0.079(5) 0.060(5) 0.040(3) -0.023(3) 0.010(3) -0.027(4) C(79) 0.066(4) 0.048(4) 0.067(4) 0.014(3) 0.030(3) 0.022(3) C(80) 0.037(3) 0.030(3) 0.030(3) -0.002(2) 0.005(2) 0.001(2) C(81) 0.031(3) 0.047(4) 0.044(3) -0.011(3) 0.003(2) 0.009(2) C(82) 0.039(3) 0.037(3) 0.034(3) -0.005(2) 0.003(2) -0.002(2) C(83) 0.028(2) 0.040(3) 0.026(2) 0.002(2) 0.0026(19) 0.005(2) C(84) 0.030(2) 0.041(4) 0.031(2) 0.003(2) 0.0013(18) 0.004(2) C(85) 0.034(3) 0.065(5) 0.049(3) -0.004(3) -0.005(2) -0.002(2) C(86) 0.034(3) 0.086(5) 0.051(3) 0.004(4) -0.002(2) -0.006(3) C(87) 0.028(2) 0.068(5) 0.044(3) 0.002(3) 0.006(2) 0.007(3) C(88) 0.042(3) 0.058(4) 0.039(3) -0.001(3) 0.001(2) 0.027(3) C(89) 0.048(3) 0.054(4) 0.051(3) 0.013(3) 0.009(3) 0.021(3) C(90) 0.042(3) 0.040(3) 0.038(3) 0.014(2) -0.002(2) 0.000(2)



S45

Table 5: Bond lengths (Å) Rh(1) - Cl(1) 2.3821(11) Rh(2) - Cl(2) 2.3779(13) Rh(1) - C(1) 2.078(4) Rh(2) - C(46) 2.050(5)

Rh(1) - C(38) 2.083(5) Rh(2) - C(83) 2.107(5) Rh(1) - C(39) 2.105(4) Rh(2) - C(84) 2.116(5) Rh(1) - C(42) 2.189(5) Rh(2) - C(87) 2.158(5) Rh(1) - C(43) 2.194(4) Rh(2) - C(88) 2.198(6)

C(1) - N(1) 1.351(5) C(46) - N(3) 1.358(6) C(1) - N(2) 1.358(5) C(46) - N(4) 1.353(5) N(1) - C(2) 1.489(5) N(3) - C(47) 1.476(5) N(1) - C(14) 1.442(5) N(3) - C(59) 1.463(6) C(2) - C(3) 1.552(6) C(47) - C(48) 1.551(7) C(2) - C(4) 1.513(5) C(47) - C(49) 1.510(7) C(3) - N(2) 1.495(5) C(48) - N(4) 1.491(5) C(3) - C(8) 1.508(6) C(48) - C(53) 1.517(6) N(2) - C(26) 1.448(5) N(4) - C(71) 1.443(5) C(4) - C(5) 1.370(6) C(49) - C(50) 1.377(8) C(4) - C(13) 1.410(6) C(49) - C(58) 1.406(7) C(5) - C(6) 1.421(6) C(50) - C(51) 1.435(9) C(6) - C(7) 1.363(7) C(51) - C(52) 1.345(10) C(7) - C(12) 1.434(6) C(52) - C(57) 1.423(9) C(8) - C(9) 1.376(6) C(53) - C(54) 1.376(7) C(8) - C(13) 1.403(6) C(53) - C(58) 1.391(7) C(9) - C(10) 1.405(6) C(54) - C(55) 1.417(8)

C(10) - C(11) 1.386(7) C(55) - C(56) 1.363(10) C(11) - C(12) 1.411(7) C(56) - C(57) 1.438(9) C(12) - C(13) 1.417(6) C(57) - C(58) 1.421(7) C(14) - C(15) 1.387(6) C(59) - C(60) 1.413(6) C(14) - C(19) 1.411(6) C(59) - C(64) 1.404(6) C(15) - C(16) 1.399(6) C(60) - C(61) 1.384(7) C(15) - C(20) 1.539(6) C(60) - C(65) 1.502(7) C(16) - C(17) 1.378(7) C(61) - C(62) 1.382(8) C(17) - C(18) 1.367(8) C(62) - C(63) 1.368(7) C(18) - C(19) 1.404(6) C(63) - C(64) 1.389(7) C(19) - C(23) 1.516(6) C(64) - C(68) 1.530(6) C(20) - C(21) 1.527(7) C(65) - C(66) 1.529(9) C(20) - C(22) 1.534(6) C(65) - C(67) 1.549(9) C(23) - C(24) 1.561(6) C(68) - C(69) 1.540(7) C(23) - C(25) 1.527(7) C(68) - C(70) 1.528(7) C(26) - C(27) 1.413(6) C(71) - C(72) 1.406(6) C(26) - C(31) 1.404(6) C(71) - C(76) 1.402(6) C(27) - C(28) 1.404(6) C(72) - C(73) 1.394(7) C(27) - C(32) 1.509(6) C(72) - C(77) 1.514(6) C(28) - C(29) 1.372(7) C(73) - C(74) 1.392(7) C(29) - C(30) 1.384(7) C(74) - C(75) 1.377(7) C(30) - C(31) 1.399(6) C(75) - C(76) 1.392(7) C(31) - C(35) 1.522(6) C(76) - C(80) 1.532(7) C(32) - C(33) 1.536(6) C(77) - C(78) 1.546(8) C(32) - C(34) 1.539(6) C(77) - C(79) 1.526(8) C(35) - C(36) 1.526(7) C(80) - C(81) 1.535(7) C(35) - C(37) 1.536(7) C(80) - C(82) 1.534(7) C(38) - C(39) 1.365(7) C(83) - C(84) 1.383(7) C(38) - C(45) 1.539(7) C(83) - C(90) 1.516(7)



S46

C(39) - C(40) 1.520(7) C(84) - C(85) 1.529(7) C(40) - C(41) 1.531(8) C(85) - C(86) 1.535(8) C(41) - C(42) 1.518(7) C(86) - C(87) 1.494(9) C(42) - C(43) 1.369(8) C(87) - C(88) 1.376(9) C(43) - C(44) 1.521(8) C(88) - C(89) 1.525(8) C(44) - C(45) 1.535(8) C(89) - C(90) 1.520(8)




S47


Cl(1) - Rh(1) - C(1) 83.53(11) Cl(2) - Rh(2) - C(46) 83.44(12) Cl(1) - Rh(1) - C(38) 163.79(14) Cl(2) - Rh(2) - C(83) 153.45(15) C(1) - Rh(1) - C(38) 98.92(18) C(46) - Rh(2) - C(83) 99.50(18) Cl(1) - Rh(1) - C(39) 157.22(15) Cl(2) - Rh(2) - C(84) 166.88(14) C(1) - Rh(1) - C(39) 101.93(18) C(46) - Rh(2) - C(84) 101.73(18) C(38) - Rh(1) - C(39) 38.0(2) C(83) - Rh(2) - C(84) 38.24(19) Cl(1) - Rh(1) - C(42) 86.11(14) Cl(2) - Rh(2) - C(87) 88.99(16) C(1) - Rh(1) - C(42) 158.29(18) C(46) - Rh(2) - C(87) 157.0(2) C(38) - Rh(1) - C(42) 96.3(2) C(83) - Rh(2) - C(87) 97.0(2) C(39) - Rh(1) - C(42) 80.98(19) C(84) - Rh(2) - C(87) 81.6(2) Cl(1) - Rh(1) - C(43) 91.12(14) Cl(2) - Rh(2) - C(88) 88.47(17) C(1) - Rh(1) - C(43) 162.25(18) C(46) - Rh(2) - C(88) 163.0(2) C(38) - Rh(1) - C(43) 81.7(2) C(83) - Rh(2) - C(88) 81.3(2) C(39) - Rh(1) - C(43) 89.53(19) C(84) - Rh(2) - C(88) 89.4(2) C(42) - Rh(1) - C(43) 36.4(2) C(87) - Rh(2) - C(88) 36.8(3)

Rh(1) - C(1) - N(1) 122.1(3) Rh(2) - C(46) - N(3) 125.0(3) Rh(1) - C(1) - N(2) 124.7(3) Rh(2) - C(46) - N(4) 122.7(3) N(1) - C(1) - N(2) 107.3(3) N(3) - C(46) - N(4) 107.2(4) C(1) - N(1) - C(2) 114.2(3) C(46) - N(3) - C(47) 113.7(4) C(1) - N(1) - C(14) 125.2(3) C(46) - N(3) - C(59) 127.0(4) C(2) - N(1) - C(14) 120.6(3) C(47) - N(3) - C(59) 119.2(3) N(1) - C(2) - C(3) 101.5(3) N(3) - C(47) - C(48) 102.4(3) N(1) - C(2) - C(4) 117.5(3) N(3) - C(47) - C(49) 118.5(4) C(3) - C(2) - C(4) 105.0(3) C(48) - C(47) - C(49) 105.4(4) C(2) - C(3) - N(2) 102.8(3) C(47) - C(48) - N(4) 101.7(3) C(2) - C(3) - C(8) 105.6(3) C(47) - C(48) - C(53) 104.6(4) N(2) - C(3) - C(8) 117.7(3) N(4) - C(48) - C(53) 117.5(3) C(1) - N(2) - C(3) 113.0(3) C(46) - N(4) - C(48) 112.9(3) C(1) - N(2) - C(26) 128.8(3) C(46) - N(4) - C(71) 123.3(3) C(3) - N(2) - C(26) 117.4(3) C(48) - N(4) - C(71) 123.7(3) C(2) - C(4) - C(5) 132.1(4) C(47) - C(49) - C(50) 132.2(5) C(2) - C(4) - C(13) 108.0(3) C(47) - C(49) - C(58) 107.6(4) C(5) - C(4) - C(13) 119.6(4) C(50) - C(49) - C(58) 119.8(5) C(4) - C(5) - C(6) 117.8(4) C(49) - C(50) - C(51) 117.8(6) C(5) - C(6) - C(7) 123.6(4) C(50) - C(51) - C(52) 122.8(6) C(6) - C(7) - C(12) 120.0(4) C(51) - C(52) - C(57) 120.7(6) C(3) - C(8) - C(9) 132.4(4) C(48) - C(53) - C(54) 132.4(5) C(3) - C(8) - C(13) 108.1(4) C(48) - C(53) - C(58) 108.1(4) C(9) - C(8) - C(13) 119.3(4) C(54) - C(53) - C(58) 119.4(5) C(8) - C(9) - C(10) 118.6(4) C(53) - C(54) - C(55) 118.7(5)


C(4) - C(13) - C(8) 113.3(4) C(49) - C(58) - C(53) 113.8(4) C(4) - C(13) - C(12) 123.4(4) C(49) - C(58) - C(57) 122.3(5) C(8) - C(13) - C(12) 123.1(4) C(53) - C(58) - C(57) 123.6(5) N(1) - C(14) - C(15) 119.4(4) N(3) - C(59) - C(60) 119.2(4) N(1) - C(14) - C(19) 118.4(4) N(3) - C(59) - C(64) 119.1(4) C(15) - C(14) - C(19) 122.1(4) C(60) - C(59) - C(64) 121.5(4)



S48

C(14) - C(15) - C(16) 118.9(4) C(59) - C(60) - C(61) 117.9(4) C(14) - C(15) - C(20) 121.6(4) C(59) - C(60) - C(65) 124.0(4) C(16) - C(15) - C(20) 119.5(4) C(61) - C(60) - C(65) 118.1(4) C(15) - C(16) - C(17) 119.9(5) C(60) - C(61) - C(62) 121.4(5) C(16) - C(17) - C(18) 120.8(5) C(61) - C(62) - C(63) 119.6(5) C(17) - C(18) - C(19) 121.8(4) C(62) - C(63) - C(64) 122.4(5) C(14) - C(19) - C(18) 116.5(4) C(59) - C(64) - C(63) 117.3(4) C(14) - C(19) - C(23) 124.0(4) C(59) - C(64) - C(68) 125.3(4) C(18) - C(19) - C(23) 119.5(4) C(63) - C(64) - C(68) 117.4(4) C(15) - C(20) - C(21) 110.9(4) C(60) - C(65) - C(66) 110.4(5) C(15) - C(20) - C(22) 111.0(4) C(60) - C(65) - C(67) 108.9(5) C(21) - C(20) - C(22) 110.9(4) C(66) - C(65) - C(67) 111.1(5) C(19) - C(23) - C(24) 111.3(4) C(64) - C(68) - C(69) 111.9(4) C(19) - C(23) - C(25) 112.7(4) C(64) - C(68) - C(70) 111.3(4) C(24) - C(23) - C(25) 107.8(4) C(69) - C(68) - C(70) 108.4(4) N(2) - C(26) - C(27) 118.0(4) N(4) - C(71) - C(72) 120.0(4) N(2) - C(26) - C(31) 119.2(4) N(4) - C(71) - C(76) 118.9(4) C(27) - C(26) - C(31) 121.9(4) C(72) - C(71) - C(76) 121.1(4) C(26) - C(27) - C(28) 117.1(4) C(71) - C(72) - C(73) 118.3(4) C(26) - C(27) - C(32) 123.7(4) C(71) - C(72) - C(77) 123.2(4) C(28) - C(27) - C(32) 119.2(4) C(73) - C(72) - C(77) 118.5(4) C(27) - C(28) - C(29) 122.3(4) C(72) - C(73) - C(74) 121.3(5) C(28) - C(29) - C(30) 118.9(4) C(73) - C(74) - C(75) 118.9(4) C(29) - C(30) - C(31) 122.4(4) C(74) - C(75) - C(76) 122.2(4) C(26) - C(31) - C(30) 117.2(4) C(71) - C(76) - C(75) 118.0(4) C(26) - C(31) - C(35) 124.2(4) C(71) - C(76) - C(80) 123.4(4) C(30) - C(31) - C(35) 118.5(4) C(75) - C(76) - C(80) 118.5(4) C(27) - C(32) - C(33) 110.3(4) C(72) - C(77) - C(78) 108.7(4) C(27) - C(32) - C(34) 112.1(4) C(72) - C(77) - C(79) 112.8(4) C(33) - C(32) - C(34) 111.0(3) C(78) - C(77) - C(79) 109.6(5) C(31) - C(35) - C(36) 112.0(4) C(76) - C(80) - C(81) 110.3(4) C(31) - C(35) - C(37) 111.3(4) C(76) - C(80) - C(82) 112.6(4) C(36) - C(35) - C(37) 109.4(4) C(81) - C(80) - C(82) 109.1(4) Rh(1) - C(38) - C(39) 71.9(3) Rh(2) - C(83) - C(84) 71.2(3) Rh(1) - C(38) - C(45) 112.0(3) Rh(2) - C(83) - C(90) 110.7(3) C(39) - C(38) - C(45) 125.7(5) C(84) - C(83) - C(90) 126.4(5) Rh(1) - C(39) - C(38) 70.1(3) Rh(2) - C(84) - C(83) 70.5(3) Rh(1) - C(39) - C(40) 114.9(3) Rh(2) - C(84) - C(85) 113.5(3) C(38) - C(39) - C(40) 123.6(5) C(83) - C(84) - C(85) 124.2(5) C(39) - C(40) - C(41) 112.7(4) C(84) - C(85) - C(86) 112.2(4) C(40) - C(41) - C(42) 112.4(4) C(85) - C(86) - C(87) 113.1(5) Rh(1) - C(42) - C(41) 109.6(3) Rh(2) - C(87) - C(86) 109.6(4) Rh(1) - C(42) - C(43) 72.0(3) Rh(2) - C(87) - C(88) 73.2(3) C(41) - C(42) - C(43) 126.5(5) C(86) - C(87) - C(88) 126.3(6) Rh(1) - C(43) - C(42) 71.6(3) Rh(2) - C(88) - C(87) 70.0(3) Rh(1) - C(43) - C(44) 111.8(3) Rh(2) - C(88) - C(89) 111.7(4) C(42) - C(43) - C(44) 123.3(4) C(87) - C(88) - C(89) 123.8(6) C(43) - C(44) - C(45) 113.0(4) C(88) - C(89) - C(90) 112.0(5) C(38) - C(45) - C(44) 112.2(4) C(83) - C(90) - C(89) 113.4(4)




S49

E. Single-crystal X-ray diffraction report for CCDC_719728_7b

Single crystals for iridium complex 7b suitable for X-ray study were grown by slow

diffusion of pentane into a saturated dichloromethane solution.

A large single crystal was cut to give a fragment having dimensions approximately

0.08 x 0.14 x 0.14 mm. This was mounted on a glass fibre using perfluoropolyether oil and

cooled rapidly to 150K in a stream of cold N2 using an Oxford Cryosystems

CRYOSTREAM unit. Diffraction data were measured using an Enraf-Nonius KappaCCD

diffractometer (graphite-monochromated MoKα radiation, λ = 0.71073 Å). Intensity data

were processed using the DENZO-SMN package1.


group to be P 21/c. The structure was solved using the direct-methods program SIR922,

which located all non-hydrogen atoms. Subsequent full-matrix least-squares refinement

was carried out using the CRYSTALS program suite3. Coordinates and anisotropic thermal

parameters of all non-hydrogen atoms were refined. The hydrogen atoms of the

coordinated alkene groups were located in a difference Fourier map and their coordinates

and isotropic thermal parameters subsequently refined. Other hydrogen atoms were

positioned geometrically after each cycle of refinement. A 3-term Chebychev polynomial

weighting scheme was applied. Refinement converged satisfactorily to give R = 0.0218,

wR = 0.0226.











S50




Hydrogen atoms not shown



S51


Crystal identification CCDC_719728_7b Chemical formula C45H54ClIrN2 Formula weight 850.61 Temperature (K) 150 Wavelength (Å) 0.71073 Crystal system Monoclinic Space group P 21/c a (Å) 11.6520(2) b (Å) 28.9269(3) c (Å) 11.7784(2) α (°) 90 β (°) 106.6717(5) γ (°) 90 Cell volume (Å3) 3803.10(10) Z 4 Calculated density (Mg/m3) 1.486 Absorption coefficient (mm-1) 3.615 F000 1728 Crystal size (mm) 0.08 x 0.14 x 0.14 Description of crystal Orange fragment Absorption correction Semi-empirical from equivalent reflections Transmission coefficients (min,max) 0.60, 0.75 θ range for data collection (°) 5.0 ≤ θ ≤ 27.5 Index ranges -15 ≤ h ≤ 14, 0 ≤ k ≤ 37, 0 ≤ l ≤ 15 Reflections measured 39394 Unique reflections 8609 Rint 0.041 Observed reflections (I > 3σ(I)) 6115 Refinement method Full-matrix least-squares on F Parameters refined 458 Weighting scheme Chebychev 3-term polynomial Goodness of fit 1.0769 R 0.0218 wR 0.0226 Residual electron density (min,max) (eÅ-3) -0.62, 0.49



S52


Atom x y z Uequiv Ir(1) 0.337256(11) 0.115754(4) 0.190006(10) 0.0147 Cl(1) 0.26517(7) 0.18772(3) 0.10476(7) 0.0213 C(1) 0.2451(3) 0.13371(10) 0.3098(3) 0.0145 N(1) 0.1258(2) 0.14149(9) 0.2811(2) 0.0156 C(2) 0.0909(3) 0.17105(11) 0.3691(3) 0.0165 C(3) 0.2136(3) 0.18595(10) 0.4531(3) 0.0149 N(2) 0.2963(2) 0.15389(9) 0.4157(2) 0.0148 C(4) 0.0257(3) 0.14795(10) 0.4487(3) 0.0164 C(5) -0.0859(3) 0.12816(13) 0.4260(3) 0.0257 C(6) -0.1253(3) 0.11387(14) 0.5241(3) 0.0281 C(7) -0.0596(3) 0.12199(13) 0.6398(3) 0.0272 C(8) 0.2012(3) 0.17926(10) 0.5768(3) 0.0161 C(9) 0.2694(3) 0.19437(11) 0.6854(3) 0.0209 C(10) 0.2282(3) 0.18435(12) 0.7857(3) 0.0232 C(11) 0.1248(3) 0.16001(12) 0.7773(3) 0.0241 C(12) 0.0518(3) 0.14497(11) 0.6647(3) 0.0207 C(13) 0.0937(3) 0.15565(11) 0.5671(3) 0.0181 C(14) 0.0319(3) 0.12361(10) 0.1829(3) 0.0166 C(15) -0.0418(3) 0.15501(11) 0.1020(3) 0.0187 C(16) -0.1403(3) 0.13750(14) 0.0139(3) 0.0310 C(17) -0.1648(4) 0.09093(15) 0.0073(4) 0.0373 C(18) -0.0930(4) 0.06088(13) 0.0866(4) 0.0347 C(19) 0.0067(3) 0.07593(11) 0.1768(3) 0.0227 C(20) -0.0251(3) 0.20739(11) 0.1058(3) 0.0203 C(21) -0.1222(3) 0.23091(13) 0.1498(3) 0.0305 C(22) -0.0287(4) 0.22744(13) -0.0161(3) 0.0307 C(23) 0.0780(3) 0.03999(12) 0.2624(3) 0.0280 C(24) 0.0105(4) 0.02254(15) 0.3479(4) 0.0454 C(25) 0.1095(4) -0.00142(13) 0.1953(4) 0.0374 C(26) 0.4147(3) 0.14590(11) 0.4946(3) 0.0191 C(27) 0.5076(3) 0.17684(12) 0.4944(3) 0.0219 C(28) 0.6178(3) 0.16964(15) 0.5779(3) 0.0331 C(29) 0.6349(3) 0.13378(16) 0.6582(3) 0.0380 C(30) 0.5423(3) 0.10365(14) 0.6565(3) 0.0313 C(31) 0.4296(3) 0.10897(12) 0.5754(3) 0.0225 C(32) 0.4914(3) 0.21695(11) 0.4082(3) 0.0209 C(33) 0.5081(3) 0.26296(13) 0.4749(3) 0.0307 C(34) 0.5760(4) 0.21358(13) 0.3305(3) 0.0319 C(35) 0.3317(3) 0.07442(12) 0.5764(3) 0.0246 C(36) 0.3123(4) 0.07006(13) 0.6990(3) 0.0340 C(37) 0.3595(4) 0.02629(13) 0.5362(3) 0.0355 C(38) 0.4749(3) 0.07426(11) 0.2963(3) 0.0213 C(39) 0.3819(3) 0.04511(11) 0.2315(3) 0.0217 C(40) 0.3914(3) 0.01631(11) 0.1272(3) 0.0254 C(41) 0.3387(4) 0.04141(12) 0.0092(3) 0.0302 C(42) 0.3553(3) 0.09314(12) 0.0214(3) 0.0219 C(43) 0.4611(3) 0.11556(13) 0.0804(3) 0.0235 C(44) 0.5785(3) 0.09109(13) 0.1387(3) 0.0295 C(45) 0.5932(3) 0.08145(12) 0.2704(3) 0.0269



S53


Atom x y z Uiso

H(1) 0.482(3) 0.0800(13) 0.374(3) 0.022(9) H(2) 0.330(4) 0.0338(14) 0.271(3) 0.030(10) H(3) 0.299(3) 0.1112(13) -0.032(3) 0.022(9) H(4) 0.467(4) 0.1481(16) 0.068(4) 0.043(12) H(21) 0.0344 0.1951 0.3242 0.0196 H(31) 0.2429 0.2184 0.4512 0.0175 H(51) -0.1380 0.1239 0.3429 0.0312 H(61) -0.2036 0.0973 0.5086 0.0346 H(71) -0.0908 0.1116 0.7062 0.0352 H(91) 0.3455 0.2118 0.6941 0.0246 H(101) 0.2765 0.1955 0.8655 0.0273 H(111) 0.1008 0.1529 0.8504 0.0305 H(161) -0.1932 0.1591 -0.0446 0.0349 H(171) -0.2354 0.0789 -0.0558 0.0421 H(181) -0.1125 0.0271 0.0798 0.0420 H(201) 0.0558 0.2136 0.1619 0.0228 H(211) -0.1099 0.2652 0.1518 0.0345 H(212) -0.1171 0.2196 0.2314 0.0345 H(213) -0.2029 0.2233 0.0951 0.0345 H(221) -0.0174 0.2617 -0.0095 0.0353 H(222) -0.1079 0.2203 -0.0742 0.0353 H(223) 0.0369 0.2134 -0.0439 0.0353 H(231) 0.1531 0.0557 0.3094 0.0355 H(241) 0.0604 -0.0010 0.4025 0.0608 H(242) -0.0062 0.0491 0.3953 0.0608 H(243) -0.0669 0.0081 0.3018 0.0608 H(251) 0.1563 -0.0246 0.2535 0.0469 H(252) 0.1585 0.0094 0.1434 0.0469 H(253) 0.0341 -0.0161 0.1455 0.0469 H(281) 0.6861 0.1909 0.5798 0.0396 H(291) 0.7147 0.1296 0.7180 0.0441 H(301) 0.5565 0.0775 0.7145 0.0378 H(321) 0.4077 0.2154 0.3543 0.0250 H(331) 0.4971 0.2890 0.4170 0.0363 H(332) 0.5905 0.2644 0.5313 0.0363 H(333) 0.4475 0.2656 0.5199 0.0363 H(341) 0.5626 0.2406 0.2751 0.0404 H(342) 0.6609 0.2138 0.3819 0.0404 H(343) 0.5600 0.1842 0.2837 0.0404 H(351) 0.2570 0.0867 0.5194 0.0299 H(361) 0.2474 0.0471 0.6957 0.0438 H(362) 0.3883 0.0595 0.7573 0.0438 H(363) 0.2887 0.1008 0.7240 0.0438 H(371) 0.2934 0.0045 0.5380 0.0446 H(372) 0.4367 0.0148 0.5908 0.0446 H(373) 0.3666 0.0282 0.4537 0.0446 H(401) 0.4778 0.0095 0.1367 0.0328 H(402) 0.3470 -0.0133 0.1262 0.0328



S54

H(411) 0.3794 0.0299 -0.0494 0.0373 H(412) 0.2511 0.0345 -0.0203 0.0373 H(441) 0.6463 0.1110 0.1318 0.0382 H(442) 0.5801 0.0611 0.0971 0.0382 H(451) 0.6350 0.1083 0.3180 0.0322 H(452) 0.6430 0.0530 0.2942 0.0322



S55


Atom U11 U22 U33 U23 U13 U12

Ir(1) 0.01851(6) 0.01372(5) 0.01357(5) 0.00093(5) 0.00712(4) 0.00223(6) Cl(1) 0.0271(4) 0.0175(3) 0.0218(4) 0.0052(3) 0.0109(3) 0.0052(3) C(1) 0.0180(14) 0.0146(13) 0.0121(13) 0.0031(11) 0.0066(12) -0.0005(12) N(1) 0.0176(12) 0.0167(13) 0.0133(12) -0.0035(10) 0.0057(10) -0.0019(10) C(2) 0.0184(15) 0.0198(15) 0.0109(13) -0.0025(11) 0.0038(12) 0.0022(12) C(3) 0.0142(14) 0.0141(14) 0.0153(14) -0.0020(11) 0.0027(12) 0.0015(11) N(2) 0.0150(12) 0.0179(12) 0.0115(11) 0.0009(10) 0.0039(9) 0.0031(10) C(4) 0.0175(15) 0.0155(14) 0.0172(14) -0.0038(12) 0.0065(12) -0.0012(12) C(5) 0.0179(16) 0.035(2) 0.0250(17) -0.0063(14) 0.0075(14) -0.0011(14) C(6) 0.0199(16) 0.0326(18) 0.0340(18) -0.0048(17) 0.0110(14) -0.0083(16) C(7) 0.0257(17) 0.033(2) 0.0291(17) 0.0058(15) 0.0178(14) 0.0016(15) C(8) 0.0190(15) 0.0135(14) 0.0165(14) -0.0016(11) 0.0061(12) 0.0032(12) C(9) 0.0207(16) 0.0226(16) 0.0182(15) -0.0005(12) 0.0039(13) 0.0015(13) C(10) 0.0278(18) 0.0282(17) 0.0122(14) -0.0017(13) 0.0034(13) 0.0086(14) C(11) 0.0273(17) 0.0309(18) 0.0180(15) 0.0050(13) 0.0127(13) 0.0088(14) C(12) 0.0250(17) 0.0212(16) 0.0174(15) 0.0020(12) 0.0083(13) 0.0042(13) C(13) 0.0184(15) 0.0170(14) 0.0199(15) 0.0001(12) 0.0069(12) 0.0033(12) C(14) 0.0146(14) 0.0205(16) 0.0155(14) -0.0031(12) 0.0059(11) -0.0022(12) C(15) 0.0198(15) 0.0227(16) 0.0149(14) -0.0011(12) 0.0070(12) -0.0020(13) C(16) 0.0268(19) 0.039(2) 0.0215(18) -0.0036(15) -0.0022(15) -0.0042(16) C(17) 0.031(2) 0.043(2) 0.032(2) -0.0081(18) -0.0020(17) -0.0118(18) C(18) 0.039(2) 0.0282(19) 0.037(2) -0.0107(17) 0.0126(18) -0.0145(17) C(19) 0.0288(18) 0.0186(16) 0.0232(17) -0.0045(13) 0.0115(14) -0.0071(13) C(20) 0.0201(16) 0.0194(16) 0.0174(15) 0.0004(12) -0.0010(13) 0.0024(13) C(21) 0.0214(17) 0.0325(19) 0.0325(19) -0.0031(16) -0.0006(15) 0.0082(15) C(22) 0.036(2) 0.0273(19) 0.0250(18) 0.0064(15) 0.0027(15) -0.0004(16) C(23) 0.037(2) 0.0176(16) 0.034(2) 0.0019(14) 0.0177(17) -0.0018(14) C(24) 0.064(3) 0.031(2) 0.057(3) 0.014(2) 0.043(2) 0.005(2) C(25) 0.041(2) 0.0247(19) 0.052(3) -0.0099(17) 0.021(2) -0.0063(16) C(26) 0.0157(15) 0.0255(17) 0.0159(14) 0.0001(13) 0.0043(12) 0.0060(13) C(27) 0.0202(16) 0.0302(18) 0.0152(15) -0.0028(13) 0.0047(12) 0.0016(14) C(28) 0.0210(18) 0.047(2) 0.031(2) 0.0000(17) 0.0069(15) -0.0026(16) C(29) 0.0236(19) 0.059(3) 0.0276(19) 0.0140(18) 0.0011(15) 0.0140(18) C(30) 0.0236(18) 0.048(2) 0.0227(17) 0.0157(16) 0.0075(14) 0.0144(16) C(31) 0.0209(15) 0.0311(19) 0.0171(14) 0.0050(13) 0.0080(12) 0.0082(14) C(32) 0.0172(15) 0.0234(16) 0.0221(16) 0.0020(13) 0.0052(13) 0.0006(13) C(33) 0.0244(18) 0.0293(19) 0.037(2) -0.0066(16) 0.0068(16) -0.0031(15) C(34) 0.039(2) 0.0287(19) 0.033(2) 0.0005(16) 0.0186(17) -0.0008(16) C(35) 0.0270(18) 0.0238(17) 0.0241(17) 0.0083(14) 0.0088(14) 0.0075(14) C(36) 0.046(2) 0.032(2) 0.031(2) 0.0105(16) 0.0229(18) 0.0065(17) C(37) 0.056(3) 0.0268(19) 0.0283(19) 0.0094(15) 0.0201(19) 0.0075(18) C(38) 0.0252(17) 0.0222(16) 0.0171(16) 0.0074(13) 0.0069(13) 0.0102(13) C(39) 0.0297(18) 0.0123(14) 0.0281(17) 0.0063(13) 0.0161(15) 0.0054(13) C(40) 0.038(2) 0.0175(16) 0.0262(17) -0.0009(13) 0.0187(16) 0.0030(14) C(41) 0.050(2) 0.0220(17) 0.0211(17) -0.0058(14) 0.0147(16) 0.0035(16) C(42) 0.0343(19) 0.0234(17) 0.0114(14) -0.0011(13) 0.0121(14) 0.0047(15) C(43) 0.0293(17) 0.0238(16) 0.0275(16) 0.0047(16) 0.0242(14) 0.0057(16) C(44) 0.0275(18) 0.0292(19) 0.039(2) 0.0066(16) 0.0203(16) 0.0086(15) C(45) 0.0216(17) 0.0241(17) 0.035(2) 0.0047(15) 0.0078(15) 0.0075(14)



S56


Ir(1) - Cl(1) 2.3587(7) C(15) - C(20) 1.527(5) Ir(1) - C(1) 2.070(3) C(16) - C(17) 1.375(5) Ir(1) - C(38) 2.104(3) C(17) - C(18) 1.371(6) Ir(1) - C(39) 2.131(3) C(18) - C(19) 1.400(5) Ir(1) - C(42) 2.158(3) C(19) - C(23) 1.519(5) Ir(1) - C(43) 2.195(3) C(20) - C(21) 1.532(5) C(1) - N(1) 1.353(4) C(20) - C(22) 1.538(5) C(1) - N(2) 1.351(4) C(23) - C(24) 1.531(5) N(1) - C(2) 1.487(4) C(23) - C(25) 1.536(5) N(1) - C(14) 1.441(4) C(26) - C(27) 1.406(5) C(2) - C(3) 1.548(4) C(26) - C(31) 1.408(4) C(2) - C(4) 1.520(4) C(27) - C(28) 1.391(5) C(3) - N(2) 1.492(4) C(27) - C(32) 1.518(5) C(3) - C(8) 1.517(4) C(28) - C(29) 1.379(6) N(2) - C(26) 1.444(4) C(29) - C(30) 1.383(6) C(4) - C(5) 1.376(4) C(30) - C(31) 1.393(5) C(4) - C(13) 1.411(4) C(31) - C(35) 1.519(5) C(5) - C(6) 1.420(5) C(32) - C(33) 1.529(5) C(6) - C(7) 1.379(5) C(32) - C(34) 1.529(5) C(7) - C(12) 1.411(5) C(35) - C(36) 1.529(5) C(8) - C(9) 1.369(4) C(35) - C(37) 1.535(5) C(8) - C(13) 1.403(4) C(38) - C(39) 1.412(5) C(9) - C(10) 1.427(4) C(38) - C(45) 1.509(5)

C(10) - C(11) 1.374(5) C(39) - C(40) 1.514(5) C(11) - C(12) 1.423(5) C(40) - C(41) 1.533(5) C(12) - C(13) 1.405(4) C(41) - C(42) 1.510(5) C(14) - C(15) 1.414(4) C(42) - C(43) 1.390(5) C(14) - C(19) 1.408(4) C(43) - C(44) 1.518(5) C(15) - C(16) 1.403(5) C(44) - C(45) 1.536(5)




S57

Table 6: Bond angles (°) Cl(1) - Ir(1) - C(1) 82.97(8) C(15) - C(14) - C(19) 121.2(3)

Cl(1) - Ir(1) - C(38) 150.95(10) C(14) - C(15) - C(16) 118.4(3) C(1) - Ir(1) - C(38) 101.16(12) C(14) - C(15) - C(20) 124.7(3) Cl(1) - Ir(1) - C(39) 167.92(10) C(16) - C(15) - C(20) 116.8(3) C(1) - Ir(1) - C(39) 102.98(12) C(15) - C(16) - C(17) 120.5(4) C(38) - Ir(1) - C(39) 38.94(14) C(16) - C(17) - C(18) 120.5(4) Cl(1) - Ir(1) - C(42) 89.58(9) C(17) - C(18) - C(19) 122.1(3) C(1) - Ir(1) - C(42) 155.55(13) C(14) - C(19) - C(18) 117.3(3) C(38) - Ir(1) - C(42) 96.64(13) C(14) - C(19) - C(23) 124.8(3) C(39) - Ir(1) - C(42) 80.71(13) C(18) - C(19) - C(23) 117.9(3) Cl(1) - Ir(1) - C(43) 88.04(10) C(15) - C(20) - C(21) 110.5(3) C(1) - Ir(1) - C(43) 163.51(14) C(15) - C(20) - C(22) 112.2(3) C(38) - Ir(1) - C(43) 80.26(13) C(21) - C(20) - C(22) 108.9(3) C(39) - Ir(1) - C(43) 88.51(13) C(19) - C(23) - C(24) 112.1(3) C(42) - Ir(1) - C(43) 37.22(13) C(19) - C(23) - C(25) 111.0(3) Ir(1) - C(1) - N(1) 124.6(2) C(24) - C(23) - C(25) 108.9(3) Ir(1) - C(1) - N(2) 124.1(2) N(2) - C(26) - C(27) 119.4(3) N(1) - C(1) - N(2) 108.0(2) N(2) - C(26) - C(31) 117.8(3) C(1) - N(1) - C(2) 112.8(2) C(27) - C(26) - C(31) 122.6(3) C(1) - N(1) - C(14) 129.1(2) C(26) - C(27) - C(28) 117.3(3) C(2) - N(1) - C(14) 118.0(2) C(26) - C(27) - C(32) 122.7(3) N(1) - C(2) - C(3) 102.6(2) C(28) - C(27) - C(32) 120.0(3) N(1) - C(2) - C(4) 117.5(3) C(27) - C(28) - C(29) 121.3(4) C(3) - C(2) - C(4) 105.2(2) C(28) - C(29) - C(30) 120.4(3) C(2) - C(3) - N(2) 101.2(2) C(29) - C(30) - C(31) 121.2(3) C(2) - C(3) - C(8) 104.7(2) C(26) - C(31) - C(30) 117.2(3) N(2) - C(3) - C(8) 116.9(2) C(26) - C(31) - C(35) 123.9(3) C(1) - N(2) - C(3) 113.0(2) C(30) - C(31) - C(35) 118.9(3) C(1) - N(2) - C(26) 127.7(3) C(27) - C(32) - C(33) 110.4(3) C(3) - N(2) - C(26) 119.2(2) C(27) - C(32) - C(34) 111.9(3) C(2) - C(4) - C(5) 132.5(3) C(33) - C(32) - C(34) 110.7(3) C(2) - C(4) - C(13) 107.6(3) C(31) - C(35) - C(36) 112.1(3) C(5) - C(4) - C(13) 119.2(3) C(31) - C(35) - C(37) 111.7(3) C(4) - C(5) - C(6) 118.1(3) C(36) - C(35) - C(37) 108.5(3) C(5) - C(6) - C(7) 122.5(3) Ir(1) - C(38) - C(39) 71.54(19) C(6) - C(7) - C(12) 120.2(3) Ir(1) - C(38) - C(45) 112.7(2) C(3) - C(8) - C(9) 131.8(3) C(39) - C(38) - C(45) 125.3(3) C(3) - C(8) - C(13) 108.3(3) Ir(1) - C(39) - C(38) 69.52(18) C(9) - C(8) - C(13) 119.8(3) Ir(1) - C(39) - C(40) 114.3(2) C(8) - C(9) - C(10) 117.8(3) C(38) - C(39) - C(40) 122.9(3)

C(9) - C(10) - C(11) 122.7(3) C(39) - C(40) - C(41) 111.8(3) C(10) - C(11) - C(12) 120.1(3) C(40) - C(41) - C(42) 112.1(3) C(7) - C(12) - C(11) 127.3(3) Ir(1) - C(42) - C(41) 110.1(2) C(7) - C(12) - C(13) 116.6(3) Ir(1) - C(42) - C(43) 72.83(18) C(11) - C(12) - C(13) 116.1(3) C(41) - C(42) - C(43) 125.5(3)

C(4) - C(13) - C(8) 113.1(3) Ir(1) - C(43) - C(42) 69.94(17) C(4) - C(13) - C(12) 123.1(3) Ir(1) - C(43) - C(44) 113.2(2) C(8) - C(13) - C(12) 123.5(3) C(42) - C(43) - C(44) 124.3(3) N(1) - C(14) - C(15) 119.0(3) C(43) - C(44) - C(45) 111.5(3) N(1) - C(14) - C(19) 119.5(3) C(38) - C(45) - C(44) 112.6(3)




S58

F. Single-crystal X-ray diffraction report for CCDC_719727_8b Single crystals for iridium complex 8b, suitable for X-ray study were grown by slow

diffusion of pentane into a saturated dichloromethane solution.

A large single crystal was cut to give a fragment having dimensions approximately

0.12 x 0.16 x 0.24 mm. was mounted on a glass fibre using perfluoropolyether oil and

cooled rapidly to 150 K in a stream of cold N2 using an Oxford Cryosystems

CRYOSTREAM unit. Diffraction data were measured using an Enraf-Nonius KappaCCD

diffractometer (graphite-monochromated MoKα radiation, λ = 0.71073 Å). Intensity data

were processed using the DENZO-SMN package1.

A preliminary inspection of the diffraction data suggested the crystal to have

orthorhombic symmetry (space group C m c m), but examination of the intensities of

symmetry-related reflections showed the true symmetry to be monoclinic. Examination of

the systematic absences of the intensity data showed the space group to be either C c or

C 2/c. The structure could not be solved in the latter space group, but a successful

solution was obtained in C c. The iridium atom was located by a Patterson synthesis and

used to obtain an initial set of reflection phases. The resulting Fourier map showed a

number of spurious peaks, but it was possible to identify the imidazole ring of the carbene

ligand. Addition of these atoms to the model allowed the remaining non-hydrogen atoms to

be located in difference Fourier maps.

Subsequent full-matrix least-squares refinement was carried out using the

CRYSTALS program suite2. Coordinates and anisotropic thermal parameters of all non-

hydrogen atoms were refined.The hydrogen atoms of the coordinated alkene groups were

located in a difference Fourier map and their coordinates and isotropic thermal parameters

subsequently refined. The C-H bond lengths were restrained to 1.00(5) Å and similarity

restraints applied to the thermal parameters of the hydrogen atoms and their parent

carbons. All other hydrogen atoms were positioned geometrically after each cycle of

refinement. A 3-term Chebychev polynomial weighting scheme was applied. Refinement

converged satisfactorily to give R = 0.0378, wR = 0.0423.



S59




Comments: The large thermal parameters of the solvent and counterion suggests that these

molecules are disordered. Attempts to include this in the model did not lead to an

improvement in the agreement with the diffraction data and were abandoned.

Refinement of the Flack enantiopole prarameter gave a value of 0.384(8), showing

the crystal to be twinned by inversion4.







4 H. D. Flack and G. Bernardinelli, J. Appl. Cryst., 2000, 33, 1143



S60

Hydrogen atoms, counter ion and solvent not shown



S61


Crystal identification CCDC_719727_8b Chemical formula C51H61Cl2F6IrN3P Formula weight 1124.15 Temperature (K) 150 Wavelength (Å) 0.71073 Crystal system Monoclinic Space group C c a (Å) 18.6624(3) b (Å) 15.6085(2) c (Å) 16.6277(3) α (°) 90 β (°) 90.0100(6) γ (°) 90 Cell volume (Å3) 4843.52(13) Z 4 Calculated density (Mg/m3) 1.542 Absorption coefficient (mm-1) 2.961 F000 2272 Crystal size (mm) 0.12 x 0.16 x 0.24 Description of crystal Orange fragment Absorption correction Semi-empirical from equivalent reflections Transmission coefficients (min,max) 0.49, 0.72 θ range for data collection (°) 5.0 ≤ θ ≤ 27.5 Index ranges -24 ≤ h ≤ 24, 0 ≤ k ≤ 20, 0 ≤ l ≤ 21 Reflections measured 22099 Unique reflections 10569 Rint 0.047 Observed reflections (I > 3σ(I)) 9261 Refinement method Full-matrix least-squares on F Parameters refined 594 Weighting scheme Chebychev 3-term polynomial Goodness of fit 1.1069 R 0.0378 wR 0.0423 Residual electron density (min,max) (eÅ-3) -1.48, 1.80



S62


Atom x y z Uequiv

Ir(1) 0.33221(5) 0.414981(11) 0.23977(6) 0.0172 C(1) 0.3391(3) 0.2837(3) 0.2138(3) 0.0128 N(1) 0.3267(2) 0.2243(3) 0.2710(3) 0.0163 C(2) 0.2988(3) 0.1415(4) 0.2383(3) 0.0174 C(3) 0.3157(3) 0.1513(4) 0.1483(3) 0.0174 N(2) 0.3327(4) 0.2434(4) 0.1406(3) 0.0132 C(4) 0.3388(3) 0.0607(4) 0.2637(3) 0.0203 C(5) 0.3325(4) 0.0098(4) 0.3317(4) 0.0305 C(6) 0.3739(5) -0.0670(4) 0.3335(4) 0.0337 C(7) 0.4199(5) -0.0905(5) 0.2704(5) 0.0407 C(8) 0.3743(3) 0.0872(4) 0.1317(4) 0.0250 C(9) 0.4136(4) 0.0675(4) 0.0633(4) 0.0338 C(10) 0.4592(5) -0.0039(5) 0.0665(5) 0.0444 C(11) 0.4659(5) -0.0562(5) 0.1325(5) 0.0402 C(12) 0.4254(4) -0.0385(4) 0.2017(4) 0.0295 C(13) 0.3820(3) 0.0349(4) 0.1996(4) 0.0218 C(14) 0.3411(5) 0.2288(5) 0.3577(5) 0.0206 C(15) 0.2864(4) 0.2457(5) 0.4093(4) 0.0253 C(16) 0.3021(4) 0.2472(5) 0.4914(3) 0.0292 C(17) 0.3708(4) 0.2306(5) 0.5187(4) 0.0288 C(18) 0.4245(4) 0.2138(5) 0.4664(4) 0.0241 C(19) 0.4122(3) 0.2098(4) 0.3829(4) 0.0212 C(20) 0.2089(3) 0.2594(5) 0.3824(4) 0.0274 C(21) 0.1636(4) 0.1798(6) 0.4042(5) 0.0403 C(22) 0.1770(4) 0.3406(6) 0.4199(5) 0.0430 C(23) 0.4737(3) 0.1860(4) 0.3270(3) 0.0196 C(24) 0.5086(3) 0.1007(4) 0.3515(4) 0.0293 C(25) 0.5314(3) 0.2557(5) 0.3252(5) 0.0319 C(26) 0.3584(4) 0.2709(5) 0.0617(4) 0.0194 C(27) 0.3086(3) 0.2685(4) -0.0022(4) 0.0186 C(28) 0.3334(4) 0.2837(4) -0.0805(4) 0.0278 C(29) 0.4049(4) 0.3013(5) -0.0947(4) 0.0324 C(30) 0.4529(4) 0.3041(4) -0.0316(4) 0.0288 C(31) 0.4303(3) 0.2891(4) 0.0482(4) 0.0218 C(32) 0.2279(4) 0.2516(5) 0.0097(4) 0.0249 C(33) 0.2070(4) 0.1663(5) -0.0311(4) 0.0377 C(34) 0.1827(4) 0.3254(5) -0.0253(5) 0.0383 C(35) 0.4867(4) 0.2927(5) 0.1149(4) 0.0270 C(36) 0.5432(4) 0.2227(6) 0.1056(5) 0.0475 C(37) 0.5214(5) 0.3803(6) 0.1156(5) 0.0469 C(38) 0.2266(4) 0.4025(4) 0.1884(5) 0.0251 C(39) 0.2725(4) 0.4371(6) 0.1299(4) 0.0258 C(40) 0.2699(5) 0.5319(5) 0.1059(5) 0.0430 C(41) 0.3195(5) 0.5879(5) 0.1534(5) 0.0421 C(42) 0.3318(8) 0.5545(3) 0.2344(9) 0.0267 C(43) 0.2821(4) 0.5273(4) 0.2922(4) 0.0256 C(44) 0.2018(4) 0.5324(5) 0.2766(5) 0.0400 C(45) 0.1707(4) 0.4545(6) 0.2312(5) 0.0379



S63

N(3) 0.4160(4) 0.4310(4) 0.3236(4) 0.0236 C(46) 0.4063(4) 0.4142(4) 0.4031(4) 0.0285 C(47) 0.4584(4) 0.4303(4) 0.4614(5) 0.0374 C(48) 0.5220(4) 0.4663(5) 0.4381(5) 0.0399 C(49) 0.5325(4) 0.4872(5) 0.3576(5) 0.0392 C(50) 0.4773(4) 0.4679(5) 0.3027(5) 0.0309

P(1) 0.05379(11) 0.18889(14) 0.17722(13) 0.0367 F(1) 0.0306(7) 0.1032(5) 0.1396(6) 0.1436 F(2) 0.0681(4) 0.2779(5) 0.2209(7) 0.1193 F(3) 0.0552(5) 0.2376(7) 0.0964(5) 0.1206 F(4) 0.0439(5) 0.1493(7) 0.2623(5) 0.1197 F(5) 0.1362(3) 0.1770(6) 0.1784(5) 0.0932 F(6) -0.0303(3) 0.2137(5) 0.1787(5) 0.0898

C(51) 0.7487(8) 0.3937(10) 0.1626(12) 0.0932 Cl(1) 0.69265(18) 0.4771(2) 0.1510(3) 0.1090 Cl(2) 0.71701(18) 0.3019(2) 0.2107(2) 0.0891



S64


Atom x y z Uiso

H(1) 0.213(4) 0.342(3) 0.185(4) 0.018(4) H(2) 0.295(4) 0.390(4) 0.098(4) 0.028(4) H(3) 0.367(3) 0.577(4) 0.273(4) 0.021(4) H(4) 0.293(4) 0.532(5) 0.353(3) 0.025(4) H(21) 0.2482 0.1334 0.2565 0.0209 H(31) 0.2777 0.1385 0.1075 0.0209 H(51) 0.3004 0.0261 0.3774 0.0366 H(61) 0.3702 -0.1054 0.3814 0.0405 H(71) 0.4487 -0.1443 0.2743 0.0488 H(91) 0.4095 0.1029 0.0134 0.0406 H(101) 0.4886 -0.0175 0.0179 0.0533 H(111) 0.4993 -0.1063 0.1312 0.0482 H(161) 0.2633 0.2604 0.5309 0.0351 H(171) 0.3807 0.2309 0.5778 0.0346 H(181) 0.4741 0.2040 0.4874 0.0289 H(201) 0.2082 0.2674 0.3228 0.0329 H(211) 0.1130 0.1889 0.3865 0.0484 H(212) 0.1649 0.1706 0.4637 0.0484 H(213) 0.1837 0.1283 0.3763 0.0484 H(221) 0.1264 0.3478 0.4012 0.0516 H(222) 0.1778 0.3356 0.4799 0.0516 H(223) 0.2059 0.3915 0.4031 0.0516 H(231) 0.4523 0.1800 0.2721 0.0235 H(241) 0.5486 0.0871 0.3136 0.0352 H(242) 0.5278 0.1055 0.4074 0.0352 H(243) 0.4720 0.0539 0.3494 0.0352 H(251) 0.5708 0.2379 0.2880 0.0383 H(252) 0.5512 0.2639 0.3805 0.0383 H(253) 0.5100 0.3106 0.3058 0.0383 H(281) 0.2990 0.2818 -0.1266 0.0334 H(291) 0.4218 0.3120 -0.1508 0.0389 H(301) 0.5045 0.3169 -0.0425 0.0345 H(321) 0.2180 0.2478 0.0687 0.0299 H(331) 0.1546 0.1556 -0.0233 0.0453 H(332) 0.2177 0.1697 -0.0900 0.0453 H(333) 0.2351 0.1184 -0.0066 0.0453 H(341) 0.1307 0.3130 -0.0169 0.0459 H(342) 0.1956 0.3801 0.0024 0.0459 H(343) 0.1926 0.3309 -0.0842 0.0459 H(351) 0.4621 0.2824 0.1674 0.0323 H(361) 0.5789 0.2273 0.1503 0.0570 H(362) 0.5682 0.2296 0.0528 0.0570 H(363) 0.5196 0.1652 0.1078 0.0570 H(371) 0.5582 0.3827 0.1592 0.0562 H(372) 0.5448 0.3911 0.0625 0.0562 H(373) 0.4840 0.4250 0.1256 0.0562 H(401) 0.2832 0.5366 0.0478 0.0516 H(402) 0.2199 0.5531 0.1139 0.0516



S65

H(411) 0.2980 0.6464 0.1577 0.0505 H(412) 0.3664 0.5915 0.1247 0.0505 H(441) 0.1921 0.5850 0.2440 0.0480 H(442) 0.1767 0.5371 0.3296 0.0480 H(451) 0.1354 0.4757 0.1905 0.0455 H(452) 0.1458 0.4167 0.2708 0.0455 H(461) 0.3596 0.3889 0.4206 0.0342 H(471) 0.4494 0.4160 0.5191 0.0449 H(481) 0.5606 0.4774 0.4785 0.0479 H(491) 0.5779 0.5151 0.3392 0.0470 H(501) 0.4848 0.4827 0.2448 0.0370

H(511) 0.7908 0.4148 0.1942 0.1119 H(512) 0.7648 0.3761 0.1077 0.1119



S66


Atom U11 U22 U33 U23 U13 U12

Ir(1) 0.01792(8) 0.01503(8) 0.01877(8) 0.00012(18) -0.00261(5) -0.00231(18) C(1) 0.017(2) 0.010(2) 0.011(2) -0.0030(14) -0.004(2) 0.0013(19) N(1) 0.014(2) 0.019(2) 0.016(2) 0.0044(15) 0.0010(17) -0.0041(17) C(2) 0.019(2) 0.025(3) 0.008(2) 0.0002(19) -0.0027(18) -0.005(2) C(3) 0.025(3) 0.019(2) 0.009(2) -0.0009(19) -0.003(2) -0.003(2) N(2) 0.020(3) 0.016(2) 0.004(2) -0.0001(19) 0.0040(19) 0.004(2) C(4) 0.022(3) 0.019(3) 0.020(3) 0.0000(19) 0.000(3) -0.005(2) C(5) 0.043(4) 0.027(3) 0.021(3) 0.007(3) -0.001(3) -0.010(3) C(6) 0.058(5) 0.019(3) 0.024(3) 0.003(2) -0.017(3) 0.001(3) C(7) 0.069(6) 0.027(4) 0.026(3) 0.000(3) -0.016(4) 0.007(3) C(8) 0.034(3) 0.022(3) 0.020(3) -0.003(2) -0.006(2) -0.003(2) C(9) 0.053(4) 0.023(3) 0.025(3) -0.004(2) 0.007(3) 0.004(3) C(10) 0.058(5) 0.036(4) 0.039(4) -0.013(3) 0.008(4) 0.010(4) C(11) 0.051(5) 0.028(4) 0.042(4) -0.011(3) -0.002(3) 0.015(3) C(12) 0.040(4) 0.017(3) 0.031(3) -0.006(2) -0.008(3) 0.002(3) C(13) 0.026(3) 0.018(3) 0.022(3) 0.000(2) -0.005(2) -0.001(2) C(14) 0.028(4) 0.023(4) 0.011(3) 0.003(2) 0.001(3) -0.002(3) C(15) 0.032(4) 0.031(4) 0.013(3) -0.007(3) -0.004(3) 0.001(3) C(16) 0.037(3) 0.040(4) 0.011(3) -0.001(3) 0.003(2) -0.010(3) C(17) 0.042(4) 0.034(4) 0.011(3) 0.000(3) -0.005(3) 0.001(3) C(18) 0.025(3) 0.023(4) 0.024(3) 0.004(3) -0.007(2) 0.001(3) C(19) 0.023(3) 0.019(3) 0.021(3) 0.002(2) -0.003(2) -0.002(2) C(20) 0.018(3) 0.047(4) 0.018(3) 0.003(3) 0.003(2) -0.002(3) C(21) 0.031(4) 0.056(5) 0.034(4) -0.003(3) 0.008(3) -0.013(3) C(22) 0.031(4) 0.056(5) 0.042(4) -0.004(4) 0.000(3) 0.009(3) C(23) 0.017(3) 0.024(3) 0.018(3) 0.002(2) -0.004(2) 0.005(2) C(24) 0.025(3) 0.023(3) 0.040(4) 0.002(3) -0.001(3) 0.002(2) C(25) 0.020(3) 0.028(3) 0.047(4) 0.010(3) -0.005(3) -0.001(3) C(26) 0.030(4) 0.017(3) 0.011(3) 0.005(2) 0.001(3) -0.005(3) C(27) 0.026(3) 0.015(3) 0.014(3) 0.006(2) -0.001(2) 0.000(2) C(28) 0.041(4) 0.026(3) 0.017(3) 0.008(2) 0.003(3) 0.000(3) C(29) 0.045(4) 0.033(4) 0.019(3) 0.003(3) 0.011(3) -0.002(3) C(30) 0.032(3) 0.030(3) 0.024(3) 0.005(3) 0.012(3) 0.002(3) C(31) 0.020(3) 0.020(3) 0.026(3) 0.007(2) 0.005(2) -0.001(2) C(32) 0.022(3) 0.031(4) 0.022(3) 0.005(3) -0.005(2) -0.005(3) C(33) 0.045(4) 0.039(4) 0.029(4) 0.002(3) -0.013(3) -0.015(3) C(34) 0.035(4) 0.046(4) 0.034(4) 0.008(3) -0.022(3) 0.004(3) C(35) 0.019(3) 0.033(4) 0.029(3) -0.002(3) -0.003(3) -0.003(3) C(36) 0.032(4) 0.065(6) 0.046(5) -0.007(4) -0.005(3) 0.014(4) C(37) 0.042(4) 0.052(5) 0.047(5) -0.002(4) -0.001(4) -0.016(4) C(38) 0.017(3) 0.018(3) 0.040(4) -0.003(3) -0.021(3) 0.002(2) C(39) 0.034(4) 0.030(4) 0.013(4) 0.000(3) -0.011(3) 0.006(3) C(40) 0.047(4) 0.034(4) 0.048(5) 0.017(3) -0.013(4) 0.005(3) C(41) 0.068(5) 0.016(3) 0.041(4) 0.015(3) 0.000(4) 0.005(3) C(42) 0.033(3) 0.0099(19) 0.037(4) -0.001(4) -0.010(3) -0.005(5) C(43) 0.034(3) 0.017(3) 0.026(3) -0.012(2) 0.000(2) 0.007(2) C(44) 0.037(4) 0.030(4) 0.053(5) -0.009(3) 0.003(3) 0.009(3) C(45) 0.019(3) 0.058(5) 0.036(4) -0.011(4) -0.006(3) 0.002(3) N(3) 0.031(4) 0.013(3) 0.027(4) -0.003(3) -0.008(3) -0.002(3)



S67

C(46) 0.040(4) 0.024(3) 0.022(3) -0.004(3) -0.007(3) -0.009(3) C(47) 0.051(4) 0.026(3) 0.036(4) -0.003(3) -0.022(3) -0.005(3) C(48) 0.045(4) 0.024(3) 0.051(5) -0.008(3) -0.028(4) -0.005(3) C(49) 0.034(4) 0.028(4) 0.055(5) 0.007(3) -0.023(3) -0.014(3) C(50) 0.023(3) 0.033(4) 0.037(4) 0.004(3) -0.011(3) -0.012(3)

P(1) 0.0311(9) 0.0447(11) 0.0342(10) 0.0084(8) -0.0094(7) -0.0102(8) F(1) 0.239(13) 0.063(5) 0.129(8) -0.045(5) -0.111(8) 0.022(6) F(2) 0.078(5) 0.064(5) 0.216(11) -0.042(6) -0.048(6) 0.003(4) F(3) 0.093(5) 0.180(10) 0.089(5) 0.083(6) -0.008(4) 0.013(6) F(4) 0.125(7) 0.171(9) 0.063(5) 0.052(5) -0.028(4) -0.068(7) F(5) 0.037(3) 0.152(8) 0.091(5) 0.022(5) -0.004(3) 0.035(4) F(6) 0.045(3) 0.110(6) 0.114(6) 0.005(5) -0.019(4) -0.004(3)

C(51) 0.069(5) 0.072(5) 0.138(7) 0.012(6) -0.010(6) -0.013(5) Cl(1) 0.0649(18) 0.080(2) 0.182(4) 0.023(2) -0.046(2) -0.0323(16) Cl(2) 0.0719(18) 0.086(2) 0.109(3) 0.0202(19) -0.0102(18) -0.0158(16)



S68


Ir(1) - C(1) 2.098(5) C(18) - C(19) 1.409(9) Ir(1) - C(38) 2.156(6) C(19) - C(23) 1.523(8) Ir(1) - C(39) 2.167(7) C(20) - C(21) 1.546(10) Ir(1) - C(42) 2.180(5) C(20) - C(22) 1.533(11) Ir(1) - C(43) 2.171(6) C(23) - C(24) 1.537(8) Ir(1) - N(3) 2.109(6) C(23) - C(25) 1.532(9) C(1) - N(1) 1.348(6) C(26) - C(27) 1.412(9) C(1) - N(2) 1.376(7) C(26) - C(31) 1.390(9) N(1) - C(2) 1.496(7) C(27) - C(28) 1.402(8) N(1) - C(14) 1.468(9) C(27) - C(32) 1.543(9) C(2) - C(3) 1.538(7) C(28) - C(29) 1.381(10) C(2) - C(4) 1.524(8) C(29) - C(30) 1.382(10) C(3) - N(2) 1.477(8) C(30) - C(31) 1.412(8) C(3) - C(8) 1.508(9) C(31) - C(35) 1.530(9) N(2) - C(26) 1.461(9) C(32) - C(33) 1.544(11) C(4) - C(5) 1.388(8) C(32) - C(34) 1.542(10) C(4) - C(13) 1.395(8) C(35) - C(36) 1.527(10) C(5) - C(6) 1.427(10) C(35) - C(37) 1.513(11) C(6) - C(7) 1.403(13) C(38) - C(39) 1.404(11) C(7) - C(12) 1.405(10) C(38) - C(45) 1.500(10) C(8) - C(9) 1.389(9) C(39) - C(40) 1.533(11) C(8) - C(13) 1.401(8) C(40) - C(41) 1.497(12) C(9) - C(10) 1.404(11) C(41) - C(42) 1.461(17)

C(10) - C(11) 1.372(12) C(42) - C(43) 1.402(17) C(11) - C(12) 1.405(11) C(43) - C(44) 1.523(10) C(12) - C(13) 1.403(9) C(44) - C(45) 1.543(11) C(14) - C(15) 1.359(12) N(3) - C(46) 1.360(10) C(14) - C(19) 1.422(10) N(3) - C(50) 1.327(10) C(15) - C(16) 1.396(9) C(46) - C(47) 1.396(9) C(15) - C(20) 1.529(10) C(47) - C(48) 1.370(12) C(16) - C(17) 1.384(10) C(48) - C(49) 1.392(12) C(17) - C(18) 1.354(10) C(49) - C(50) 1.408(9)

P(1) - F(1) 1.538(7) P(1) - F(4) 1.555(7) P(1) - F(2) 1.590(8) P(1) - F(5) 1.548(6) P(1) - F(3) 1.544(7) P(1) - F(6) 1.617(7)

C(51) - Cl(1) 1.681(16) C(51) - Cl(2) 1.745(16)




S69


C(1) - Ir(1) - C(38) 83.5(2) C(15) - C(16) - C(17) 120.8(6) C(1) - Ir(1) - C(39) 90.8(3) C(16) - C(17) - C(18) 120.8(6) C(38) - Ir(1) - C(39) 37.9(3) C(17) - C(18) - C(19) 121.4(6) C(1) - Ir(1) - C(42) 165.4(5) C(14) - C(19) - C(18) 115.7(6) C(38) - Ir(1) - C(42) 94.0(4) C(14) - C(19) - C(23) 125.1(6) C(39) - Ir(1) - C(42) 78.7(4) C(18) - C(19) - C(23) 119.3(5) C(1) - Ir(1) - C(43) 153.9(2) C(15) - C(20) - C(21) 109.6(7) C(38) - Ir(1) - C(43) 80.7(2) C(15) - C(20) - C(22) 111.4(6) C(39) - Ir(1) - C(43) 89.3(3) C(21) - C(20) - C(22) 111.0(6) C(42) - Ir(1) - C(43) 37.6(5) C(19) - C(23) - C(24) 111.6(5) C(1) - Ir(1) - N(3) 101.9(2) C(19) - C(23) - C(25) 111.7(5) C(38) - Ir(1) - N(3) 161.7(3) C(24) - C(23) - C(25) 108.8(5) C(39) - Ir(1) - N(3) 156.8(2) N(2) - C(26) - C(27) 116.9(6) C(42) - Ir(1) - N(3) 84.9(4) N(2) - C(26) - C(31) 121.4(6) C(43) - Ir(1) - N(3) 87.6(3) C(27) - C(26) - C(31) 121.2(6) Ir(1) - C(1) - N(1) 121.1(4) C(26) - C(27) - C(28) 118.5(6) Ir(1) - C(1) - N(2) 128.6(4) C(26) - C(27) - C(32) 123.4(6) N(1) - C(1) - N(2) 107.1(5) C(28) - C(27) - C(32) 118.1(6) C(1) - N(1) - C(2) 113.4(4) C(27) - C(28) - C(29) 120.7(6) C(1) - N(1) - C(14) 128.9(5) C(28) - C(29) - C(30) 120.2(6) C(2) - N(1) - C(14) 117.5(5) C(29) - C(30) - C(31) 120.9(6) N(1) - C(2) - C(3) 101.3(4) C(26) - C(31) - C(30) 118.4(6) N(1) - C(2) - C(4) 116.4(5) C(26) - C(31) - C(35) 123.7(6) C(3) - C(2) - C(4) 104.6(5) C(30) - C(31) - C(35) 117.9(5) C(2) - C(3) - N(2) 103.1(4) C(27) - C(32) - C(33) 109.7(6) C(2) - C(3) - C(8) 105.0(5) C(27) - C(32) - C(34) 110.9(6) N(2) - C(3) - C(8) 118.2(5) C(33) - C(32) - C(34) 109.9(6) C(1) - N(2) - C(3) 112.8(5) C(31) - C(35) - C(36) 112.1(6) C(1) - N(2) - C(26) 129.2(6) C(31) - C(35) - C(37) 109.5(6) C(3) - N(2) - C(26) 115.8(5) C(36) - C(35) - C(37) 110.6(7) C(2) - C(4) - C(5) 131.1(6) Ir(1) - C(38) - C(39) 71.5(4) C(2) - C(4) - C(13) 108.1(5) Ir(1) - C(38) - C(45) 113.5(4) C(5) - C(4) - C(13) 120.4(6) C(39) - C(38) - C(45) 123.0(7) C(4) - C(5) - C(6) 116.8(6) Ir(1) - C(39) - C(38) 70.6(4) C(5) - C(6) - C(7) 122.4(6) Ir(1) - C(39) - C(40) 112.9(5) C(6) - C(7) - C(12) 120.1(7) C(38) - C(39) - C(40) 122.1(7) C(3) - C(8) - C(9) 132.9(6) C(39) - C(40) - C(41) 114.0(6) C(3) - C(8) - C(13) 108.3(5) C(40) - C(41) - C(42) 112.0(7) C(9) - C(8) - C(13) 118.4(6) Ir(1) - C(42) - C(41) 113.2(7) C(8) - C(9) - C(10) 117.8(7) Ir(1) - C(42) - C(43) 70.8(4)

C(9) - C(10) - C(11) 123.9(7) C(41) - C(42) - C(43) 129.5(12) C(10) - C(11) - C(12) 119.3(7) Ir(1) - C(43) - C(42) 71.6(4) C(7) - C(12) - C(11) 126.3(7) Ir(1) - C(43) - C(44) 113.4(4) C(7) - C(12) - C(13) 116.7(7) C(42) - C(43) - C(44) 121.2(8) C(11) - C(12) - C(13) 116.8(6) C(43) - C(44) - C(45) 114.3(6)

C(4) - C(13) - C(8) 112.8(6) C(38) - C(45) - C(44) 113.4(6) C(4) - C(13) - C(12) 123.4(6) Ir(1) - N(3) - C(46) 121.4(5) C(8) - C(13) - C(12) 123.7(6) Ir(1) - N(3) - C(50) 121.2(6) N(1) - C(14) - C(15) 119.5(7) C(46) - N(3) - C(50) 116.9(6) N(1) - C(14) - C(19) 116.7(7) N(3) - C(46) - C(47) 123.2(7) C(15) - C(14) - C(19) 123.8(7) C(46) - C(47) - C(48) 118.8(7)



S70

C(14) - C(15) - C(16) 117.5(7) C(47) - C(48) - C(49) 119.3(6) C(14) - C(15) - C(20) 123.6(7) C(48) - C(49) - C(50) 118.1(7) C(16) - C(15) - C(20) 118.8(6) N(3) - C(50) - C(49) 123.6(7)

F(1) - P(1) - F(2) 172.8(7) F(3) - P(1) - F(5) 93.1(4) F(1) - P(1) - F(3) 94.5(6) F(4) - P(1) - F(5) 93.3(5) F(2) - P(1) - F(3) 88.0(7) F(1) - P(1) - F(6) 86.6(6) F(1) - P(1) - F(4) 89.5(6) F(2) - P(1) - F(6) 86.9(4) F(2) - P(1) - F(4) 87.2(6) F(3) - P(1) - F(6) 84.9(5) F(3) - P(1) - F(4) 171.7(6) F(4) - P(1) - F(6) 88.1(5) F(1) - P(1) - F(5) 100.4(6) F(5) - P(1) - F(6) 172.8(5) F(2) - P(1) - F(5) 86.1(5)

Cl(1) - C(51) - Cl(2) 118.6(10)



stable crystalline annulated diaminocarbenes: coordination with … · stable crystalline annulated...

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