Eur. J. Inorg. Chem. 2008 · © WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2008 · ISSN 1434–1948

SUPPORTING INFORMATION

Title: Author(s): Ref. No.: I200701159

Cartesian coordinates obtained from DFT optimisation for 1, 2, 3, 4 -------------- NiRu2(dpa)4Cl2 ------------- BASIS USED D95V for C.H D95* for N LANL2DZ for Ni, Ru Symbolic Z-matrix: Charge = 0 Multiplicity = 5 --------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z -------------------------------------------------------------------- 2 44 0 0.000000 0.000000 -0.062349 3 44 0 0.000000 0.000000 2.274731 4 28 0 0.000000 0.000000 -2.566681 5 17 0 0.000000 0.000000 4.914302 6 17 0 0.000000 0.000000 -5.079107 1 6 0 -1.355906 -2.446172 0.989080 7 6 0 -1.993266 -2.117382 3.238874 8 6 0 -2.285544 -3.525628 0.895417 9 6 0 -2.889216 -3.187475 3.214062 10 1 0 -1.840537 -1.526369 4.135921 11 6 0 -3.045209 -3.895925 2.002686 12 1 0 -2.421172 -4.022915 -0.057205 13 1 0 -3.453212 -3.439526 4.105406 14 1 0 -3.761551 -4.709869 1.922475 15 6 0 -2.117382 1.993266 3.238874 16 6 0 -2.446172 1.355906 0.989080 17 6 0 -3.187475 2.889216 3.214062 18 1 0 -1.526369 1.840537 4.135921 19 6 0 -3.525628 2.285544 0.895417 20 6 0 -3.895925 3.045209 2.002686 21 1 0 -3.439526 3.453212 4.105406 22 1 0 -4.022915 2.421172 -0.057205 23 1 0 -4.709869 3.761551 1.922475 24 6 0 1.355906 2.446172 0.989080 25 6 0 1.993266 2.117382 3.238874 26 6 0 2.285544 3.525628 0.895417 27 6 0 2.889216 3.187475 3.214062 28 1 0 1.840537 1.526369 4.135921 29 6 0 3.045209 3.895925 2.002686 30 1 0 2.421172 4.022915 -0.057205 31 1 0 3.453212 3.439526 4.105406 32 1 0 3.761551 4.709869 1.922475 33 6 0 2.117382 -1.993266 3.238874 34 6 0 2.446172 -1.355906 0.989080 35 6 0 3.187475 -2.889216 3.214062 36 1 0 1.526369 -1.840537 4.135921 37 6 0 3.525628 -2.285544 0.895417 38 6 0 3.895925 -3.045209 2.002686 39 1 0 3.439526 -3.453212 4.105406 40 1 0 4.022915 -2.421172 -0.057205 41 1 0 4.709869 -3.761551 1.922475 42 6 0 0.221244 2.795723 -1.137456

43 6 0 -0.476747 2.872525 -3.368873 44 6 0 0.000000 4.197213 -1.010955 45 6 0 -0.683226 4.258036 -3.331035 46 1 0 -0.646461 2.295060 -4.274451 47 6 0 -0.449916 4.927586 -2.113529 48 1 0 0.142607 4.680185 -0.051548 49 1 0 -1.025275 4.780077 -4.218431 50 1 0 -0.630952 5.995906 -2.020514 51 6 0 -2.795723 0.221244 -1.137456 52 6 0 -2.872525 -0.476747 -3.368873 53 6 0 -4.197213 0.000000 -1.010955 54 6 0 -4.258036 -0.683226 -3.331035 55 1 0 -2.295060 -0.646461 -4.274451 56 6 0 -4.927586 -0.449916 -2.113529 57 1 0 -4.680185 0.142607 -0.051548 58 1 0 -4.780077 -1.025275 -4.218431 59 1 0 -5.995906 -0.630952 -2.020514 60 6 0 -0.221244 -2.795723 -1.137456 61 6 0 0.476747 -2.872525 -3.368873 62 6 0 0.000000 -4.197213 -1.010955 63 6 0 0.683226 -4.258036 -3.331035 64 1 0 0.646461 -2.295060 -4.274451 65 6 0 0.449916 -4.927586 -2.113529 66 1 0 -0.142607 -4.680185 -0.051548 67 1 0 1.025275 -4.780077 -4.218431 68 1 0 0.630952 -5.995906 -2.020514 69 6 0 2.795723 -0.221244 -1.137456 70 6 0 2.872525 0.476747 -3.368873 71 6 0 4.197213 0.000000 -1.010955 72 6 0 4.258036 0.683226 -3.331035 73 1 0 2.295060 0.646461 -4.274451 74 6 0 4.927586 0.449916 -2.113529 75 1 0 4.680185 -0.142607 -0.051548 76 1 0 4.780077 1.025275 -4.218431 77 1 0 5.995906 0.630952 -2.020514 78 7 0 -0.603533 -1.980693 -0.070022 79 7 0 -1.980693 0.603533 -0.070022 80 7 0 1.980693 -0.603533 -0.070022 81 7 0 0.603533 1.980693 -0.070022 82 7 0 -1.243648 -1.743978 2.169315 83 7 0 1.743978 -1.243648 2.169315 84 7 0 2.151539 0.041928 -2.310765 85 7 0 0.041928 -2.151539 -2.310765 86 7 0 -0.041928 2.151539 -2.310765 87 7 0 1.243648 1.743978 2.169315 88 7 0 -2.151539 -0.041928 -2.310765 89 7 0 -1.743978 1.243648 2.169315

-------- CuRu2(dpa)4Cl2 -------- BASIS USED D95V for C.H D95* for N LANL2DZ for Ni, Ru Symbolic Z-matrix: Charge = 0 Multiplicity = 4 Ru 0. 0. -0.07515 Ru 0. 0. 2.25619 Cu 0. 0. -2.747 Cl 0. 0. 4.82442 Cl 0. 0. -5.1396 C 0. 2.79191 1.00007 C 0.79248 2.80275 3.22411 C 0.26902 4.19169 0.90926 C 1.04836 4.17442 3.19972 H 0.97964 2.20991 4.11241 C 0.78741 4.87887 2.00343 H 0.10394 4.69791 -0.03384 H 1.45053 4.66375 4.07999 H 1.00578 5.94098 1.92452 C 2.80275 -0.79248 3.22411 C 2.79191 0. 1.00007 C 4.17442 -1.04836 3.19972 H 2.20991 -0.97964 4.11241 C 4.19169 -0.26902 0.90926 C 4.87887 -0.78741 2.00343 H 4.66375 -1.45053 4.07999 H 4.69791 -0.10394 -0.03384 H 5.94098 -1.00578 1.92452 C 0. -2.79191 1.00007 C -0.79248 -2.80275 3.22411 C -0.26902 -4.19169 0.90926 C -1.04836 -4.17442 3.19972 H -0.97964 -2.20991 4.11241 C -0.78741 -4.87887 2.00343 H -0.10394 -4.69791 -0.03384 H -1.45053 -4.66375 4.07999 H -1.00578 -5.94098 1.92452 C -2.80275 0.79248 3.22411 C -2.79191 0. 1.00007 C -4.17442 1.04836 3.19972 H -2.20991 0.97964 4.11241 C -4.19169 0.26902 0.90926 C -4.87887 0.78741 2.00343 H -4.66375 1.45053 4.07999 H -4.69791 0.10394 -0.03384 H -5.94098 1.00578 1.92452 C 1.21471 -2.5727 -1.09378 C 1.85048 -2.3745 -3.32881 C 2.12602 -3.6511 -0.91147 C 2.74378 -3.45314 -3.24414 H 1.70241 -1.82832 -4.25864 C 2.88855 -4.09323 -1.99717 H 2.24921 -4.09727 0.06893 H 3.30684 -3.76417 -4.11805 H 3.59328 -4.9116 -1.86903

C 2.5727 1.21471 -1.09378 C 2.3745 1.85048 -3.32881 C 3.6511 2.12602 -0.91147 C 3.45314 2.74378 -3.24414 H 1.82832 1.70241 -4.25864 C 4.09323 2.88855 -1.99717 H 4.09727 2.24921 0.06893 H 3.76417 3.30684 -4.11805 H 4.9116 3.59328 -1.86903 C -1.21471 2.5727 -1.09378 C -1.85048 2.3745 -3.32881 C -2.12602 3.6511 -0.91147 C -2.74378 3.45314 -3.24414 H -1.70241 1.82832 -4.25864 C -2.88855 4.09323 -1.99717 H -2.24921 4.09727 0.06893 H -3.30684 3.76417 -4.11805 H -3.59328 4.9116 -1.86903 C -2.5727 -1.21471 -1.09378 C -2.3745 -1.85048 -3.32881 C -3.6511 -2.12602 -0.91147 C -3.45314 -2.74378 -3.24414 H -1.82832 -1.70241 -4.25864 C -4.09323 -2.88855 -1.99717 H -4.09727 -2.24921 0.06893 H -3.76417 -3.30684 -4.11805 H -4.9116 -3.59328 -1.86903 N -0.45461 2.02595 -0.05014 N 2.02595 0.45461 -0.05014 N -2.02595 -0.45461 -0.05014 N 0.45461 -2.02595 -0.05014 N 0.28258 2.1174 2.16793 N -2.1174 0.28258 2.16793 N -1.94008 -1.1054 -2.29061 N -1.1054 1.94008 -2.29061 N 1.1054 -1.94008 -2.29061 N -0.28258 -2.1174 2.16793 N 1.94008 1.1054 -2.29061 N 2.1174 -0.28258 2.16793

-------- [CuRu2(dpa)4Cl2]+

-------- BASIS USED D95V for C.H D95* for N LANL2DZ for Ni, Ru Symbolic Z-matrix: Charge = 1 Multiplicity = 5 Ru 0. 0. -0.00374 Ru 0. 0. 2.30447 Cu 0. 0. -2.6449 Cl 0. 0. 4.79691 Cl 0. 0. -5.067 C 0.58109 2.73675 1.00051 C 1.28518 2.63189 3.24791 C 1.14043 4.04072 0.89139 C 1.81754 3.92197 3.20944 H 1.32506 2.03511 4.15165 C 1.75241 4.63530 1.99474 H 1.11942 4.54825 -0.0652 H 2.28150 4.33912 4.09604 H 2.18749 5.62708 1.90786 C 2.63189 -1.28518 3.24791 C 2.73675 -0.58109 1.00051 C 3.92197 -1.81754 3.20944 H 2.03511 -1.32506 4.15165 C 4.04072 -1.14043 0.89139 C 4.63530 -1.75241 1.99474 H 4.33912 -2.28150 4.09604 H 4.54825 -1.11942 -0.0652 H 5.62708 -2.18749 1.90786 C -0.58109 -2.73675 1.00051 C -1.28518 -2.63189 3.24791 C -1.14043 -4.04072 0.89139 C -1.81754 -3.92197 3.20944 H -1.32506 -2.03511 4.15165 C -1.75241 -4.63530 1.99474 H -1.11942 -4.54825 -0.0652 H -2.28150 -4.33912 4.09604 H -2.18749 -5.62708 1.90786 C -2.63189 1.28518 3.24791 C -2.73675 0.58109 1.00051 C -3.92197 1.81754 3.20944 H -2.03511 1.32506 4.15165 C -4.04072 1.14043 0.89139 C -4.63530 1.75241 1.99474 H -4.33912 2.28150 4.09604 H -4.54825 1.11942 -0.0652 H -5.62708 2.18749 1.90786 C 0.62912 -2.69266 -1.12281 C 1.37885 -2.5226 -3.34836 C 1.25432 -3.96689 -1.01308 C 1.98524 -3.78193 -3.31271 H 1.39123 -1.91301 -4.24734 C 1.92702 -4.51166 -2.10851 H 1.23842 -4.48884 -0.06424 H 2.48848 -4.16433 -4.19357 H 2.41196 -5.48027 -2.0214

C 2.69266 0.62912 -1.12281 C 2.5226 1.37885 -3.34836 C 3.96689 1.25432 -1.01308 C 3.78193 1.98524 -3.31271 H 1.91301 1.39123 -4.24734 C 4.51166 1.92702 -2.10851 H 4.48884 1.23842 -0.06424 H 4.16433 2.48848 -4.19357 H 5.48027 2.41196 -2.0214 C -0.62912 2.69266 -1.12281 C -1.37885 2.5226 -3.34836 C -1.25432 3.96689 -1.01308 C -1.98524 3.78193 -3.31271 H -1.39123 1.91301 -4.24734 C -1.92702 4.51166 -2.10851 H -1.23842 4.48884 -0.06424 H -2.48848 4.16433 -4.19357 H -2.41196 5.48027 -2.0214 C -2.69266 -0.62912 -1.12281 C -2.5226 -1.37885 -3.34836 C -3.96689 -1.25432 -1.01308 C -3.78193 -1.98524 -3.31271 H -1.91301 -1.39123 -4.24734 C -4.51166 -1.92702 -2.10851 H -4.48884 -1.23842 -0.06424 H -4.16433 -2.48848 -4.19357 H -5.48027 -2.41196 -2.0214 N 0. 2.05226 -0.05819 N 2.05226 0. -0.05819 N 0. -2.05226 -0.05819 N -2.05226 0. -0.05819 N 0.68109 2.04065 2.18371 N -2.04065 0.68109 2.18371 N -0.68109 -2.04065 2.18371 N 2.04065 -0.68109 2.18371 N -1.98635 -0.71693 -2.29402 N -0.71693 1.98635 -2.29402 N 1.98635 0.71693 -2.29402 N 0.71693 -1.98635 -2.29402

------------------ [NiRu2(dpa)4Cl2]+

------------------ BASIS USED D95V for C.H D95* for N LANL2DZ for Ni, Ru Symbolic Z-matrix: Charge = 1 Multiplicity = 6 Ru 0. 0. -0.03328 Ru 0. 0. 2.28381 Ni 0. 0. -2.61981 Cl 0. 0. 4.74391 Cl 0. 0. -4.94834 C -1.21857 -2.51169 0.9783 C -1.91539 -2.22391 3.21277 C -2.07701 -3.64117 0.86255 C -2.74823 -3.34335 3.16621 H -1.82504 -1.63131 4.11544 C -2.83680 -4.05955 1.95448 H -2.16085 -4.14647 -0.09178 H -3.31783 -3.62740 4.04385 H -3.49977 -4.91526 1.86123 C -2.22391 1.91539 3.21277 C -2.51169 1.21857 0.9783 C -3.34335 2.74823 3.16621 H -1.63131 1.82504 4.11544 C -3.64117 2.07701 0.86255 C -4.05955 2.8368 1.95448 H -3.62740 3.31783 4.04385 H -4.14647 2.16085 -0.09178 H -4.91526 3.49977 1.86123 C 1.21857 2.51169 0.9783 C 1.91539 2.22391 3.21277 C 2.07701 3.64117 0.86255 C 2.74823 3.34335 3.16621 H 1.82504 1.63131 4.11544 C 2.83680 4.05955 1.95448 H 2.16085 4.14647 -0.09178 H 3.31783 3.62740 4.04385 H 3.49977 4.91526 1.86123 C 2.22391 -1.91539 3.21277 C 2.51169 -1.21857 0.9783 C 3.34335 -2.74823 3.16621 H 1.63131 -1.82504 4.11544 C 3.64117 -2.07701 0.86255 C 4.05955 -2.8368 1.95448 H 3.62740 -3.31783 4.04385 H 4.14647 -2.16085 -0.09178 H 4.91526 -3.49977 1.86123 C 0. 2.78830 -1.12384 C -0.7878 2.82821 -3.332 C -0.30575 4.17083 -0.98522 C -1.08462 4.19437 -3.27521 H -0.95769 2.25478 -4.23787 C -0.84377 4.87451 -2.06509 H -0.15639 4.66088 -0.03086 H -1.49604 4.69628 -4.14384

H -1.08668 5.92860 -1.961 C -2.78830 0. -1.12384 C -2.82821 -0.7878 -3.332 C -4.17083 -0.30575 -0.98522 C -4.19437 -1.08462 -3.27521 H -2.25478 -0.95769 -4.23787 C -4.87451 -0.84377 -2.06509 H -4.66088 -0.15639 -0.03086 H -4.69628 -1.49604 -4.14384 H -5.92860 -1.08668 -1.961 C 0. -2.78830 -1.12384 C 0.7878 -2.82821 -3.332 C 0.30575 -4.17083 -0.98522 C 1.08462 -4.19437 -3.27521 H 0.95769 -2.25478 -4.23787 C 0.84377 -4.87451 -2.06509 H 0.15639 -4.66088 -0.03086 H 1.49604 -4.69628 -4.14384 H 1.08668 -5.92860 -1.961 C 2.78830 0. -1.12384 C 2.82821 0.7878 -3.332 C 4.17083 0.30575 -0.98522 C 4.19437 1.08462 -3.27521 H 2.25478 0.95769 -4.23787 C 4.87451 0.84377 -2.06509 H 4.66088 0.15639 -0.03086 H 4.69628 1.49604 -4.14384 H 5.92860 1.08668 -1.961 N -0.47016 -1.99909 -0.07171 N -1.99909 0.47016 -0.07171 N 0.47016 1.99909 -0.07171 N 1.99909 -0.47016 -0.07171 N -1.16476 -1.80576 2.16 N 1.80576 -1.16476 2.16 N 1.16476 1.80576 2.16 N -1.80576 1.16476 2.16 N 2.13345 0.25765 -2.29704 N 0.25765 -2.13345 -2.29704 N -2.13345 -0.25765 -2.29704 N -0.25765 2.13345 -2.29704

Fig. S1 ORTEP view of complex 2, solvent are omitted, thermal ellipsoid was drawn at 30% probability

Fig. S2 ORTEP view of complex 3, solvent are omitted, thermal ellipsoid was drawn at 30% probability

Fig. S3 ORTEP view of complex 4, solvent are omitted, thermal ellipsoid was drawn at 30% probability

Fig. S4 400 MHz 1H NMR spectrum of complex 1 (upper) and 3 (lower) in CD2Cl2 at 25°C. Several peaks between 0 and 5 ppm should be assigned to solvent and to some minor impurities.

-3

-4

-5

-6

-7

-8

-9

-10

-11

Ru RuCl Cl

Unoccupied MOsSingly occupied MOsDoubly occupied MOs

Ni

Ru RuCl ClCu

M = NiM = Cu

MRu2(dpa)4Cl2

z

xy

α spinα spin β spinβ spin

-12

-13

eV-2

Figure S5. Diagram of the frontier orbitals with major metal character obtained from Unrestricted DFT calculations for the quintet ground state of 2 (left hand-side) and for the sextet state of 4 (right hand-side). Energy scale is in eV.

Fig. S6. EPR Spectrum of 1 in powder form at 4 K. Observed g value were g|| = 1.99 and g┴ = 3.99.

Fig. S7. EPR Spectrum of 4 in powder form at 4 K. Observed g value were g|| = 2.05 and g┴ = 6.26.