coordination modes of hydroxylamine ligands at elements ... · 1 coordination modes of...
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1
Coordination Modes of Hydroxylamine Ligands
at Elements Through the Periodic Table
WESTFÄLISCHEWILHELMS-UNIVERSITÄT
MÜNSTER
Norbert W. Mitzel
UNIVERSITÄT
BIELEFELD
2
Gas electron diffraction
@ MS (soon BI)RaphaelBerger
3
BeLi B C N O F Ne
He
Na
K
Rb
Cs
Fr
Mg
Ca
Sr
Ba
Ra
Sc
Y
La
Ac
Ti
Zr
Hf
Rf
V
Nb
Ta
Db
Cr
Mo
W
Sg
Mn
Tc
Re
Bh
Fe
Ru
Os
Hs
Co
Rh
Ir
Mt
Ni
Pd
Pt
__
Cu
Ag
Au
__
Zn
Cd
Hg
__
Al
Ga
In
Tl
Si
Ge
Sn
Pb
P
As
Sb
Bi
S
Se
Te
Po
Cl
Br
I
At
Ar
Kr
Xe
Rn
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Yb LuTm
H
Th U Np Pu Am Cm Bk Cf Es Fm No LrMdPa
43 5 6 7 8 9 10
2
11
19
37
55
87
12
20
38
56
88
21
39
57
89
22
40
72
104
23
41
73
105
24
42
74
106
25
43
75
107
26
44
76
108
27
45
77
109
28
46
78
110
29
47
79
111
30
48
80
112
13
31
49
81
14
32
50
82
15
33
51
83
16
34
52
84
17
35
53
85
18
36
54
86
58 59 60 61 62 63 64 65 66 67 68 70 7169
1
90 92 93 94 95 96 97 98 99 100 102 10310191
1Ia
2IIa
3IIIb
4IVb
5Vb
6VIb
7VIIb
8 9VIIIb
10 11Ib
12IIb
13IIIa
14IVa
15Va
16VIa
17VIIa
18VIIIa
Overview
114
E-O-NR2
4
XRDsolid
77.1(1)1.963(1)
74.1(1)1.904(2)
GEDgas
94.3(9)2.273(17)
79.4(6)2.011(17)
Å, °
<SiONd(Si···N)
<SiONd(Si···N)
F3SiONMe2
F3CF2SiONMe2
SiF
FF
O
N C
C
P21/nmp. -69°C
Si
F
FF
O
NC
CF
F
C
1.912 Å
Pnmamp. -43°C
F3SiONMe2 / (F3C)F2SiONMe2
* Mitzel, Losehand, Wu, Cremer, Rankin, J. Am. Chem. Soc. 2000, 122, 4471# Mitzel, Vojinović, Fröhlich, Foerster, Rankin, J. Am. Chem. Soc. 2005, 127, 13705
5
Si
O
N
C
FF
F2
F
F
C
Si
N
O
MP2/6-311++G(d,p)
(F3C)F2SiONMe2 – electron density
6
[4+4]-Coordination in SiON compounds
SiN
O
N.W. Mitzel, A.J. Blake, D.W.H. Rankin, J. Am. Chem. Soc. 1997, 119, 4143
Si(ONMe2)4
109.1(av)°
7
O
H3GeONMe2
GeN
C‘
C
<GeON104.6(1)105.2(5)°
Ge···N 2.601(1)2.587(6) Å
Me2O-96°C
Me2NOLi + H3GeBr H3GeONMe2 + LiBr
XRD GEDsolid gas
Pnmam.p. -22°C
Decomp. > -20°C :
H-H2Ge-ONMe2 →→→→
HONMe2 + (GeH2)∞∞∞∞
Decomp. > -20°C :
H-H2Ge-ONMe2 →→→→
HONMe2 + (GeH2)∞∞∞∞
N.W. Mitzel, U. Losehand, S.L. Hinchley, D.W.H. Rankin, Inorg. Chem. 2001, 40, 661
8
O‘ C
C‘N
<OSnC‘108.1(6)→→→→118.1(av)°
<OSnC‘108.1(6)→→→→118.1(av)°
<SnON102.5(8) →→→→101.5(4)°
<SnON102.5(8) →→→→101.5(4)°
GED → XRDgas → solid
Sn O
Me3SnONMe2
<OSnC99.6(10)→→→→99.7(4)°
<OSnC99.6(10)→→→→99.7(4)°
O
Sn N
O‘
N. W. Mitzel, U. Losehand, A. D. Richardson, Organometallics 1999, 18, 2610
2.745(9) Å
C‘
CC‘‘
mp. -85°CP2/n
2.998(10) ÅO
Sn N
O
Sn N
9
Al
N
Al O
OOAl
N
N 96.4° 88.0°
86.5°
AlO
N
Al
O
N
140.8°102.7°
Ga
GaN
N
O
O
GaGa
N
N
O
O
107.7(5)° 131.1(5)°
Hausen,Schmöger,Schwarz,J. Organomet. Chem.
1978, 153, 271
(Me2GaONMe2)2
(tBu2AlONMe2)2(Me2AlONMe2)3
(tBu2GaONMe2)2
N. W. Mitzel, C. Lustig, M. Woski, Dalton Trans. 2004, 397
MR3 + HONMe2 RH + ⅛ [R2M-ONMe2]nn
(M = Al, Ga)
10
P21/n
2.33
2(4)
GaO
N
[HONMe]2CH2 as ligand
M = Al, Ga
MM
N
O
NO
BuLi-BuH -LiCl
-MeH
Me2MCl
GaMe3
N
OLi
N
OLi
N
OH
N
OH
N. W. Mitzel, C. Lustig, Angew. Chem. 2001, 113, 4521
11
AlAl
Al
N O
O
O
O
N
N
NCP1
[HONMe]2CH2 as ligand
N. W. Mitzel, C. Lustig, Angew. Chem. 2001, 113, 4521
O
AlO O
O
Al
Al
N
N
N
N
Me
N
Al
O
O O
Al
N
N
Al
O
N
Me
-MeHAlMe3
N
OH
N
OH
B3LYP/6-31G(d):∆E = 5 kJ/mol
1H-NMR:-80°C → +20°Cdynamic system
12Patrick Bösing, 2006
OO N
R
OH
H+
NR
OH
NR
OH
R = Me, tBu, Ph
ON
N
O
Ga
Ga
C C
CC
C
C
NR
O
NR
ONaBH4
Me3Ga
[HON(R)CH2]2 as ligand
O
N
NO
Ga
Ga
CO
NO
NC
H HP1
C2/c
N
N
OGa
OGa
Bu
Bu
BuBu
ONH
N
OH
tBu3Ga
t t
t
t
⊕⊕⊕⊕-
13
Zn
C
O
O
O
N
NN C
ZnZn
Zn
Zn
Zn(ZnR)4(ONMe2)6
C2/c
M. Ullrich, C. Lustig, R. J. F. Berger, N. W. Mitzel, Eur. J. Inorg. Chem. 2006, 4219
N OH + 5 ZnMe26
- 6 CH4
N
Zn
O
O
O
N
Zn
ZnZn
Zn
Pccn
O
ON
N
N
N OH + 5 ZniPr26
- 6 C3H8
∆T ZnOPyrolysis / Ar
14Matthias Ullrich, 200660 40 20 0 δ / ppm70 50 30 10
VT-13C-NMR –[Zn(ZnEt)4(ONEt2)6]
H2C(NEt2)13C{1H}-NMR,
C7D8, RT
13C{1H}-DEPT-135C7D8, -70°C
H3C(NEt2)
H3C(ZnEt)
H2C(ZnEt)
R = R‘ = Et
15
→ 3 x change = full period
6 O−N ligands, C2-symmetry
[Zn(ZnEt)4(ONEt2)6] - molecular dynamics
Matthias Ullrich, 2005R. J. F. Berger, 2006
für [Zn(ZnMe)4(ONMe2)6]:DFT(BP)/SV(P): ∆E = 5.4 kcal / mol
16S. Jana, R. Fröhlich, N. W. Mitzel, Chem. Eur. J. 2006, 12, 592
4 Me2N-NH2 + 4 ZnEt2
- 4 C2H6Zn
N N
Zn
Zn
Zn
N
N
NN
N
NN
ZnZn
ZnN N
ZnEt
NMe2
NHHN
N
Me2N
Me2
Me2
Et
Et
H
Et
N
ZnZn
ZnN N
Zn
N
NN
N
N
> 350°CZn3N2
(ZnEt)4[N(H)NMe2]4
P21/n
Zn(CN2)
∆T / Ar
17
Zn(ZnMe)4[N(H)NMe2]2(ONEt2)4
Mixed zinc-hydrazide/hydroxylamide
5 ZnMe2 + 2 H2NNMe2 + 4 HONEt2
- 6 CH4
N
Zn
Zn
Zn
N
N
N
N
O
NZn
ZnN
O
O
NYield 87 %mp. 164 °C (dec.)IR [KBr, cm-1]: 3184 (br, N-H)
Pbca
S. Jana, R. Fröhlich, R. J. F. Berger, N. W. Mitzel, Chem. Commun. 2006, 3993.
C24H66N6O4Zn5
18Alexander Willner, 2006/7
ON-Ligands in CVD precursors
Ti(NMe2)4
RN
O
MR 4
• M = Ti, Zr; R = Et: Wieghardt et al. Z. Anorg. Allg. Chem. 1982, 490, 182
• M = Ti, Zr, Hf; R = Me: Mitzel, Blake, Rankin, J. Chem. Soc. Dalton Trans. 1996, 2089
- 4 HNMe2
Yield: 72%; EA: �; MS: m/z = 284 1H NMR: 2.85 s, 3.29 m; 13C-NMR: 48.5, 55.7
Hf(ONEt2)4 HfO2
• A. C. Jones et al. J. Chem. Mater. 2004, 14, 3101 & Chem. Vap. Depos. 2003, 9, 309
Liquid InjectionMOCVD
NR
OH
NR
OHTiO
N
N
O
High-κ-Dielectrics
Subl. 60°C / 10-2 mbar
19
Ti
C
C
O
CC
O
N
C
NC
C
NR
OH
NR
OH
R = Me, tBu, Ph
Yield.: 78%, EA: �MS: m/z = 301 [M+ - Me]1H NMR: -0.06, 1.97, 2.41, 2.4313C NMR: 10.9, 26.2, 46.6, 60.0,117.9
Pbca
Ti-O: 1.911 / 1.936(3) ÅTi-N: 2.109 / 2.132(3) ÅTi-C: 2.172(4) Å
TiMe3
-2 CH4
ON-Ligands in polymerisation catalysts
Cp*TiCl3, 3 MeLi
-2 CH4
Alexander Willner, 2006
20Ajay Venugopal, 2006
K{Y[ON(iPr)2]}4
YCl3K[ON(iPr)2] THF
HON(iPr)2
KH -H2; THF Y
OON
NNO O
KK
Yield: 73%, EA: �;1H NMR: 1.10, 3.08; 13C NMR: 20.4, 54.7
21
MCl3, THFK[ONEt2]HONEt2
KH-H2; THF
Cp*(ONEt2)M-[µ2(O)-η2-ONEt2]2-M(ONEt2)Cp*
M = Y, La, Ho, Er, Lu
Er Er
N
N
N
N
O
O
O
O
Organolanthanoid complexes
Ajay Venugopal, 2006
NaCp*, -KCl
Er-O 2.136Er-N 2.415
Er-N 2.417
2.2682.304
22
{Be2[ON(iPr)2]4}
BeCl2Et2O
HON(iPr)2 LiON(iPr)2 {Be2[ON(iPr)2]4}n-BuLi
Et2O
Raphael J. F. Berger, Surajit Jana, 2006
O O
O
N
NN
N
O
Be
Be
113.4°
110.1°
126.8°
113.9°
23
K[ONMe2]HONMe2KH HONMe2
insoluble
K[ONMe2][HONMe2]
Potassium aggregates
K
O
N
K
O
N
K
O
N
KO
N
K O
O
O
OO
O
O
NN
K
THFTHF soluble
-H2; THF
Ajay Venugopal, 2007
24
K2
K2‘ K1‘
K1O2N2 O4
N4
O1
N1 O3N3
O10(THF)
K[ONiPr2]HONiPr2KH
-H2; THFHONMe2
insoluble [K(iPr2NO-H-ONiPr2)(THF)]
THF soluble
Potassium aggregates
Ajay Venugopal, 2007
THF
25
O
K
NO
K
N
O K
N
O
O
O
OK
N
O
K
NK
N
THF
THF
THF
OTHF
{[K6[ON(CH2Ph)2]6(THF)4}
Ajay Venugopal, 2007
26
M
O
N
Metal hydroxylamine compounds
• different bridging and binding modes
• hemilabile ligands
• flexible coordination and aggregation modi
M
ON
M M
O
N
MSi, Ge, SnTi, Zr, Hf
------------ K, Y, La, Sm, Ho, Er, Lu -----------
-------- Al, Ga, In, Zn, Cd ------
27
Fabian
Conrady
Patrick
Bösing
Ajay
Venugopal
Alexander
Willner
Michael
Hagemann
Raphael
Berger
Benjamin
Hellmann
Ingo
Gronde
Matthias
Ullrich
Denise
Defayay
Constantin
Sicking
Ulf
Strasser
Ina
Kamps
Jasmin
Chmiel