Synthesis of Base-Free Silyl (silylene) and Germyl (germylene) Complexes
| Project/Area Number |
11640554
|
|---|
| Research Category |
Grant-in-Aid for Scientific Research (C)
|
| Allocation Type | Single-year Grants |
|---|
| Section | 一般 |
|---|
| Research Field |
Inorganic chemistry
|
|---|
| Research Institution | Tohoku University |
|---|
Principal Investigator |
UENO Keiji Graduate School of Science, Tohoku University, Research Associate, 大学院・理学研究科, 助手 (20203458)
|
|---|
| Project Period (FY) |
1999 – 2000
|
| Project Status |
Completed (Fiscal Year 2000)
|
| Budget Amount *help |
¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 2000: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1999: ¥2,400,000 (Direct Cost: ¥2,400,000)
|
|---|
| Keywords | Silylene Complexes / Germylene Complexes / Reactivity / Migration / Tungsten Complexes / Unsaturated Bonding / Isomerization / Isocarbonyl Complexes / ガリレン錯体 / 1,3-転移 / 動的挙動 |
|---|
| Research Abstract |
1. Photolysis of Cp^*W(CO)_3Me (Cp^*=η-C_5Me_5) in the presence of excess HSiMe_2SiMe_3 afforded yellow crystals of a self-stabilized silyl (silylene) tungsten complex with a dimeric structure, [Cp^*W(CO)_2(=SiMe_2)(SiMe_3)]_2(1). In contrast, photolysis of Cp^*W(CO)_3Me in the presence of HSiMe_2SiMeMes_2 (Mes=2,4,6-Me_3C_6H_2) afforded a silyl (silylene) tungsten complex Cp^*W(CO)_2(=SiMes_2)(SiMe_3)(2). Complex 2 is the first "base-free" silyl (silylene) complex. X-ray crystal structure analysis of complex 1 and 2 revealed the significantly short W=Si bond compared to the W-Si bond. The ^<29> Si NMR signal of the silylene ligand for 2 appeared at remarkably low field (δ380.9 ppm) with a tungsten satellite having a large coupling constant (^1J_<SiW>=154.9 Hz). These results clearly demonstrate the double bond character of tungsten-silylene bonding.
2. Photolysis of Cp^*W(CO)_3GeMe_2GeMe_3 resulted in the formation of a "base-free" germyl (germylene) tungsten complex Cp^*W(CO)_2(=GeMe_2)(GeMe_3)(3) quantitatively. Complex 3 is the first germylene complex having only small methyl groups on the germanium atoms. Reaction of complex 3 with Fe_2(CO)_9 resulted in the formation of a germylene-bridged dimetal complex Cp^*(OC)_3W(μ-GeMe_2)Fe(CO)_3GeMe_3 quantitatively.
|
Report
(3 results)
Research Products
(21 results)
-
-
-
-
-
-
-
-
-
-
-
-
-
[Publications] Keiji Ueno, Takahito Watanabe, and Hiroshi Ogino: "Synthesis of Cationic Diiron Complexes Bridged by a Base-Stabilized Gallium Atom [Fp_2(μ-Ga Do_2)]^+X^-(Fp=(η-C_5H_5)Fe(CO)_2, Do_2=2,2'-Bipyridine, N,N,N', N'-Tetramethylethylenediamine, 1,10-Phenanthroline, (4-(Dimethylamino) pyridine)_2, X^-=[Fp_2GaCl_2]^-, BPh_4^-)"Organometallics. 19. 5679-5682 (2000)
Description
「研究成果報告書概要(欧文)」より
Related Report
-
-
-
-
-
-
-
-
