| Project/Area Number |
13440193
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Inorganic chemistry
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| Research Institution | The University of the Air |
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Principal Investigator |
OGINO Hiroshi The University of the Ai, Miyagi Study Center, Professor, 宮城学習センター, 教授 (00004292)
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| Co-Investigator(Kenkyū-buntansha) |
UENO Keiji Gunma University, Faculty of Engineering, Associate Professor, 工学部, 助教授 (20203458)
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| Project Period (FY) |
2001 – 2003
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| Project Status |
Completed (Fiscal Year 2003)
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| Budget Amount *help |
¥8,900,000 (Direct Cost: ¥8,900,000)
Fiscal Year 2003: ¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 2002: ¥1,800,000 (Direct Cost: ¥1,800,000)
Fiscal Year 2001: ¥5,600,000 (Direct Cost: ¥5,600,000)
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| Keywords | 1,3-migration / 1,2-migration / silylene complexes / germylene complexes / silylyne complexes / sigmatropy / triplet complex / 1、2-転位 / 1、3-転位 / シリル錯体 / シリル(シリレン)錯体 / オリゴシラン / C-C結合生成 / Si-C結合生成 / 1,3転位反応 / 脱水素縮合反応 / タングステン錯体 / ロジウム錯体 / 鉄錯体 / 脱アルコール反応 |
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| Research Abstract |
In this research project, we have investigated (1) synthesis of transition-metal complexes with unsaturated bonding between metal and main group elements such as silylene and germylene complexes and (2) reactivities of the unsaturated bonding, especially sigmatropic rearrangement between the M-E and M=E bonds (M = transition metal, E = main group element).
Silyl(silylene) complexes have been proposed as key intermediates in many transformations of organosilicon compounds mediated by transition metal compounds. However, such complexes are too unstable to isolate due to the electron-deficient nature of the silylene ligand. We have succeeded to stabilize the silyl(silylene) complexes kinetically using bulky Mes substituents (Mes = 2,4,6-C_6H_2Me_3) and isolated the first silyl(silylene)tungsten, molybdenum, and iron complexes. Reaction of the isolated silyl(silylene)iron complex with 'BuNC afforded a disilanyliron complex produced by 1,3-substituent migration from silyl to silylene ligand followed by 1,2-silyl migration from iron to silylene ligand.
Photo-irradiation of Cp^*W(CO)_3Me (Cp^* = η-C_5Me_5) in the presence of (2-N,N-dimethylaminophenyl)dimethylsilane gave a silyl complex in which the amino group was coordinated to the tungsten atom. Further irradiation of the silyl complex caused 1,2-aryl migration from silyl to tungsten to form abase-stabilized silylene complex.
Irradiation of phosphinosilyliron complex CpFe(CO)_2SiMe_2PPh_2 afforded a novel metallacycle complex with Fe-Si-P three-membered ring. The Fe-Si bond bears unsaturated character due to the contribution of a resonance form with a phosphino-coordinated silylene ligand. Thus reaction of the complex with acetone proceeded via coordination of acetone oxygen to the silylene ligand followed by insertion into the Si-P bond to form a Fe-Si-O-C-P five-membered ring.
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