1992 Fiscal Year Final Research Report Summary
Silylation of Dinitrogen Coordinated to Transition Metals and its Application to Catalytic Nitrogen Fixation
| Project/Area Number |
03453097
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
Synthetic chemistry
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| Research Institution | The University of Tokyo |
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Principal Investigator |
HIDAI Masanobu Univ. of Tokyo, Fac. of Eng. Professor, 工学部, 教授 (60011011)
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| Co-Investigator(Kenkyū-buntansha) |
MIZOBE Yasushi Univ. of Tokyo, Fac. of Eng. Lecturer, 工学部, 講師 (40175609)
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| Project Period (FY) |
1991 – 1992
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| Keywords | Dinitrogen / Catalysis Silylamine / Silylation / Germylation / Silyldiazenido / Silylhydrazido |
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| Research Abstract |
1. Treatment of a dinitrogen complex cis-[W(N_2)_2(PMe_2Ph)_4](1a) with R_3SiCl/NaI mixtures afforded a variety of silyldiazenido complexed trans-[WI(NNSiR_3)(PMe_2Ph)_4], while the reactions of 1a or its Mo analogue 1b with ClSiMe_2CH_2CH_2SiMe_2Cl/NaI resulted in the formation of silylhydrazido(2-) complexes cis, mer-[WI_2(NNSiMe_2CH_2CH_2SiMe_2)(PMe_2Ph)_3](2). Complex 1a also reacted with R_3GeCl/NaI to give germyldiazenido complexes trans-[WI(NNGeR_3)(PMe_2Ph)_4].
2. By treatment with R_3SiCl and Na in the presence of a catalytic amount of 1b, molecular nitrogen has been converted into silylamines under ambient conditions. The yields of silylamines produced by these novel catalytic reactions considerably depended upon the nature of the substituents attached to the Si atom.
3. One PMe_2Ph ligand in 2 was replaced readily by a series of pi-acceptor ligands at room temperature, affording various disilylhydrazido(2-) complexes cis, trans-[WI_2(NNSiMe_2CH_2CH_2SiMe_2)(PMe_2Ph)_2(L)](L = CO, CH_2=CH_2, RCN). In contrast, from the reaction mixture of 2 with 'BuNC a cationic complex mer-[WI(NNSiMe_2CH_2CH_2SiMe_2)(PMe_2Ph)_3]I has been isolated as the major product. Furthermore, 2 reacted with CH_2X_2 (X = I, Cl) to give paramagnetic W(V) complexes mer, trans-[WX_3(NNSiMe_2CH_2CH_2SiMe_2)(PMe_2Ph)_2]. Hydrolysis of this W(V) complex (X = I) and the subsequent condensation reaction with ketones afforded new W(V) complexes [WI_3(NNH_2)(PMe_2Ph)_2] and mer, trans-[WI_3(NN=CRR')(PMe_2Ph)_2], respectively.
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