2004 Fiscal Year Final Research Report Summary
Synthesis of Silyl- and Germyl-substituted Borates and their Application to Catalytic Reactions
| Project/Area Number |
15550041
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Organic chemistry
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| Research Institution | Gakushuin University |
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Principal Investigator |
MOCHIDA Kunio Gakushuin University, Faculty of Science, Professor, 理学部, 教授 (20118772)
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| Co-Investigator(Kenkyū-buntansha) |
NANJO Masato Gakushuin University, Faculty of Science, Assistant professor, 理学部, 助手 (50302352)
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| Project Period (FY) |
2003 – 2004
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| Keywords | silylborate / germyiborate / X-ray diffraction analysis / group 14 element ketone / nucleophile / photochemical reaction / CIDEP / triplet state |
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| Research Abstract |
Silylborats, (Li[Ph_nMe_<3-n>SiBPh_3], n = 1-3), and germylborates, (Li[Ph_nMe_<3-n>GeBPh_3], n = 1-3) and (E[Et_3GeBPh_3], E = Li, Na, K), were prepared by the reaction of the corresponding silyl- and germylalkali metals with triphenylborane in a hexane/benzene mixed solvent The silyl- and germylborates were fully identified by ^1H, ^<13>C, ^<11>B, and ^7Li NMR spectroscopic methods. Germylborates, Li[Ph_3GeBPh_3] and E[Et_3GeBPh_3] (E = Li and Na), were also determined by X-ray diffraction analyses. The polymeric structure of E[Et_3GeBPh_3] was observed in the solid state and in a hydrocarbon solvent. The alkali metal atoms were located near the center of the benzene ring of triphenylborane and interacted with the neighboring borate molecules by the Li^+-π interaction. The polymeric structure was destroyed by the addition of MeOH, however, E[Et_3GeBPh_3] was coordinated by three MeOH molecules to form the dimeric structure without methanolysis reaction. The primary processes in photochemical reactions of silyl- and germylborates were investigated by chemical trapping experiments and CIDEP method. The cleavage of Ge-B (or Si-B) bonds of germylborates (or silylborates) was most probably considered to occur from their triplet states.
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