2015 Fiscal Year Final Research Report
Synthesis of Coordinatively Unsaturated Complexes with Metal-Metal Bonds
| Project/Area Number |
25288026
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Partial Multi-year Fund |
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| Section | 一般 |
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| Research Field |
Inorganic chemistry
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| Research Institution | Tokyo Institute of Technology |
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Principal Investigator |
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| Project Period (FY) |
2013-04-01 – 2016-03-31
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| Keywords | 金属間結合 / フェノキシド配位子 / 二核錯体 / ヒドリド錯体 |
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| Outline of Final Research Achievements |
The starting complex (ArO)2NbCl2 (1) is prepared by the reaction of NbCl4(THF)2 with LiOAr in TH. The complex 1 is monomeric, and the metal center adopts a distorted tetrahedral geometry. Addition of KBHEt3 to 1 resulted in formation of diamagnetic [(ArO)2Nb]2(μ-H)4 (2),in which two metal centers are bridged by four hydride ligands. Exposure of 2 to CO led to formation of the vinylidene complex (3). The reaction process leading to 3 includes CO hydrogenation, deoxygenation, and C-C coupling accompanied by loss of four hydride ligands and one adamantyl group. When carbonylation of 2 was monitored by NMR spectroscopy, an intermediate [(AdArO)2Nb]2(μ-O)(μ-CH2) (4) was observed and it cleanly converted to the vinylidene complex 3 over a period of several hours. In this study, we have shown that the reactive metal-metal bond play an important role in CO activation.
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| Free Research Field |
錯体化学
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