| Budget Amount *help |
¥18,590,000 (Direct Cost: ¥14,300,000、Indirect Cost: ¥4,290,000)
Fiscal Year 2015: ¥5,460,000 (Direct Cost: ¥4,200,000、Indirect Cost: ¥1,260,000)
Fiscal Year 2014: ¥6,240,000 (Direct Cost: ¥4,800,000、Indirect Cost: ¥1,440,000)
Fiscal Year 2013: ¥6,890,000 (Direct Cost: ¥5,300,000、Indirect Cost: ¥1,590,000)
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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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