1991 Fiscal Year Final Research Report Summary
Electrosynthesis and Reactions of Platinum Triad Metal Cluster Containing Bidentate Phosphine
| Project/Area Number |
02640484
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| Research Category |
Grant-in-Aid for General Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Research Field |
無機・錯塩・放射化学
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| Research Institution | Toho University |
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Principal Investigator |
YAMAMOTO Yasuhiro Toho University, Faculty of Science, Professor, 理学部, 教授 (40087515)
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| Co-Investigator(Kenkyū-buntansha) |
TANASE Tomoaki Toho University, Assistant Professor, 理学部, 講師 (50207156)
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| Project Period (FY) |
1990 – 1991
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| Keywords | EHMO calculations of dinuclear and trinuclear platinum complexes / Naked platinum complex / A-frame complex / 配位不飽和白金錯体 / Aーframe錯体 / 白金錯体のESCA |
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| Research Abstract |
Electrochemical reductionsof isocyanide. complexes of platinum and palladium [M(RNC)_2(diphos)]^<2+> (1) (M = Pt, Pd ; diphos = PP_2P(CH_2)_nPPh_2, n = 1, 2, 3, 4) containing bidentate phosphine ligands were carried out. One electron reduction of (1) gave [M_2(RNC)_2(diphos)_2]^<2+>. The dppm (n = 1) complex has a trans-dppm structure, containing a mu-coordination to two metals and other diphosphine complexes (n = 2, 3, 4) have a chelate structure. A 1.5 electron reduction of (1) gave tri-nuclear complexes, [M_3(RNC)_4(diphos)_2]^<2+> (M = pt. Pd ; ri = 1, 2, 4) (2) and [Pt_3(RNC)_2(diphos)_2]^<2+> (n = 3) (3), depending on diphosphine ligands. In the complex (2), the dppm (n = 1) complex has a A-frame structure and other ones have a linear structure which two diphosphines chelated to two outer metals. The remarkable feature of (3) is the central platinum atom, which is bound only to other Pt atoms. To our knowledge, this is the first example of an electron-deficient tri-platinum compound. The electronic structure of the naked platinum of (3) was estimated by EHMO calculations of the model complexes, in which the charge separation of outer and central atoms was observed. This was confirmed by ESCA of (3). Reactions of dinuclear complexes with d^<10> ML_2 fragments led to an insertion of ML_2 one into a metal-metal bond to give homo-, heteronuclear or A-frame complexes. Reaction with RNC was also carried out.
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Research Products
(4 results)
