Synthesis and Characterization of Mono- and Tri-nuclear Ruthenium Complexes of 2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl and Their Catalytic Activity

DOI: 10.1039/DT9920002099

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Journal of the Chemical Society, Dalton Transactions p. 2099 - 2108 (1992)

Update date:2022-07-30

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Authors:

Mashima, Kazushi

Hino, Takahiro

Takaya, Hidemasa

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Article abstract of DOI:10.1039/DT9920002099

The structures of ruthenium(II) complexes formed in solution from Y (S)-3 (X, Y = halide and/or BF4^-; binap = 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl; arene = benzene or p-cymene) depend on the solvent.In acetonitrile-methanol (1:1) dicationic complexes X(Y) (S)-4 (X = Y = Cl a; X = Cl, Y = BF4 b; X = Y = Br c; or X = Y = I d) are predominantly formed, while monocationic species X (S)-6 (X = Cl a, Br b or I c) were observed in acetonitrile.These mono- and di-cationic species could not be isolated pure, while (S)-5 was isolated from (S)-4a or (S)-6a upon concentration of the reaction mixture.In methanol without donor molecules such as acetonitrile, cationic trinuclear complexes Y (S)-7 (X = Y = Cl a; X = Cl, Y = BF4 b or X = Y = Br c) were exclusively formed by heating at 60 deg C or UV irradiation of a solution of (S)-3.The structure of (S)-7 was characterized by spectral data and an X-ray crystallographic analysis of (S)-7b 12₁2₁, a = 26.328(5), b = 18.140(3), c = 26.374(4), Z = 4, R'= 0.083>.The relationship between the structure of the Ru^II(binap) complexes and their catalytic activities for asymmetric hydrogenation of methyl 3-oxobutanoate has been investigated.

Full text of DOI:10.1039/DT9920002099

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