1992•Bulletin of the Chemical Society of JapanRequires access

Syntheses and Structures of Novel Ruthenium(II)-Chiral Diphosphine Complexes

Hiroyuki Kawano, Takao Ikariya, Youichi Ishii, Teruyuki Kodama, Masahiko Saburi, Sadao Yoshikawa, Yasuzo Uchida, Susumu Akutagawa

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Abstract

Abstract Novel ruthenium complexes coordinated with various chiral diphosphines were synthesized by reactions of polynuclear [RuCl2(cycloocta-1,5-diene)]n with the respective diphosphines in the presence of triethylamine. The compositions of the complexes thus obtained were varied according to the solvent used (toluene or ethanol). The structures and dynamic properties of the complexes bearing 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (binap) in solution were elucidated by the 1H and 31P{1H} NMR measurements. The X-ray diffraction analysis of trans-RuHCl((R)-binap)2 indicated that the conformation of seven-membered chelate rings and the edge-face manner of phenyl groups were almost the same as those of corresponding rhodium complexes.

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Abstract Novel ruthenium complexes coordinated with various chiral diphosphines were synthesized by reactions of polynuclear [RuCl2(cycloocta-1,5-diene)]n with the respective diphosphines in the presence of triethylamine. The compositions of the complexes thus obtained were varied according to the solvent used (toluene or ethanol). The structures and dynamic properties of the complexes bearing 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (binap) in solution were elucidated by the 1H and 31P{1H} NMR measurements. The X-ray diffraction analysis of trans-RuHCl((R)-binap)2 indicated that the conformation of seven-membered chelate rings and the edge-face manner of phenyl groups were almost the same as those of corresponding rhodium complexes.

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Available abstract

Abstract Novel ruthenium complexes coordinated with various chiral diphosphines were synthesized by reactions of polynuclear [RuCl2(cycloocta-1,5-diene)]n with the respective diphosphines in the presence of triethylamine. The compositions of the complexes thus obtained were varied according to the solvent used (toluene or ethanol). The structures and dynamic properties of the complexes bearing 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (binap) in solution were elucidated by the 1H and 31P{1H} NMR measurements. The X-ray diffraction analysis of trans-RuHCl((R)-binap)2 indicated that the conformation of seven-membered chelate rings and the edge-face manner of phenyl groups were almost the same as those of corresponding rhodium complexes.

Key concepts: Diphosphines, Chemistry, BINAP, Ruthenium, Triethylamine, Rhodium, Chelation, Medicinal chemistry

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