Vinylidene transition-metal complexes
作者： H. Werner , J. Wolf , F.J.G. Alonso , M.L. Ziegler , O. Serhadli
DOI: 10.1016/0022-328X(87)85200-2
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摘要: Abstract The syntheses of the novel cyclopentadienylphosphinevinylidenerhodium complexes C 5 H Rh(CCHR)(PPr i 3 ) (R = Ph, Me, H) and, for R isomeric alkynyl hydrido compound RhH(C 2 Ph)(PPr are reported. square-planar trans -[RhCl(RC H)(PPr ] (IIa, IIb), which in solution equi-librium with five-coordinated pyridine to give octahedral compounds RhHCl(C R)(PRr (py) (VIa, VIb). Treatment Via, VIb NaC gives vinylidene IVa, IVb good yield. Rh(CCH )(PPr (IVc) is directly obtained from -[RhCl(C (IIc) and . Mechanistic studies confirm that reaction VIa, cyclopentadienide anion primarily gives, by elimination HCl, rhodium(I) -[Rh(C R)(py)(PPr (VIIIa, VIIIb), react cyclopentadiene, possibly via R)(η -C 6 ](X) as an intermediate, VIIIa cyclopentadiene presence water complex ), isomerizes only slowly form IVa therefore, not intermediate IVa. crystal structure has been determined. RhCC arrangement almost linear. RhC distance significantly shorter than carbenerhodium complexes, which, agreement 13 NMR data MO calculations, indicates a high degree multiple bonding.
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sci-hub.se 参考文章(24)
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