John M. Brown, P. A. Chaloner, A. Kent
Aug 18, 1981
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Journal
Journal of Organometallic Chemistry
Abstract
Abstract Bicyclo [2,2,1]hepta-2,5-diene and cycloocta-1,5 diene(biphosphine)rhodium tetrafluoroborates react with hydrogen at 1 atmosphere in methanol or other polar solvents. The initial product may be either a solvated dihydride or a sol- vate; depending on phosphine structure the equilibrium between these two species varies widely. Dihydrides are normally the stable product when the ligand is a monophosphine although ( o -methoxyphenyl)methylphenylphos- phine is an exception. cis -Chelating biphosphines normally form solvate com plexes with no affinity for hydrogen. R -Phenyl bis-diphenylphosphinoethane falls into this category, but the 31 P NMR spectra of its complexes demonstrate an equilibrium between monomeric and dimeric species, and addition of triethylamine gives rise to a trimer. trans -Chelating biphosphines show more variable behaviour, and in the case of bis-1,5-diphenylphosphinopentane, a number of complexes, including one requiring C—H activation, are observed.