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Photochechemistry of transition-metal polyhydrides: dimerization of OsH4(PMe2Ph)3following photodissociation of dihydrogen

Authors
Journal
Journal of Organometallic Chemistry
0022-328X
Publisher
Elsevier
Publication Date
Volume
243
Issue
4
Identifiers
DOI: 10.1016/s0022-328x(00)98584-x

Abstract

Abstract UV (254 nm) photolysis of OsH 4P 3 (P  PMe 2Ph) proceeds, by photodissociation of H 2, to give the transient OsH 2P 3. This species exchanges deuterium with C 6D 6, reacts with phosphine to give cis-H 2 OsP 4, and with OsH x P 3 to give us Os 2H 2(μ-H) 2P 6, whose structure was determined by X-ray diffraction. This OsOs dimer participates in a unique reversible (25°C) phosphin dissociation equilibrium to produce Os 2H 4P 5, containing an OsOs bond. A structural analog of this dimer was produced by acidolysis of Os 2H 4P 6 to give Os 2H 3P 6 +, which X-ray diffraction reveals to have a P 3Os(μ-H) 3OsP 3 + structure.

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