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

Mark Green, John C. Huffman, Kenneth G. Caulton

Research output: Contribution to journalArticle

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Abstract

UV (254 nm) photolysis of OsH4P3 (P PMe2Ph) proceeds, by photodissociation of H2, to give the transient OsH2P3. This species exchanges deuterium with C6D6, reacts with phosphine to give cis-H2 OsP4, and with OsHxP3 to give us Os2H2(μ-H)2P6, whose structure was determined by X-ray diffraction. This OsOs dimer participates in a unique reversible (25°C) phosphin dissociation equilibrium to produce Os2H4P5, containing an OsOs bond. A structural analog of this dimer was produced by acidolysis of Os2H4P6 to give Os2H3P6+, which X-ray diffraction reveals to have a P3Os(μ-H)3OsP3+ structure.

Original languageEnglish
JournalJournal of Organometallic Chemistry
Volume243
Issue number4
DOIs
StatePublished - Feb 22 1983

Fingerprint

Photodissociation
phosphine
Dimerization
dimerization
X-Ray Diffraction
Dimers
photodissociation
Transition metals
Metals
transition metals
dimers
X ray diffraction
Deuterium
Photolysis
diffraction
phosphines
photolysis
deuterium
x rays
dissociation

ASJC Scopus subject areas

  • Biochemistry
  • Chemical Engineering (miscellaneous)
  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Science (miscellaneous)
  • Materials Chemistry

Cite this

Photochechemistry of transition-metal polyhydrides : dimerization of OsH4 (PMe2Ph)3 following photodissociation of dihydrogen. / Green, Mark; Huffman, John C.; Caulton, Kenneth G.

In: Journal of Organometallic Chemistry, Vol. 243, No. 4, 22.02.1983.

Research output: Contribution to journalArticle

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abstract = "UV (254 nm) photolysis of OsH4P3 (P PMe2Ph) proceeds, by photodissociation of H2, to give the transient OsH2P3. This species exchanges deuterium with C6D6, reacts with phosphine to give cis-H2 OsP4, and with OsHxP3 to give us Os2H2(μ-H)2P6, whose structure was determined by X-ray diffraction. This OsOs dimer participates in a unique reversible (25°C) phosphin dissociation equilibrium to produce Os2H4P5, containing an OsOs bond. A structural analog of this dimer was produced by acidolysis of Os2H4P6 to give Os2H3P6+, which X-ray diffraction reveals to have a P3Os(μ-H)3OsP3+ structure.",
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AU - Caulton, Kenneth G.

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N2 - UV (254 nm) photolysis of OsH4P3 (P PMe2Ph) proceeds, by photodissociation of H2, to give the transient OsH2P3. This species exchanges deuterium with C6D6, reacts with phosphine to give cis-H2 OsP4, and with OsHxP3 to give us Os2H2(μ-H)2P6, whose structure was determined by X-ray diffraction. This OsOs dimer participates in a unique reversible (25°C) phosphin dissociation equilibrium to produce Os2H4P5, containing an OsOs bond. A structural analog of this dimer was produced by acidolysis of Os2H4P6 to give Os2H3P6+, which X-ray diffraction reveals to have a P3Os(μ-H)3OsP3+ structure.

AB - UV (254 nm) photolysis of OsH4P3 (P PMe2Ph) proceeds, by photodissociation of H2, to give the transient OsH2P3. This species exchanges deuterium with C6D6, reacts with phosphine to give cis-H2 OsP4, and with OsHxP3 to give us Os2H2(μ-H)2P6, whose structure was determined by X-ray diffraction. This OsOs dimer participates in a unique reversible (25°C) phosphin dissociation equilibrium to produce Os2H4P5, containing an OsOs bond. A structural analog of this dimer was produced by acidolysis of Os2H4P6 to give Os2H3P6+, which X-ray diffraction reveals to have a P3Os(μ-H)3OsP3+ structure.

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