Structure and Reactivity of ReH4(PMe2Ph)4+

Diane M. Lunder, Mark A. Green, William E. Streib, Kenneth G. Caulton

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19 Scopus citations

Abstract

Protonation of ReH3P4 (P = PMe2Ph) with HBF4·OEt2 in Et2O gives ReH4P4+, which neither exchanges with D2 nor reacts with PhC≡CPh, CO, MeCN, or C2H4 under mild conditions. These results, together with an X-ray crystal structure determination, are consistent with a "classical" tetrahydride formulation for this cation, and the lack of reactivity correlates with the absence of coordinated H2 as a ligand. NEt3 will not deprotonate ReH4P4+ since it is a weaker base than ReH3P4. The implied electron-rich character of ReH3P4 thus rationalizes why protonation results in formal oxidation to Re(V), rather than retention of Re(III) as in Re(H)2(H2)P4+. The T1 value of the hydrogens bound to rhenium is 97 ms at -70°C and 360 MHz.

Original languageEnglish (US)
Pages (from-to)4527-4531
Number of pages5
JournalInorganic Chemistry
Volume28
Issue number25
DOIs
StatePublished - Dec 1 1989

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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