Structure and Reactivity of ReH4(PMe2Ph)4+

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

Research output: Contribution to journalArticle

18 Citations (Scopus)

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

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Protonation
rhenium
reactivity
Rhenium
formulations
cations
ligands
oxidation
crystal structure
hydrogen
Carbon Monoxide
Cations
Hydrogen
electrons
x rays
Crystal structure
Ligands
X rays
Oxidation
Electrons

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Lunder, D. M., Green, M. A., Streib, W. E., & Caulton, K. G. (1989). Structure and Reactivity of ReH4(PMe2Ph)4+. Inorganic Chemistry, 28(25), 4527-4531. https://doi.org/10.1021/ic00324a020

Structure and Reactivity of ReH4(PMe2Ph)4+. / Lunder, Diane M.; Green, Mark A.; Streib, William E.; Caulton, Kenneth G.

In: Inorganic Chemistry, Vol. 28, No. 25, 01.12.1989, p. 4527-4531.

Research output: Contribution to journalArticle

Lunder, DM, Green, MA, Streib, WE & Caulton, KG 1989, 'Structure and Reactivity of ReH4(PMe2Ph)4+', Inorganic Chemistry, vol. 28, no. 25, pp. 4527-4531. https://doi.org/10.1021/ic00324a020
Lunder, Diane M. ; Green, Mark A. ; Streib, William E. ; Caulton, Kenneth G. / Structure and Reactivity of ReH4(PMe2Ph)4+. In: Inorganic Chemistry. 1989 ; Vol. 28, No. 25. pp. 4527-4531.
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N2 - 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.

AB - 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.

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