Mechanism of white phosphorus activation by three-coordinate molybdenum(III) complexes: A thermochemical, kinetic, and quantum chemical investigation

Frances H. Stephens, Marc J A Johnson, Christopher C. Cummins, Olga P. Kryatova, Sergey V. Kryatov, Elena V. Rybak-Akimova, J. Eric McDonough, Carl Hoff

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Abstract

White phosphorus (P4) reacts with three-coordinate molybdenum(III) trisamides or molybdaziridine hydride complexes to produce either bridging or terminal phosphide (P3-) species, depending upon the ancillary ligand steric demands. Thermochemical measurements have been made that place the Mo=P triple bond dissociation enthalpy at 92.2 kcal·mol-1. Thermochemical measurements together with computational analysis rule out simple P-atom abstraction from P4 as a step in the phosphorus activation mechanism. Kinetic measurements made by the stopped-flow method show that the reaction between the monomeric molybdenum complexes and P4 is first-order both in metal complex and in P 4. cyclo-P3 complexes can be obtained when ancillary ligand steric demands are small, but kinetic measurements rule them out as monometallic intermediates in the P4 activation mechanism. Also studied by calorimetric, kinetic, and in one case variable-temperature NMR methods is the process of μ-phosphide bridge formation. Post-rate-determining steps of the P4 activation process were examined in a search for minima on the reaction's potential energy surface, leading to the proposal of two plausible, parallel, bimetallic reaction channels.

Original languageEnglish
Pages (from-to)15191-15200
Number of pages10
JournalJournal of the American Chemical Society
Volume127
Issue number43
DOIs
StatePublished - Nov 2 2005

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Molybdenum
Phosphorus
Chemical activation
Kinetics
Ligands
Coordination Complexes
Potential energy surfaces
Metal complexes
Hydrides
Enthalpy
Temperature
Nuclear magnetic resonance
Atoms

ASJC Scopus subject areas

  • Chemistry(all)

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Mechanism of white phosphorus activation by three-coordinate molybdenum(III) complexes : A thermochemical, kinetic, and quantum chemical investigation. / Stephens, Frances H.; Johnson, Marc J A; Cummins, Christopher C.; Kryatova, Olga P.; Kryatov, Sergey V.; Rybak-Akimova, Elena V.; McDonough, J. Eric; Hoff, Carl.

In: Journal of the American Chemical Society, Vol. 127, No. 43, 02.11.2005, p. 15191-15200.

Research output: Contribution to journalArticle

Stephens, Frances H. ; Johnson, Marc J A ; Cummins, Christopher C. ; Kryatova, Olga P. ; Kryatov, Sergey V. ; Rybak-Akimova, Elena V. ; McDonough, J. Eric ; Hoff, Carl. / Mechanism of white phosphorus activation by three-coordinate molybdenum(III) complexes : A thermochemical, kinetic, and quantum chemical investigation. In: Journal of the American Chemical Society. 2005 ; Vol. 127, No. 43. pp. 15191-15200.
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