Synthesis, structure, and thermochemistry of the formation of the metal-metal bonded dimers [Mo(μ-TeAr)(CO)3(PiP 3)]2 (Ar = phenyl, naphthyl) by phosphine elimination from Mo(TePh)(CO)3(PiPr3) 2

John J. Weir, James E. McDonough, George Fortman, Derek Isrow, Carl D. Hoff, Brian Scott, Gregory J. Kubas

Research output: Contribution to journalArticlepeer-review

2 Scopus citations

Abstract

The complexes (TeAr)Mo(CO)3(P iPr3)2 (Ar = phenyl, naphthyl; iPr = isopropyl) slowly eliminate PiPr3 at room temperature in a toluene solution to quantitatively form the dinuclear complexes [Mo(μ-TeAr)(CO)3(PiPr3)]2. The crystal structure of [Mo(μ-Te-naphthyl)(CO)3(PiPr 3)]2 is reported and has a Mo-Mo distance of 3.2130 Å. The enthalpy of dimerization has been measured and is used to estimate a Mo-Mo bond strength on the order of 30 kcal mol-1. Kinetic studies show the rate of formation of the dimeric chalcogen bridged complex is best fit by a rate law first order in (TeAr)Mo(CO)3(P iPr3)2 and inhibited by added PiPr3. The reaction is proposed to occur by initial dissociation of a phosphine ligand and not by radical recombination of 2 mol of (TeAr)Mo(CO) 3(PiPr3)2. Reaction of ( TePh)Mo(CO)3(PiPr3) 2, with L = pyridine (py) or CO, is rapid and quantitative at room temperature to form PhTeTePh and Mo(L)(CO)3(PiPr 3)2, in keeping with thermochemical predictions. The rate of reaction of (TeAr)W-(CO)3(PiPr 3)2 and CO is first-order in the metal complex and is proposed to proceed by the associative formation of the 19 e- radical complex (TePh)W(CO)4(PiPr 3)2 which extrudes a TePh radical.

Original languageEnglish (US)
Pages (from-to)652-659
Number of pages8
JournalInorganic Chemistry
Volume46
Issue number3
DOIs
StatePublished - Feb 5 2007
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Fingerprint Dive into the research topics of 'Synthesis, structure, and thermochemistry of the formation of the metal-metal bonded dimers [Mo(μ-TeAr)(CO)<sub>3</sub>(P<sup>i</sup>P <sub>3</sub>)]<sub>2</sub> (Ar = phenyl, naphthyl) by phosphine elimination from <sup>•</sup>Mo(TePh)(CO)<sub>3</sub>(P<sup>i</sup>Pr<sub>3</sub>) <sub>2</sub>'. Together they form a unique fingerprint.

Cite this