Solution Calorimetric and Stopped-Flow Kinetic Study of Ligand Substitution for the Complexes M(CO)3(PCy3)2(L) (M = Cr, Mo, W). Comparison of First-, Second-, and Third-Row Transition-Metal-Ligand Bonds at a Sterically Crowded Metal Center

Kai Zhang, Alberto A. Gonzalez, Shakti L. Mukerjee, Shou Jiau Chou, Carl D. Hoff, Kimberly A. Kubat-Martin, David Barnhart, Gregory J. Kubas

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59 Scopus citations

Abstract

The substitution of pyridine by trimethyl phosphite in the complexes M(CO)3(PCy3)2(py) (M = Cr, Mo) has been studied by stopped-flow kinetics. Direct reactions of the proposed intermediate complexes M(CO)3(PCy3)2 (M = Cr, Mo) have also been studied. The crystal structure of Cr(CO)3(PCy3)2 has been determined and shows an an agostic M-H-C interaction. Cell parameters: a = 10.127 (2) Å, b = 12.524 (3) Å, c = 15.329 (3) Å, β = 90.93 (3)°, γ = 103.28 (3)°, space group P1, Z = 2. These results are combined with calorimetric measurements, and with earlier data on the isostructural W complex, to give a complete picture of ligand substitution in these sterically crowded complexes. The relative rates of dissociation of the M-py bond are in the order Cr > Mo > W in the approximate ratio 4800/300/1. The relative rates of reaction of the formally coordinatively unsaturated complexes M(CO)3(PCy3)2 with trimethyl phosphite are in the order Mo > W > Cr in the approximate ratio 80/36/1. Due to these changes in relative magnitude for the rate constants, the chromium complex does not obey simple steady-state kinetics. Solution calorimetric measurements show that the enthalpies of binding of pyridine and trimethyl phosphite are as follows: W, -19 and -26 kcal/mol; Mo, -17 and -24 kcal/mol; Cr, -16 and -11 kcal/mol. Enthalpies of activation for dissociation of pyridine: W,-22.6 kcal/mol; Mol; -21.9 kcal/mol; Cr, -15.1 kcal/mol. The activation energy for addition of py to M(CO)3(PCy3)2 is about 4 kcal/mol for all three metals and probably involves concerted attack at the agostic bond.

Original languageEnglish (US)
Pages (from-to)9170-9176
Number of pages7
JournalJournal of the American Chemical Society
Volume113
Issue number24
DOIs
StatePublished - Nov 1 1991

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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