Bond Dissociation Energies and Kinetics for the Reaction of W(CO)5 with the Unlikely Ligands N2O and CF2Cl2

Paula L. Bogdan, J. R. Wells, Eric Weitz*

*Corresponding author for this work

Research output: Contribution to journalArticle

20 Scopus citations

Abstract

Transient infrared spectroscopy has been used to study reactions of W(CO)5, the coordinatively unsaturated tungsten carbonyl generated by 351- or 355-nm photolysis of W(CO)6. W(CO)5 is highly reactive toward CO, CF2Cl2, and N2O with bimolecular rate constants of 1.4 ± 0.1, 1.2 ± 0.2, and 0.5 ±0.1 × 10-10 cm3 molecule-1 s-1, respectively, at 298 K. Infrared absorptions for the transiently stable W(CO)5(CF2Cl2) and W(CO)5(N2O) complexes were observed. The rate of dissociative loss of the CF2Cl2 and N2O ligands from these complexes can be determined by observation of the rate of regeneration of W(CO)6 in a reaction mixture consisting of W(CO)5L, CO, and L, where L is either CF2C12 or N2O. The bond dissociation energy for the loss of the chlorofluorocarbon ligand from W(CO)5(CF2Cl2) is 19.6 ± 0.6 kcal/mol. A bond dissociation energy was estimated for the loss of the N2O ligand from W(CO)5(N2O).

Original languageEnglish (US)
Pages (from-to)1294-1299
Number of pages6
JournalJournal of the American Chemical Society
Volume113
Issue number4
DOIs
StatePublished - Jan 1 1991

ASJC Scopus subject areas

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

Fingerprint Dive into the research topics of 'Bond Dissociation Energies and Kinetics for the Reaction of W(CO)<sub>5</sub> with the Unlikely Ligands N<sub>2</sub>O and CF<sub>2</sub>Cl<sub>2</sub>'. Together they form a unique fingerprint.

  • Cite this