TY - JOUR
T1 - Bond Dissociation Energies and Kinetics for the Reaction of W(CO)5 with the Unlikely Ligands N2O and CF2Cl2
AU - Bogdan, Paula L.
AU - Wells, J. R.
AU - Weitz, Eric
PY - 1991
Y1 - 1991
N2 - 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).
AB - 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).
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U2 - 10.1021/ja00004a033
DO - 10.1021/ja00004a033
M3 - Article
AN - SCOPUS:0001312078
SN - 0002-7863
VL - 113
SP - 1294
EP - 1299
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 4
ER -