Date: May 1986
Creator: Mansour, Saber E. (Saber El-Sayed)
Description: Pulsed laser time-resolved ligand-substitution photochemistry for (DTO)W(CO)4, (DTN)W(CO)4, and (NP)Mo(CO)4 (DTO = 2,2,7,7-tetramethyl-3,6-diathiaoctane; DTN = 2,2,8,8- tetramethyl-3,7-diathianonane; NP = l-diethylamino-2- diphenylphosphinoethane) proceeds via initial fission of the W-S and Mo-P bonds, affording Cs and C4v five-coordinate intermediates for DTN and NP but largely Cs for DTO. The rates of reaction of these intermediates, via chelate ring closure and competitive bimolecular interaction with Lewis bases (= L, alkylphosphines and alkyl phosphites) for the Cs intermediates and via bimolecular interaction of L with the C4v intermediates, together with activation parameters for these processes have been determined. The rates of interactions at the Cs intermediates are significantly faster than at the C4v intermediates.
Contributing Partner: UNT Libraries