The Nature of Intermediates Produced Through Ligand-Substitution Reactions of Octahedral Metal Carbonyls

• Main Author: Mansour, Saber E. (Saber El-Sayed)
• Other Authors: Dobson, Gerard R.
• Format: Others
• Language: English
• Published: North Texas State University 1986
• Subjects: ligand-substitution; ring formation; carbonyl compounds; Ligands.; Carbonyl compounds.
• Online Access: https://digital.library.unt.edu/ark:/67531/metadc331634/

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.