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

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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 ... continued below

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ix, 149 leaves: ill.

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Mansour, Saber E. (Saber El-Sayed) May 1986.

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  • Mansour, Saber E. (Saber El-Sayed)

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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.

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ix, 149 leaves: ill.

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  • May 1986

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  • Aug. 22, 2014, 6 p.m.

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Mansour, Saber E. (Saber El-Sayed). The Nature of Intermediates Produced Through Ligand-Substitution Reactions of Octahedral Metal Carbonyls, dissertation, May 1986; Denton, Texas. (digital.library.unt.edu/ark:/67531/metadc331634/: accessed November 23, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; .