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.
| Identifer | oai:union.ndltd.org:unt.edu/info:ark/67531/metadc331634 |
| Date | 05 1900 |
| Creators | Mansour, Saber E. (Saber El-Sayed) |
| Contributors | Dobson, Gerard R., Conlin, Robert T., Theriot, L. J., Desiderato, Robert, Schwartz, Martin |
| Publisher | North Texas State University |
| Source Sets | University of North Texas |
| Language | English |
| Detected Language | English |
| Type | Thesis or Dissertation |
| Format | ix, 149 leaves: ill., Text |
| Rights | Public, Mansour, Saber E. (Saber El-Sayed), Copyright, Copyright is held by the author, unless otherwise noted. All rights reserved. |
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