Thermal and flash photolysis studies of ligand-substitution reactions of cis-(pip)(L)M(CO)_4 by L' (pip = piperidine; L, L' = CO, phosphines, phosphites; M = Cr, Mo) implicate square-pyramidal [(L)M(CO)_4], in which L occupies a coordination site in the equatorial plane, as the reactive species. In chlorobenzene (= CB) solvent, the predominant species formed after flash photolysis and a steady-state intermediate for the thermal reaction is cis—[(CB)(L)M(CO)_4], for which rates of CB-dissociation increase with increasing steric demands of coordinated L. Rates of CB-dissociation from trans-[(CB)(L)M(CO)_4] intermediates, formed after photolysis but not thermally, exhibit no observable dependence on the steric properties of the coordinated L.
| Identifer | oai:union.ndltd.org:unt.edu/info:ark/67531/metadc332097 |
| Date | 05 1900 |
| Creators | Awad, Hani H. (Hani Hanna) |
| Contributors | Dobson, Gerard R., Conlin, Robert T., Thomas, Ruthanne D., Schwartz, Martin, Jones, Paul R., Kunz, Daniel A. |
| Publisher | University of North Texas |
| Source Sets | University of North Texas |
| Language | English |
| Detected Language | English |
| Type | Thesis or Dissertation |
| Format | xii, 174 leaves : ill., Text |
| Rights | Public, Awad, Hani H. (Hani Hanna), Copyright, Copyright is held by the author, unless otherwise noted. All rights reserved. |
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