The reactivity of the [(Phen)Cr(CO)_3] intermediate with phosphines and phosphites (L) has been investigated through ligand-competition studies. This intermediate possesses virtually no ability to discriminate among L. The agreement between reactivity data for the thermal and photochemically-generated intermediates indicates that the same intermediate is produced via each process. Pulsed laser flash photolysis of (n^2-NP)M(CO)_4 (I) (M = Cr, Mo; NP = 1-diethylamino-2-diphenylphosphinoethane) in the absence and presence of P (OPr-i)_3 (L) in 1,2-dichloroethane and chlorobenzene induces unimolecular ring-opening to afford [(n^1-NP)M(CO)_4] (II), in which the bidentate ligand is coordinated through P. Reaction of this intermediate takes place through competitive ring-reclosure and attack at (II) by L to afford (I) and cis-(n^1-NP) (L)M(CO)_4.
| Identifer | oai:union.ndltd.org:unt.edu/info:ark/67531/metadc504014 |
| Date | 12 1900 |
| Creators | Mansour, Saber E. (Saber El-Sayed) |
| Contributors | Dobson, Gerard R., Theriot, L. J. |
| Publisher | North Texas State University |
| Source Sets | University of North Texas |
| Language | English |
| Detected Language | English |
| Type | Thesis or Dissertation |
| Format | vii, 58 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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