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 …
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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.
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Mansour, Saber E. (Saber El-Sayed).Reactivity of Five-Coordinate Intermediates Derived from (Chelate) Tetracarbonylmetal (0) Complexes,
thesis,
December 1983;
Denton, Texas.
(https://digital.library.unt.edu/ark:/67531/metadc504014/:
accessed June 11, 2024),
University of North Texas Libraries, UNT Digital Library, https://digital.library.unt.edu;
.