Reactivity of Five-Coordinate Intermediates Derived from (Chelate) Tetracarbonylmetal (0) Complexes

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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 ... continued below

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vii, 58 leaves : ill.

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Mansour, Saber E. (Saber El-Sayed) December 1983.

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

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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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vii, 58 leaves : ill.

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  • December 1983

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  • May 10, 2015, 6:16 a.m.

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  • Dec. 8, 2016, 9:06 a.m.

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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. (digital.library.unt.edu/ark:/67531/metadc504014/: accessed September 21, 2018), University of North Texas Libraries, Digital Library, digital.library.unt.edu; .