Octahedral metal carbonyls. 62. The mechanism of piperidine (pip) displacement by phosphines and phosphites (L') from cis-(pip)(L)W(CO)/sub 4/ complexes in chlorobenzene
Parallel thermal and pulsed laser flash photolysis studies of cis-(pip)(L)W(CO)/sub 4/ complexes (pip = piperidine; L = phosphines and phosphites) in their reactions with L' in chlorobenzene (CB) solvent and in CB/CH mixtures (CH = cyclohexane) indicate these reactions to proceed via reversible fission of the W-pip bond to produce square-pyramidal ((L)W(CO)/sub 4/) intermediates in which L occupies a position in the equatorial plane. These species undergo very rapid competitive reaction with pip, with L', and with CB to afford, ultimately, the thermally stable cis-(L')(L)W(CO)/sub 4/ products, which may undergo subsequent isomerization. The competition ratios for reactions of chlorobenzene, pip, and L' with ((L)W(CO)/sub 5/) have been measured photochemically and/or thermally, and these ratios have assisted in the identification of cis-((CB)(L)W(CO)/sub 4/), in which CB functions as a coordinating ligand, as the predominant species formed after photolysis. Rate constants and activation parameters for most steps in the ligand-substitution process are reported and are discussed in terms of the steric and electronic properties of both coordinated L, incoming L', and solvent.
- Research Organization:
- Texas State Univ., Denton
- OSTI ID:
- 6041343
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:18; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400500* -- Photochemistry
AROMATICS
CARBONYLS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
CHLORINATED AROMATIC HYDROCARBONS
COMPLEXES
DATA
DECOMPOSITION
EXPERIMENTAL DATA
HALOGENATED AROMATIC HYDROCARBONS
HYDROGEN COMPOUNDS
INFORMATION
INORGANIC ACIDS
KINETICS
LASERS
LIGANDS
NUMERICAL DATA
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
PHOSPHINES
PHOSPHOROUS ACID
PHOSPHORUS COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PHOTOLYSIS
PULSE TECHNIQUES
REACTION KINETICS
SOLVENTS
TRANSITION ELEMENT COMPLEXES
TUNGSTEN COMPLEXES