Octahedral metal carbonyls. 67. Rates of reaction of olefins with cis((chlorobenzene)(triphenylphosphine tetracarbonyltungsten(O))) produced via pulsed laser flash photolysis
- Univ. of North Texas, Denton (USA)
Rates of reaction of olefins and diolefins (1-hexene, cyclohexene, norbornene, cis-2-heptene, trans-4-octene, 1,5-hexadiene, 2,3-dimethyl-2-butene) with cis-((CB)(PPh{sub 3})W(CO){sub 4}) (CB = chlorobenzene) produced upon pulsed laser flash photolysis of cis-(pip)(PPh{sub 3})W(CO){sub 4} in CB solution have been determined, for some systems at several temperatures. Olefin-coordination takes place after reversible CB-dissociation from cis-((CB)(PPh{sub 3})W(CO){sub 4}), a predominant species present in solution after flash photolysis. These rates have been compared to those for analogous reactions with Lewis bases coordinating through N (piperidine) and P (P(O-i-Pr){sub 3}); all rates are roughly similar. Thus, despite the greater thermodynamic stability of complexes containing W-N and W-P bonds, olefin coordination to W is competitive with W-N and W-P coordination. The implications of these conclusions with respect to mechanisms of olefin catalysis by coordinatively unsaturated Group VI-B metal carbonyl intermediates are discussed.
- OSTI ID:
- 6903215
- Journal Information:
- Journal of Coordination Chemistry; (USA), Journal Name: Journal of Coordination Chemistry; (USA) Vol. 20:2; ISSN 0095-8972; ISSN JCCMB
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
360100 -- Metals & Alloys
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400000* -- Chemistry
400200 -- Inorganic
Organic
& Physical Chemistry
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
COMPLEXES
DATA
DATA ANALYSIS
DECOMPOSITION
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
KINETICS
MEASURING INSTRUMENTS
MEASURING METHODS
NUMERICAL DATA
ORGANIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOLYSIS
REACTION KINETICS
TRANSITION ELEMENT COMPLEXES
TUNGSTEN COMPLEXES