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Kinetics Studies of Substituted Tungsten Carbonyl Complexes

Thermal reactions and flash photolysis are used to study the olefin bond-migration promoted by tungsten carbonyls. Substitution of piperidine (pip) by 2- allylphenyldiphenylphosphine (adpp) in the cis-(pip)(η^1- adpp)W(CO)-4 complex was investigated, and no olefin bond-migration was observed. This suggests that a vacant coordinated site adjacent to the coordinated olefin is an essential requirement for olefin bond rearrangement.
The rates of olefin attack on the photogenerated coordinatively unsaturated species, cis-[(CB)(η^1-ol- P)W(CO)-4] (CB = chlorobenzene, p-ol = Ph-2P(CH-2)-3CH=CH-2; n = 1-4) were measured. Kinetics data obtained both in pure CB
and in CB/cyclohexane mixtures support a dissociative mechanism in which the W-CB bond is broken in the transition state. In contrast to results observed in studies of other related systems, no olefin bond-migration is noted. This observation is attributed to P-W coordination at all stages of the reaction, which precludes formation of a reactive intermediate containing a vacant coordination site adjacent to a P-ol bond.

Identiferoai:union.ndltd.org:unt.edu/info:ark/67531/metadc330797
Date08 1900
CreatorsWang, I-Hsiung, 1950-
ContributorsDobson, Gerard R., Schwartz, Martin, Roberts, James Andrew, Jones, Paul R., Brady, William Thomas
PublisherUniversity of North Texas
Source SetsUniversity of North Texas
LanguageEnglish
Detected LanguageEnglish
TypeThesis or Dissertation
Formatix, 144 leaves: ill., Text
RightsPublic, Wang, I-Hsiung, 1950-, Copyright, Copyright is held by the author, unless otherwise noted. All rights reserved.

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