Kinetics Studies of Substituted Tungsten Carbonyl Complexes

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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 ... continued below

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ix, 144 leaves: ill.

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Wang, I-Hsiung, 1950- August 1989.

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  • Wang, I-Hsiung, 1950-

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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.

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ix, 144 leaves: ill.

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  • August 1989

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  • Aug. 22, 2014, 6 p.m.

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  • Sept. 3, 2015, 12:50 p.m.

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Wang, I-Hsiung, 1950-. Kinetics Studies of Substituted Tungsten Carbonyl Complexes, dissertation, August 1989; Denton, Texas. (digital.library.unt.edu/ark:/67531/metadc330797/: accessed September 19, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; .