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- W2897714885 abstract "The linkage isomers [(OC)5W{κ1-PPh2CH2CH(PPh2)[P(p-tol)2]}] 3a, [(OC)5W{κ1-P(p-tol)2CH(PPh2)CH2PPh2}] 3b, and [(OC)5W{κ1-PPh2CH[P(p-tol)2]CH2PPh2}] 3c isomerize at ambient temperatures to give a mixture of the three isomers in equilibrium. Rates of isomerization and equilibrium constants have been measured at temperatures from 10 to 55 °C, and from these, enthalpies and entropies have been determined. The isomerization reactions are initiated by a nucleophilic attack of a pendant phosphine on a bound carbonyl group followed by dissociation of a coordinated phosphine. These studies lead us to suggest that the k2 term in the rate law for CO replacement by phosphines is based on a similar mechanism and offers a plausible clarification of the currently accepted understanding. The crystal structure of 3b, the most stable of the three isomers, has been determined." @default.
- W2897714885 created "2018-10-26" @default.
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- W2897714885 date "2018-10-16" @default.
- W2897714885 modified "2023-09-25" @default.
- W2897714885 title "Three Isomers in Equilibrium: Phosphine Exchange of Coordinated and Pendant Phosphines in a Unique Complex, (OC)5WL (L = 1,2-Bis(diphenylphosphino)-1-di-p-tolylphosphinoethane), and Implications for Understanding the k2 Term in the Rate Law for Phosphine Substitution in Group 6 Metal Carbonyl Complexes" @default.
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- W2897714885 doi "https://doi.org/10.1021/acs.organomet.8b00471" @default.
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