Effect of Organic Groups on the Carbonyl-insertion Reaction of Platinum(II)

Article abstract of DOI:10.1039/DT9810002317

The equilibria between the isomers of which undergo CO insertion and their halide-bridged insertion products have been examined for 12 ortho-, meta-, and para-substituted aryl groups, R.Values of the equilibrium constants, enthalpy, and entropy of the reactions are presented.The electronic effects of the aryl groups on this R migration reaction are found to be at least as critical as any previously reported factors influencing this process.Electron-donating substituents in meta- or para-positions promote the insertions, whereas electron-withdrawing groups inhibit them.A correlation with Hammett ? values is found.Ortho-substituents tend to prevent the reaction for steric reasons.Enthalpies of the reactions become less negative with electron-withdrawing groups, and this may reflect strengthening Pt-aryl bonds.

Full text of DOI:10.1039/DT9810002317

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