Effect of organic groups on the carbonyl-insertion reaction of platinum(II)
- 1 January 1981
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 12,p. 2317-2320
- https://doi.org/10.1039/dt9810002317
Abstract
The equilibria between the isomers of [PtCl(R)(CO)(PMePh2)] which undergo CO insertion and their halidebridged insertion products [Pt2Cl2(COR)2(PMePh2)2] 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 σ 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.Keywords
This publication has 0 references indexed in Scilit: