Influence of Electronically and Sterically Tunable Cinnamate Ligands on the Spectroscopic, Kinetic, and Thermodynamic Properties of Bis(triphenylphosphine)palladium(0) Olefin Complexes

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• 作者：Magnus R. Buchner ; Bettina Bechlars ; Bernhard Wahl ; Klaus Ruhland
• 刊名：Organometallics
• 出版年：2012
• 出版时间：January 23, 2012
• 年：2012
• 卷：31
• 期：2
• 页码：588-601
• 全文大小：911K
• 年卷期：v.31,no.2(January 23, 2012)
• ISSN：1520-6041

文摘

A detailed study of the influence of electronic and steric characteristics of cinnamic acid esters on the spectroscopic, kinetic, and thermodynamic properties of bis(triphenylphosphine)palladium(0) cinnamic acid ester complexes is presented (51 different new complexes included). These complexes show a dynamic behavior on the NMR spectroscopic time scale. Therefore, the rotational barriers of the olefin about the metal鈥搊lefin bond as well as the dissociation entropy and enthalpy of the olefin and the dissociation mechanism could be determined. These findings are interpreted together with the NMR spectroscopic, IR spectroscopic, and X-ray structural data (7 new structures included) concerning the influence of the different olefin ligands on the complex properties by means of Hammett plots. DFT calculations were performed to support the mechanistic conclusions.