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• W2079896245 endingPage "5755" @default.
• W2079896245 startingPage "5744" @default.
• W2079896245 abstract "A combined kinetic and DFT study of the uncatalyzed isomerization of cationic solvent complexes of the type cis-[Pt(R‘)(S)(PR3)2]+ (R‘ = linear and branched alkyls or aryls and S = solvents) to their trans isomers has shown that the reaction goes through the rate-determining dissociative loss of the weakly bonded molecule of the solvent and the interconversion of two geometrically distinct T-shaped 14-electron three-coordinate intermediates. The Pt−S dissociation energy is strongly dependent on the coordinating properties of S and independent of the nature of R‘. The energy barrier for the fluxional motion of [Pt(R‘)(PR3)2]+ is comparatively much lower (≈8−21 kJ mol-1). The presence of β-hydrogens on the alkyl chain (R‘ = Et, Prn, and Bun) produces a great acceleration of the reaction rate. This accelerating effect has been defined as the β-hydrogen kinetic effect, and it is a consequence of the stabilization of the transition state and of the cis-like three-coordinate [Pt(R‘)(PR3)2]+ intermediate through an incipient agostic interaction. The DFT optimization of [Pt(R‘)(PMe3)2]+ (R‘ = Et, Prn, and Bun) reproduces a classical dihapto Pt····η2-HC agostic mode between the unsaturated metal and a dangling C−H bond. The value of the agostic stabilization energy (in the range of ≈21−33 kJ mol-1) was estimated by both kinetic and computational data and resulted in being independent of the length of the hydrocarbon chain of the organic moiety. A better understanding of such interactions in elusive reaction intermediates is of primary importance in the control of reaction pathways, especially for alkane activation by metal complexes." @default.
• W2079896245 created "2016-06-24" @default.
• W2079896245 creator A5017449753 @default.
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• W2079896245 creator A5030230442 @default.
• W2079896245 creator A5076307493 @default.
• W2079896245 creator A5078495537 @default.
• W2079896245 date "2007-04-05" @default.
• W2079896245 modified "2023-10-08" @default.
• W2079896245 title "β-Hydrogen Kinetic Effect" @default.
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• W2079896245 doi "https://doi.org/10.1021/ja0702162" @default.

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