蟽-Bond Metathesis between M鈥揦 and RC(O)X鈥?(M = Pt, Pd; X, X鈥?= Cl, Br, I): Facile Determination of the Relative 螖G Values of the Oxidative Additions of RC(O)X to an M(0) Complex, Evidence by De

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• 作者：Hitoshi Kuniyasu ; Atsushi Sanagawa ; Daisuke Nakane ; Takanori Iwasaki ; Nobuaki Kambe ; Karan Bobuatong ; Yunpeng Lu ; Masahiro Ehara
• 刊名：Organometallics
• 出版年：2013
• 出版时间：March 25, 2013
• 年：2013
• 卷：32
• 期：6
• 页码：2026-2032
• 全文大小：410K
• 年卷期：v.32,no.6(March 25, 2013)
• ISSN：1520-6041

文摘

The novel utility of the ligand exchange reaction between M鈥揦 and RC(O)X鈥?(X, X鈥?= halogen; R = aryl, alkyl) is described. The relative 螖Gs (螖螖Gs) of the oxidative additions of acid halides RC(O)X to M(PPh₃)₂L_n (M = Pt, Pd) were determined using the halogen-exchange reactions between X of trans-M(X)[C(O)R](PPh₃)₂ and X鈥?of RC(O)X鈥? Experimental thermodynamics data are reasonably consistent with those obtained by density functional theory (DFT) calculations. Activation parameters obtained by experiments as well as a systematic DFT study supported the fact that reactions occurred through slightly distorted quadrangular pentacoordinated 蟽-bond metatheses, in which the Cl atom underwent a more indirect course than the Br atom. Moreover, exchange reactions were employed as the accessible prototype for the conversion of halogen ligands of nickel triad complexes into heavier halogen ligands.