σ-Bond metathesis between M–X and RC(O)X′ (M = Pt, Pd; X, X′ = Cl, Br, I) : facile determination of the relative ΔG values of the oxidative additions of RC(O)X to an M(0) complex, evidence by density functional theory calculations, and synthetic applications

• Main Authors: Kuniyasu, Hitoshi, Sanagawa, Atsushi, Nakane, Daisuke, Iwasaki, Takanori, Kambe, Nobuaki, Bobuatong, Karan, Lu, Yunpeng, Ehara, Masahiro
• Other Authors: School of Physical and Mathematical Sciences
• Format: Article
• Language: English
• Published: 2013
• Subjects: DRNTU::Science::Mathematics::Applied mathematics
• Online Access: https://hdl.handle.net/10356/99939; http://hdl.handle.net/10220/16543
• Institution: Nanyang Technological University

The novel utility of the ligand exchange reaction between M–X and RC(O)X′ (X, X′ = halogen; R = aryl, alkyl) is described. The relative ΔGs (ΔΔGs) of the oxidative additions of acid halides RC(O)X to M(PPh3)2Ln (M = Pt, Pd) were determined using the halogen-exchange reactions between X of trans-M(X)[C(O)R](PPh3)2 and X′ of RC(O)X′. 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 σ-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.