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Title: 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
Authors: Kuniyasu, Hitoshi
Sanagawa, Atsushi
Nakane, Daisuke
Iwasaki, Takanori
Kambe, Nobuaki
Bobuatong, Karan
Lu, Yunpeng
Ehara, Masahiro
Keywords: DRNTU::Science::Mathematics::Applied mathematics
Issue Date: 2013
Source: Kuniyasu, H., Sanagawa, A., Nakane, D., Iwasaki, T., Kambe, N., Bobuatong, K. et al. (2013). 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. Organometallics, 32(6), 2026-2032.
Series/Report no.: Organometallics
Abstract: 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.
DOI: 10.1021/om400157a
Fulltext Permission: none
Fulltext Availability: No Fulltext
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