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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
|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.||URI:||https://hdl.handle.net/10356/99939
|DOI:||http://dx.doi.org/10.1021/om400157a||Fulltext Permission:||none||Fulltext Availability:||No Fulltext|
|Appears in Collections:||SPMS Journal Articles|
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