18517-48-1Relevant articles and documents
Regioselective competition between the formation of seven-membered and five-membered cyclometalated platinacycles preceded by Csp2-Csp3 reductive elimination
Anderson, Craig M.,Greenberg, Matthew W.,Spano, Lucia,Servatius, Labeeby,Tanski, Joseph M.
, p. 27 - 36 (2016)
A mixture of seven-membered and five-membered platinacycle complexes are eventually formed after a series of substitution, oxidative addition, and reductive elimination reactions between the platinum dimer, cis-[Pt2Me4(μ-SMe2)2] and the naphthyl-derived ?N chelate ligands, (8-XC10H6CH = N-R), X = I, Br; R = phenyl and 4-Cl-benzyl. From the tethered ligand, either an sp2 C-H bond can be activated forming a five-membered ring or an sp3 C-H bond can be activated forming a seven-membered ring. All compounds have the imine included in the platinacycle. The ratio of complexes as a function of ring size varies depending on ligand architecture of the chelate ligand and the nature of other ligands in the coordination sphere. The cyclometalated platinum complexes have been characterized by NMR spectroscopy. One complex with a seven-membered ring was characterized crystallographically. Reductive elimination reactions of isolated and/or identified cyclometalated, six-membered platinum(IV) compounds [PtMe2Br{C10H6CH = NCH2(4-ClC6H4)}L] and [PtMe2Br{C10H6CH = N(C6H5)}L] (L = SMe2) to form Csp3-Csp2 bonds, followed by competition between Csp2-H and Csp3-H bond activation are also reported.
σ-bond metathesis between M-X and RC(O)X′ (M = Pt, Pd; X, X′ = Cl, Br, I): Facile determination of the relative Δ G values of the oxidative additions of RC(O)X to an M(0) complex, evidence by density functional theory calculations, and synthetic applications
Kuniyasu, Hitoshi,Sanagawa, Atsushi,Nakane, Daisuke,Iwasaki, Takanori,Kambe, Nobuaki,Bobuatong, Karan,Lu, Yunpeng,Ehara, Masahiro
supporting information, p. 2026 - 2032 (2013/05/09)
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.
Diverse C-C bond-forming reactions of bis(carbene)platinum(II) complexes
Klet, Rachel C.,Labinger, Jay A.,Bercaw, John E.
, p. 6652 - 6657 (2012/11/07)
The platinum(0) complex Pt(PPh3)4 catalyzes coupling of the carbene ligands of (CO)5Cr{C(OMe)(p-MeOC6H 4)} (1). The stable bis(carbene)platinum(II) complexes Cl 2Pt{C(OMe)(Me)}2
