306308-08-7Relevant academic research and scientific papers
Baeyer-Villiger oxidation of ketones catalyzed by platinum(II) lewis acid complexes containing coordinated electron-poor fluorinated diphosphines
Michelin, Rino A.,Pizzo, Erika,Scarso, Alessandro,Sgarbossa, Paolo,Strukul, Giorgio,Tassan, Augusto
, p. 1012 - 1017 (2008/10/09)
The synthesis and characterization of new hydroxo-bridged platinum(II) complexes of the type [P(μ-OH)(P-P)]2[BF4]2, (1-4), where P-P = (C6H5-nFn) 2PCH2CH2P(C6H5-nF n)2 (n = 2 (2Fdppe) (1), 3 (3Fdppe) (2), 4 (4Fdppe) (3), 5 (dfppe) (4), are reported. These compounds have been used in the Baeyer-Villiger oxidation of 2-methylcyclohexanone using 35% hydrogen peroxide as oxidant. The reactions were performed at 25, 50, and 70°C in a chlorinated solvent/H 2O two-phase system. Among the fluorinated catalysts, complex 4 was found to be the best one in the oxidation of cyclic ketones; however, it is ineffective toward acyclic ketones. The Lewis acidity of the platinum(II) complexes with coordinated fluorinated diphosphines was investigated through the determination of the wavenumber shift Δν = ν(C≡N) coord - ν(C≡N)free of the isocyanide group in complexes of the type [PtCl(CN-2,6-(CH3)2C 6H3)(P-P)[BF4] (P-P = 2Fdppe, 3Fdppe, 4Fdppe, dfppe, dppe). This latter parameter, which represents a measure of the electrophilicity of the metal center, was then correlated to the catalytic activity of complexes 1-4 in the Baeyer-Villiger oxidation of ketones.
Electron-poor olefin polymerization catalysts based on semi-fluorinated bis(phosphane)s
Wursche, Roland,Debaerdemaeker, Tony,Klinga, Martti,Rieger, Bernhard
, p. 2063 - 2070 (2007/10/03)
Two semi-fluorinated bis(phosphane)s, P,P'-(1,2-ethanediyl)-bis[bis(2,4,5-trifluorophenyl)phosphane] (3a), P,P'-(1,2-ethanediyl)bis[bis(2,4-difluorophenyl)phosphane] (3b), and their corresponding Pd(II) and Pt(II)-dichloro complexes (4a,b and 6a,b) have been synthesized. Complexation of P,P'-(1,2-ethanediyl)bis{bis[3,5-di(trifluoromethyl)phenyl]phosphane} (3c) and P,P'-(1,2-ethanediyl)bis[bis(pentafluorophenyl)phosphane] (3d) afforded the related compounds 4c,d and 6c. The Pd(II)-diiodo complexes 5c,d have been obtained from 4c,d by halide exchange with NaI. The solid-state structures of compounds 4b and 5c,d have been determined by single-crystal X-ray diffraction analysis. Activation of 4b-d with MAO produced efficient catalysts for the polymerization of 2-norbornene, which have proved to be superior to the Pd(II)-dichlorides derived from the more electron-rich, structurally related P,P'-(1,2-ethanediyl)bis(diphenylphosphane) (DPPE) or P,P'-(1,3-propanediyl)bis(diphenylphosphane) (DPPP).
