13517-35-6Relevant articles and documents
Reaction of silafluorenes with (Ph3P) 2Pt(η2-C2H4): Generation and characterization of Pt-Si monomers, dimers and trimers
Braddock-Wilking, Janet,Corey, Joyce Y.,Trankler, Kevin A.,Dill, Kimberly M.,French, Lisa M.,Rath, Nigam P.
, p. 4576 - 4584 (2004)
The reaction of silafluorene (1; H2SiC12H 8) with (Ph3P)2Pt(η2-C 2H4) (2) at room temperature in C7D8 initially provided the mononuclear complex (Ph3P) 2Pt(H)[Si(H)C12H8] (3), followed by the appearance of the unsymmetrical dinuclear complex (Ph3P) 2(H)Pt(μ-SiC12H8)(μ-η2- HSiC12H8)Pt(PPh3) (4) and finally the novel trinuclear complex [(Ph3P)Pt(μ-SiC12H 8)]3 (5). The three complexes were characterized by multinuclear NMR spectroscopy and by X-ray crystallography (5). The molecular structure of 5 exhibits a nonplanar Pt3Si3 core. When the reaction was conducted at low temperature until the silafluorene was consumed and the mixture then warmed to room temperature, the dinuclear complex 4 could be isolated. The related substituted silafluorene system 3,7-di-tert- butylsilafluorene (6; H2SiC20H24) also reacted with 2 to provide both mono- and dinuclear complexes (7 and 8) analogous to 3 and 4. The dinuclear complex 8 was isolated and crystallographically characterized. Each of the two Pt centers in complex 8 exhibits a unique environment. In solution at low temperature 8 is best described as having one platinum center with a terminal hydride, [Pt(H)(PPh3)2], and the second platinum with a nonclassical [Si...H...Pt(PPh 3)] unit. However, in the solid state, the two hydrides may both adopt a bridging environment. Heating a sample of the unsymmetrical dimer 8 led to the formation of several products, one of which was the trimer 9, analogous to 5.
Reactivity of o-Diphenylphosphinobenzaldehyde toward . X-Ray Structure of *C6H6
Ghilardi, Carlo A.,Midollini, Stefano,Moneti, Simonetta,Orlandini, Annabella
, p. 1833 - 1836 (1988)
The compound o-diphenylphosphinobenzaldehyde reacts with under mild conditions to give the acyl hydride .In the presence of butanol a complete decarbonylation of the aldehyde occurs with formation of .The X-ray crystal structure of the acyl complex has been determined.The crystals are orthorombic, space group Pn21a, with a = 17.673(9), b = 16.586(8), and c = 12.160(6) Angstroem.The structure has been solved by three-dimensional Patterson and Fourier syntheses and refined by least squares to final R and R' of 0.049 and 0.046 respectively.The metal atom is surrounded in a distored square-planar geometry by the acyl ligand, a triphenylphosphine and hydride ligand.
The Mechanism of Hydrogenolysis of Dineopentylbis(triethylphosphine)platinum(II)
Reamey, Robert H.,Whitesides, George M.
, p. 81 - 85 (1984)
Dineopentylbis(triethylphosphine)platinum(II) reacts with H2 (34 psi) at 32 deg C in hydrocarbon solvents and yields neopentane and trans-dihydridobis(triethylphosphine)platinum(II).The addition of triethylphosphine (L) changes the rate-limiting step of the reaction.When = 0 M, the overall rate-limiting step is the dissociation of triethylphosphine from L2PtR2: no isotope effect is observed on substitution of D2 for H2, and the rate is independent of pressure of H2.When > 0.1M, phosphine loss is reversible,and a later step,either addition of H2 to platinum or (more probably) elimination of neopentane from platinum, is rate limiting: the rate of reaction depends on the first order of the H2 pressure, and an isotope effect of kH/kD ca. 1.9 is observed on substitution of H2 by D2.Activation parameters obtained at 0.0, 0.1 and 0.5 M triethylphosphine are presented.These data are useful in understanding the differences in rates of inter- and intramolecular oxidative additions to platinum(II).The rate of reaction of H2 with several structurally related bis(phosphine)dialkylplatinum(II) compounds was surveyed under similar reaction conditions.In general, bulky substituents on platinum accelerate the reaction.This observation suggests that phosphine dissociation is a general feature of reaction of bis(phosphine)dialkylplatinum(II) compounds with dihydrogen.
A new approach to light-gated Pt catalysts for the hydrosilylation
Buchner, Magnus R.,Bechlars, Bettina,Ruhland, Klaus
, p. 60 - 67 (2013/10/01)
A new concept for a light-gated transition metal catalyst is presented based on a photo-active moiety in the outer ligand sphere of the complex which on irradiation reacts irreversibly with some part of the inner ligand sphere releasing a free coordination site. The principle is exemplified on a platinum complex for the hydrosilylation. It is proven that the catalytic properties of the complex and the properties of the photo-gate can be fine-tuned on the chemical problem independently of each other.
Expedient, direct synthesis of (L)Pt(0)(1,6-diene) complexes from H 2PtCl6
Berthon-Gelloz, Guillaume,Schumers, Jean-Marc,Lucaccioni, Fabio,Tinant, Bernard,Wouters, Johan,Marko, Istvan E.
, p. 5731 - 5734 (2008/10/09)
The one-pot synthesis of useful [Pt2(0)(η4-1,6- diene)3] complexes, directly from H2PtCl 6·xH2O, has remained an unaddressed problem. We have found that the treatment of an i-PrOH solution of H2PtCl 6-XH2O by (Me3SiO)2MeSi(CH=CH 2), in the presence of allyl ether (AE), followed by reaction of the in situ generated Pt(O) species with IPr carbene (IPr =1,3-bis(2,6- diisopropylphenyl)imidazol-2-ylidene) enables the isolation of (IPr)Pt(AE) (I) in 50-70% yield. The scope of this method has been extended to other (L)Pt(1,6-diene) complexes (L = 1,3-dicyclohexylimidazol-2-ylidene, triphenylphoshine; 1,6-diene = diethyl 2,2-diallylmalonate (DAM)), and the molecular structure of the (IPr)Pt(DAM) (4) complex has been unequivocally determined by a single-crystal X-ray diffraction analysis. These results are significant for the formation of active L-Pt(O) fragments in catalysis.
