102286-39-5Relevant academic research and scientific papers
Preparation and reactivity of mononuclear platinum(0) complexes containing a η2-coordinated alkynylphosphine
Bennett, Martin A.,Kwan, Laurence,Rae, A. David,Wenger, Eric,Willis, Anthony C.
, p. 226 - 233 (2007/10/03)
Displacement of ethene from [Pt(η2-C2H4)(dcpe)] by Ph2PC≡CMe gives the monomeric η2-alkynylphosphine complex [Pt(η2-Ph2PC≡CMe)(dcpe)] (5). Reaction of 5 with one equivalent of HCl forms, in benzene, the four-coordinate η1-vinyl-platinum(II) complex [PtCl{C(=CHMe)PPh2}(dcpe)] (6) by regiospecific addition of the proton to the alkyne carbon atom bearing the methyl group. In dichloromethane, reversible dissociation of the chloride ion from 6 takes place and the cation [Pt{C(=CHMe)PPh2-κP,C1}(dcpe)]+ (6′) that contains a three-membered methylenephosphaplatinacycle fragment can be observed. Treatment of complex 5 with methyl iodide results in the formation of a phosphonium salt [Pt{η2-C(=CH2)=CHPPh2Me}(dcpe)] +I-, [8]I, in which the alkynylphosphine has rearranged to the corresponding allene. The alkynylphosphine complex 5 is cleanly oxidised at phosphorus in the presence of sulfur or air to give the corresponding sulfide or oxide [Pt(η2-Ph2P(X)C≡CMe)(dcpe)] (X = S (9), O (10)). Complexes 5, 6, 8, 9 and 10 have been structurally characterised by single-crystal X-ray diffraction analysis.
Platinum Ethyl Complexes with β-Agostic Pt-H-C Bonding
Carr, Nicholas,Mole, Laura,Orpen, A. Guy,Spencer, John L.
, p. 2653 - 2662 (2007/10/02)
Protonation with non-co-ordinating acids of the complexes 2-C2H4)(L-L)> t2P(CH2)2PBut2, 1b, (H11C6)2P(CH2)3P(C6H11)2, 1c, But2P(CH2)3PBut2, 1d or o-But2PCH2C6H4CH2PBut2, 1e> and 2a-2d affords a series of cationic platinum(II) complexes 3a-3e which in the case of 3a-3c adopt a cis ethene/hydride ground state whereas in 3d and 3e the otherwise electron-deficient metal centre is stabilized by a two-electron, three-centre agostic interaction with the β-CH bond of the ethyl ligand.Complexes 1-3 were characterized by 1H, 13C and 31P NMR spectroscopy and for 2d and 3d by single-crystal X-ray crystallography.The influence of the chelating diphosphine ligand on the strength of the agostic bond was monitored by NMR spectroscopy.This revealed that the cations undergo two fluxional processes in solution: (a) agostic methyl rotation and (b) β-elimination/ethene rotation, a combination of which scrambles all five protons and both carbon atoms of the 'C2H5' moiety.The 31P nuclei, however, remain inequivalent at temperatures up to 300 K.The agostic interaction was displaced by a small two-electron donor molecule L to form the series of adducts + (L = acetonitrile or pyridine) in which the 'normal' ethyl complex is the first formed species.The adducts are unstable to loss of C2H4 by β-elimination to form the series of cationic hydrides +.For comparison, the complex t2P(CH2)3PBut2>> was synthesised and characterized by 1H and 31P NMR spectroscopy and X-ray crystallography.
platinum(0). Reactions with Alkyl, (Trimethylsilyl)methyl, Aryl, Benzyl, and Alkynyl Carbon-Hydrogen Bonds
Hackett, Marifaith,Whitesides, George M.
, p. 1449 - 1462 (2007/10/02)
cis-Hydridoneopentylplatinum(II) (1) reductively eliminates neopentane and generates platinum(0) (2).This bent bis(phosphine)platinum(0) complex was not observed directly; its intermediac
