79328-82-8Relevant academic research and scientific papers
Some reactions of the platinum(II) carbene complex cis-dichloro(dimethylaminomethylene)(triphenylphosphine)-platinum(II) and the X-ray crystal and molecular structures of ...
Ferguson, George,Li, Yiwei,McAlees, Alan J.,McCrindle, Robert,Zang, Erie
, p. 671 - 680 (2007/10/03)
Title full: Some reactions of the platinum(II) carbene complex cis-dichloro(dimethylaminomethylene)(triphenylphosphine)-platinum(II) and the X-ray crystal and molecular structures of the products trans-(CH 2,P)-chloro(chloromethyl)(dimethylaminomethylene)(triphenylphosphine) platinum(II) and [1,2-bis(diphenylphosphino)ethane](dimethylaminomethylene)-(triphenylphosphine) platinum(II) bis(hexafluorophosphate). The reaction of the title complex 1 with excess diazomethane results in the exclusive insertion of a methylene group into the Pt-Cl bond trans to the phosphine ligand, to give the chloromethyl complex 6. The reactions of 1 with the diphosphines, Ph2P(CH2)nPPh2(n = 2, dppe, n = 3, dppp), and with the organometallic reagents Ph4Sn, Ph2Hg, or PhSnMe3, can also all be interpreted as proceeding via initial displacement of the chlorine trans to PPh3. The chelating phosphine ligands give equilibrium mixtures of the products [(LL)Pt(CHNMe2)(PPh3)]2+2Cl- and [(LL)Pt(CHNMe2)Cl]+Cl- (LL = dppe, dppp), and treatment of the mixture [(LL) = dppe] with excess aqueous KPF6 gave [(dppe)Pt(CHNMe2)(PPh3)]2+2PF6 - (9b).
Reactions of (chloromethyl)platinum(II) derivatives with nucleophiles. Formation of (dimethylamino)carbene complexes using N,N,N′,N′-tetramethylmethanediamine as nucleophile and the X-ray crystal and molecular structures of cis-[(Ph3P)Pt(CH2NMe3)Cl2]
Ferguson, George,Li, Yiwei,McAlees, Alan J.,McCrindle, Robert,Xiang, Ke
, p. 2428 - 2439 (2008/10/08)
Reaction, in chloroform solution, of (COD)Pt(CH2Cl)Cl (5) with Me2NCH2NMe2 in the presence of 1 equiv (vs 5) of a monodentate ligand L (L = Ph3P, (p-MeOC6H4)3P, (p-FC6H4)3P, Et3P, Ph3As) gives the (dimethylamino)carbene complexes cis-[LPt(CHNMe2)Cl2] (1a-e) via the cyclic ylide intermediates [LPt(CH2NMe2CH2NMe2)Cl]Cl (2a-e). Major byproducts of the reaction are the (trimethylammonio)methyl ylide complexes cis-[LPt(CH2NMe3)Cl2] (11a-e). With L = Ph3As, carbene product 1e is accompanied by a second carbene complex, trans(As,CH2)-[(Ph3As)Pt(CHNMe2)(CH 2NHMe2)Cl]Cl (25). When the reaction with L = Ph3P is carried out in acetonitrile, the amide chelate [(Ph3P)Pt(CH2CH2CONMe2)Cl] (24) is formed in addition to 1a and 11a. A deuterium labeling experiment indicates that formation of 24 involves condensation of a CH2Cl (or derived) moiety with a molecule of solvent. The structures of complexes 11a and 24, and of the hexafluorophosphate analogue (26) of complex 25, have been confirmed by X-ray crystallographic analyses. Carbene complex 1a, along with other products, is also obtained upon reaction of 5 and Ph3P (1:1) with dimethylamine. Formation of 1a in this case can proceed via two pathways, one involving cyclic ylide species 2a as intermediate and the other the N-protonated (dimethylamino)methyl complex cis-[(Ph3P)Pt(CH2NHMe2)Cl2] (20). The mechanistic pathways involved in formation of carbene complexes 1a-e and 25, ylide complexes 2a-e and 11a-e, and (dimethylamino)methyl complex 20 are discussed. It is suggested that formation of the ylide complexes and 20 proceeds via initial attack of amine at platinum and that carbene formation proceeds via platinum(IV) carbene hydride intermediates.
Organometallic chemistry of carbon-nitrogen multiple bonds. 3. Reaction of tris(triphenylphosphine)platinum(0) with dimethylmethyleniminium chloride. X-ray structures of the products [(Ph3P)PtCH2N(CH3)2CH 2
Barefield,Carrier,Sepelak,Van Derveer
, p. 103 - 110 (2008/10/08)
Tris(triphenylphosphine)platinum(0) reacts with [(CH3)2N=CH2]Cl in THF to yield [(Ph3P)-PtCH2N(CH3)2CH 2N(CH3)2(Cl)]Cl (A) which may be considere
