25879-12-3Relevant articles and documents
Diplatinum complexes: Chemoselective reactions of the μ-orthometalated, metal-metal bonded complex
Archambault, Christine,Bender, Robert,Dusausoy, Yves,Welter, Richard,Braunstein, Pierre
, p. 545 - 552 (2013/06/26)
In order to investigate further the chemoselectivity of reactions involving the μ-orthometalated, metal-metal bonded dinuclear Pt(I) complex [Pt 2(μ-o-C6H4PPh2)(μ-PPh 2)(PPh3)2](Pt-Pt) (1), it was reacted with HCl and HI using various stoichiometries. The first step was the breaking of the metal-carbon bond and the formation of C-H and Pt-X bonds. When a 1:1 ratio was used, the complexes [Pt2X(μ-PPh2)(PPh3) 3](Pt-Pt) (2, X = Cl; 3, X = I) have been obtained but the use of a 2:1 ratio resulted instead in the formation of the complexes [Pt 2(μ-H)(μ-PPh2)X2(PPh3) 2](Pt-Pt) (4, X = Cl; 6, X = I). The latter transformed into [Pt 2(μ-X)(μ-PPh2)X2(PPh3) 2] (5, X = Cl; 7, X = I) in the presence of an additional equivalent of HX. The cis,cis- and cis,trans-isomers of 7 were also obtained by oxidation of 3 with one equivalent of iodine. Whereas compounds 4, cis,cis-5, and cis,trans-7 have been characterized in solution, the complexes 2·1/2C7H8, 3, 6 and cis,cis-7 have been isolated and structurally characterized by X-ray diffraction.
Synthesis of TiRu2 heterobimetallic and TiRuM (M = Rh, Ir, Pd, Pt) heterotrimetallic sulfido clusters from a hydrosulfido-bridged titanium-ruthenium complex
Kuwata,Kabashima,Sugiyama,Ishii,Hidai
, p. 2034 - 2040 (2008/10/08)
Treatment of the hydrosulfido-bridged titanium-ruthenium heterobimetallic complex [Cp2Ti(μ2-SH)2RuCl (η5-C5Me5)] (1; Cp = η5-C5H5) with an excess of triethylamine followed by addition of [RuCl2(PPh3)3] and [{(cod)M}2-(μ2-Cl)2] (M = Rh, Ir; cod = 1,5-cyclooctadiene) led to the formation of the TiRu2 and TiRuM mixed-metal sulfido clusters [(CpTi){(η5-C5Me5)Ru}{Ru (PPh3)2}(μ3-S)2 (μ2-Cl)2] (3) and [(CpTi){η5-C5Me5)Ru}{M(cod)}- (μ3-S)2(μ2-Cl)] (M = Rh (4a), Ir (4b)), respectively. On the other hand, the reactions of 1 with [M(PPh3)4] (M = Pd, Pt) afforded the TiRuM trinuclear clusters [(CpTiCl){(η5-C5Me5)Ru}{M (PPh3)2}(μ3-S)(μ2-S) (μ2-H)] (M = Pd (5a), Pt (5b)) with an unprecedented M3(μ3-S)(μ2-S) core. The detailed structures of these triangular clusters 3-5 have been determined by X-ray crystallography. Crystal data: 3, triclinic, P1, a = 12.448(4) A, b = 12.773-(4) A, c = 17.270(4) A, α = 100. 16(2)°, β = 99.93(2)°, γ = 114.11(3)°, V = 2373(1) A3, Ζ = 2; 4a, triclinic, P1, a = 7.714(2) A, b = 11.598(3) A, c = 14.802(4) A, α = 80.46(2)°, β = 82.53(2)°, γ = 71.47(2)°, V = 1234.0(6) A3, Z = 2; 4b, triclinic, P1, a = 7.729(1) A, b = 11.577(2) A, c = 14.766(3) A, α = 80.14(1)°, β = 82.71(1)°, γ = 71.55(1)°, V = 1231.1(4) A3, Ζ = 2; 5a, monoclinic, P21/c, a = 11.259(4) A, b = 16.438(4) A, c = 26.092(5) A, β = 102.23(3)°, V = 4719(2) A3, Z = 4; 5b, monoclinic, P21/n, a = 11.369(2) A, b = 16.207-(3) A, c = 26.116(2) A, β = 102.29(1)°, V = 4701(1) A3, Ζ = 4.
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.
