Forniés Juan, Garcia Ana, Gil Belén, Lalinde Elena, Moreno M Teresa
Departamento de Quimica Inorganica, Instituto de Ciencia de Materiales de Aragon, Universidad de Zaragoza-Consejo Superior de Investigaciones Cientificas, 50009 Zaragoza, Spain.
Dalton Trans. 2004 Nov 21(22):3854-63. doi: 10.1039/b412487a. Epub 2004 Oct 21.
A series of mononuclear platinum complexes containing diynyldiphenylphosphine ligands cis-Pt(C(6)F(5))(2)(PPh(2)C[triple bond]CC(6)H(4)C[triple bond]CR)L(n= 0, L = tht, R = Ph 2a, Bu(t)2b; L = PPh(2)C[triple bond]CC(6)H(4)C[triple bond]CR, 4a, 4b; n=-1, L = CN(-), 3a, 3b) has been synthesized and the X-ray crystal structures of 4a and 4b have been determined. In order to compare the eta2-bonding capability of the inner and outer alkyne units, the reactivity of towards [cis-Pt(C(6)F(5))(2)(thf)(2)] or [Pt(eta2)-C(2)H(4))(PPh(3))(2)] has been examined. Complexes coordinate the fragment "cis-Pt(C(6)F(5))(2)" using the inner alkynyl fragment and the sulfur of the tht ligand giving rise the binuclear derivatives [(C(6)F(5))(2)Pt(mu-tht)(mu-1kappaP:2eta2-C(alpha),C(beta)-PPh(2)C[triple bond]CC(6)H(4)C[triple bond]CR)Pt(C(6)F(5))(2)](R = Ph 5a, Bu(t)5b). The phenyldiynylphosphine complexes 2a, 3a and 4a react with [Pt(eta2)-C(2)H(4))(PPh(3))(2)] to give the mixed-valence Pt(II)-Pt(0) complexes ((C(6)F(5))(2)LPt(mu-1kappaP:2eta2)-C(5),C(6)-PPh(2)C[triple bond]CC(6)H(4)C[triple bond]CPh))Pt(PPh(3))(2)(L = tht 6a, CN 8a and PPh(2)C[triple bond]CC(6)H(4)C[triple bond]CPh 9a) in which the Pt(0) fragment is eta2-complexed by the outer fragment. Complex 6a isomerizes in solution to a final complex [((C(6)F(5))(2)(tht)Pt(mu-1kappaP:2eta2)-C(alpha),C(beta)-PPh(2)C[triple bond]CC(6)H(4)C[triple bond]CPh))Pt(PPh(3))(2)]7a having the Pt(0) fragment coordinated to the inner alkyne function. In contrast, the tert-butyldiynylphosphine complexes 2b and 3b coordinate the Pt(0) unit through the phosphorus substituted inner acetylenic entity yielding 7b and 8b. By using 4a and 2 equiv. of [Pt(eta2)-C(2)H(4))(PPh(3))(2)] as precursors, the synthesis of the trinuclear complex [cis-((C(6)F(5))(2)Pt(mu-1kappaP:2eta2)-C(5),C(6)-PPh(2)C[triple bond]CC(6)H(4)C[triple bond]CPh)(2))(Pt(PPh(3))(2))(2)]10a, bearing two Pt(0)(PPh(3))(2)eta2)-coordinated to the outer alkyne functions is achieved. The structure of 7a has been confirmed by single-crystal X-ray diffraction.
一系列含有二炔基二苯基膦配体的单核铂配合物[顺式-Pt(C₆F₅)₂(PPh₂C≡CC₆H₄C≡CR)L]ₙ(n = 0, L = tht, R = Ph 2a, Buⁱ 2b; L = PPh₂C≡CC₆H₄C≡CR, 4a, 4b; n = -1, L = CN⁻, 3a, 3b)已被合成，并且已确定了4a和4b的X射线晶体结构。为了比较内炔单元和外炔单元的η²键合能力，研究了其与[顺式-Pt(C₆F₅)₂(thf)₂]或[Pt(η²)-C₂H₄)(PPh₃)₂]的反应活性。配合物使用内炔基片段和tht配体的硫原子配位“顺式-Pt(C₆F₅)₂”片段，生成双核衍生物[(C₆F₅)₂Pt(μ-tht)(μ-1κP:2η²-Cα,Cβ-PPh₂C≡CC₆H₄C≡CR)Pt(C₆F₅)₂](R = Ph 5a, Buⁱ 5b)。苯基二炔基膦配合物2a、3a和4a与[Pt(η²)-C₂H₄)(PPh₃)₂]反应，生成混合价态的Pt(II)-Pt(0)配合物[((C₆F₅)₂LPt(μ-1κP:2η²)-C₅,C₆-PPh₂C≡CC₆H₄C≡CPh))Pt(PPh₃)₂]ₙ(L = tht 6a, CN 8a和PPh₂C≡CC₆H₄C≡CPh 9a)，其中Pt(0)片段通过外片段进行η²配位。配合物6a在溶液中异构化为最终配合物[((C₆F₅)₂(tht)Pt(μ-1κP:2η²)-Cα,Cβ-PPh₂C≡CC₆H₄C≡CPh))Pt(PPh₃)₂]7a，其中Pt(0)片段与内炔官能团配位。相比之下，叔丁基二炔基膦配合物2b和3b通过磷取代的内炔实体配位Pt(0)单元，生成7b和8b。以4a和2当量的[Pt(η²)-C₂H₄)(PPh₃)₂]为前体，实现了三核配合物[顺式-((C₆F₅)₂Pt(μ-1κP:2η²)-C₅,C₆-PPh₂C≡CC₆H₄C≡CPh)₂)(Pt(PPh₃)₂)₂]10a的合成，该配合物带有两个通过η²配位在外炔官能团上的Pt(0)(PPh₃)₂。7a的结构已通过单晶X射线衍射得到证实。
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