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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Titanium thiosalicylate complexes: functional metalloligands for the construction of redox-active heterometallic architectures
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Titanium thiosalicylate complexes: functional metalloligands for the construction of redox-active heterometallic architectures

机译：硫化钛酸酯复合物：用于氧化还原活性的杂动机架构的函数金属溶胶配体

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The titanium complex [TiCp*(thiosal)(thiosalH)] (1) has been synthesised by reaction of [TiCp*Me-3], Cp* = (5)-C5Me5, with thiosalicylic acid (H(2)thiosal). Complex 1 reacts with [M(-OH)(COD)](2) (M = Rh, Ir) to yield the corresponding early-late heterobimetallic complexes [TiCp*(thiosal)(2)M(COD)] (M = Rh (2); Ir (3)). Carbon monoxide replaces the COD ligand in 2 and 3 leading to the respective dicarbonyl complexes [TiCp*(thiosal)(2)M(CO)(2)] (M = Rh (4); Ir (5)). Compound 4 reacts with PPh3 to yield the monocarbonyl derivative [TiCp*(thiosal)(2)Rh(CO)(PPh3)] (6). The reaction of compound 1 with (LiBu)-Bu-n yields the tetrametallic complex [{TiCp*(thiosal)(2)Li}(2)(THF)(3)(H2O)] (7). Compound 7 reacts with [RuCp*Cl(COD)] yielding the heterometallic complex [TiCp*(thiosal)(2)RuCp*] (8). The molecular structures of compounds 4, 5 and 7 have been studied by X-ray diffraction. From cyclic voltammetric (CV) and square wave voltammetric (SWV) experiments, we observed that attachment of the titanium moiety of precursor 1 to a late transition metal moiety through the sulfur atoms has a significant influence on the reduction behaviour of the Ti(iv) metal centre. Thus, monometallic 1 exhibits an irreversible reduction process at -1.15 V vs. SCE, whereas the CVs of heterobimetallic compounds 2-6 are characterized by the reversible or quasi-reversible one-electron reduction of the Ti(iv)/Ti(iii) system, suggesting a significant stabilization of the Ti(iii) reduced species. Likewise, substitution of the M(COD) diolefin fragment in 2 and 3 by the M(CO)(2) carbonyl-containing moiety (in compounds 4 and 5) leads to a significant anodic shift in the titanium E-1/2 reduction redox potentials.
机译：通过[TICP * ME-3]，CP * =（5）-C5ME5，用硫代硅酸（H（2）硫化）反应合成钛复合物[TICP *（硫磷）]（1）。复合物1与[M（-OH）（COD）]（2）（M = RH，IR）反应，得到相应的早期偏异化物复合物[TICP *（硫磷）（2）m（COD）]（M = RH（2）; IR（3））。一氧化碳取代了2和3中的鳕鱼配体，导致各自的二羰基配合物[TICP *（硫氰酸酯）（2）m（2）（共2））（m = RH（4）; IR（5））。化合物4与PPH3反应，得到单羰基衍生物[TICP *（硫氰酸酯）（2）RH（CO）（PPH3）]（6）。化合物1与（Libu）-Bu-N的反应产生四甘白复合物[{TICP *（硫氰）（2）Li}（2）（THF）（3）（H2O）]（7）。化合物7与[RUCP * Cl（COD）]反应，得到杂象复合物[TICP *（硫氰）（2）RUCP *]（8）。已经通过X射线衍射研究了化合物4,5和7的分子结构。从循环伏安（CV）和方波伏安（SWV）实验中，我们观察到通过硫原子将前体1的钛部分的钛部分与后过渡金属部分的附着对Ti（IV）的还原行为有显着影响金属中心。因此，单金属1在-1.15V与SCE上表现出不可逆的还原过程，而异质化合物2-6的CV的特征在于Ti（IV）/ Ti（III）的可逆或准可逆的单电子减少系统，表明Ti（III）的显着稳定性降低。同样地，M（CO）（2）含羰基部分（化合物4和5）中的M（COD）Diolefin片段中的M（COD）Diolefin片段取代（在化合物4和5中）导致钛E-1/2的显着阳极转变氧化还原潜力。

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    Fandos Rosa; Bruna Sonia; Hernandez Carolina; Otero Antonio; Rodriguez Ana; Ruiz Maria Jose; Terreros Pilar; Cuadrado Isabel;

  • 作者单位

    Univ Castilla La Mancha Dept Quim Inorgan Organ &

    Bioquim Inst Nanociencia Nanotecnol &

    Mat Mol INAMOL Fac Ciencias Medio Ambiente Avd Carlos III S-N Toledo 45071 Spain;

    Univ Autonoma Madrid Dept Quim Inorgan Fac Ciencias E-28049 Madrid Spain;

    Univ Castilla La Mancha Dept Quim Inorgan Organ &

    Bioquim Inst Nanociencia Nanotecnol &

    Mat Mol INAMOL Fac Ciencias Medio Ambiente Avd Carlos III S-N Toledo 45071 Spain;

    Univ Castilla La Mancha Dept Quim Inorgan Organ &

    Bioquim Fac Ciencias &

    Tecnol Quim Campus Ciudad Real Avd Camilo Jose Cela 10 E-13071 Ciudad Real Spain;

    Univ Castilla La Mancha Dept Quim Inorgan Organ &

    Bioquim ETS Ingenieros Ind Campus Ciudad Real Avd Camilo Jose Cela 3 E-13071 Ciudad Real Spain;

    Univ Castilla La Mancha Dept Quim Inorgan Organ &

    Bioquim Inst Nanociencia Nanotecnol &

    Mat Mol INAMOL Fac Ciencias Medio Ambiente Avd Carlos III S-N Toledo 45071 Spain;

    CSIC Inst Catalisis &

    Petroleoquim E-28049 Madrid Spain;

    Univ Autonoma Madrid Dept Quim Inorgan Fac Ciencias E-28049 Madrid Spain;

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  • 正文语种 eng
  • 中图分类 化学;无机化学;
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