Ferrer Montserrat, Giménez Leticia, Gutiérrez Albert, Lima João Carlos, Martínez Manuel, Rodríguez Laura, Martín Avelino, Puttreddy Rakesh, Rissanen Kari
Departament de Química Inorgànica i Orgànica, Secció de Química Inorgànica. Universitat de Barcelona, c/Martí i Franquès 1-11, 08028 Barcelona, Spain.
LAQV-REQUIMTE, Departamento de Química, Universidade Nova de Lisboa, Monte de Caparica, Portugal.
Dalton Trans. 2017 Oct 17;46(40):13920-13934. doi: 10.1039/c7dt02732j.
A series of alkynyl gold(i) tri and tetratopic metallaligands of the type [Au(C[triple bond, length as m-dash]C-R)(μ-triphosphane)] (R = 2,2'-bipyridin-5-yl or CHN, 2,2':6',2''-terpyridin-4-yl or CHN; triphosphane = 1,1,1-tris(diphenylphosphanyl)ethane or triphos, 1,3,5-tris(diphenylphosphanyl)benzene or triphosph) and [Au(C[triple bond, length as m-dash]C-R)(μ-tetraphosphane)] (R = CHN, CHN; tetraphosphane = tetrakis(diphenylphosphanylmethyl)methane or tetraphos, 1,2,3,5-tetrakis(diphenylphosphanyl)benzene or tpbz, tetrakis(diphenylphosphaneylmethyl)-1,2-ethylenediamine or dppeda) were obtained in moderate to good yields. All complexes could be prepared by a reaction between the alkynyl gold(i) polymeric species [Au(C[triple bond, length as m-dash]C-R)] and the appropriate polyphosphane. An alternative strategy that required the previous synthesis of the appropriate acetylacetonate precursors [Au(acac)(μ-polyphosphane)] ("acac method") was assayed, nevertheless only the polyacac derivatives [Au(acac)(μ-triphosphane)] (triphosphane = triphos and triphosph) and [Au(acac)(μ-tetraphos)] could be isolated and characterized. All compounds were characterized by IR, multinuclear NMR spectroscopy and ESI(+) mass spectrometry. The X-ray crystal structure of complexes [Au(C[triple bond, length as m-dash]C-CHN)(μ-tetraphos)] and [Au(C[triple bond, length as m-dash]C-CHN)(μ-tpbz)] showed the involvement of all the gold atoms in close intramolecular AuAu contact as well as intermolecular π stacking interactions between the aromatic rings of the polypyridyl ligands. The photophysical properties of the synthesized compounds were carefully studied and used as a probe of their possible use as multidentate ligands for Cu(i) and Zn(ii). The UV-Vis speciation studies of the complexation reactions were conducted via metal titration and, in most cases the dangling units of the ligand were found to behave in a fairy independent manner. While in the case of Cu(i) multiple equilibria exist in solution a single complex is detected for Zn(ii) under the conditions studied.
通过中等至良好的产率获得了一系列炔基金（I）三齿和四齿金属配体，其类型为[Au(C≡C-R)(μ-三膦)]（R = 2,2'-联吡啶-5-基或CHN，2,2':6',2''-三联吡啶-4-基或CHN；三膦 = 1,1,1-三（二苯基膦基）乙烷或三膦，1,3,5-三（二苯基膦基）苯或三磷）和[Au(C≡C-R)(μ-四膦)]（R = CHN，CHN；四膦 = 四（二苯基膦基甲基）甲烷或四膦，1,2,3,5-四（二苯基膦基）苯或tpbz，四（二苯基膦基甲基）-1,2-乙二胺或dppeda）。所有配合物都可以通过炔基金（I）聚合物[Au(C≡C-R)]与适当的多膦之间的反应制备。还尝试了一种需要先前合成适当的乙酰丙酮化物前体[Au(acac)(μ-多膦)]的替代策略（“acac方法”），然而，只有聚acac衍生物[Au(acac)(μ-三膦)]（三膦 = 三膦和三磷）和[Au(acac)(μ-四膦)]可以被分离和表征。所有化合物都通过红外光谱、多核核磁共振光谱和ESI(+)质谱进行了表征。配合物[Au(C≡C-CHN)(μ-四膦)]和[Au(C≡C-CHN)(μ-tpbz)]的X射线晶体结构表明，所有金原子都参与了紧密的分子内AuAu接触以及多吡啶配体芳环之间的分子间π堆积相互作用。对合成化合物的光物理性质进行了仔细研究，并将其用作它们作为Cu(I)和Zn(II)的多齿配体可能用途的探针。通过金属滴定进行了络合反应的紫外可见光谱研究，在大多数情况下，发现配体的悬挂单元表现出相当独立的行为。虽然在Cu(I)的情况下溶液中存在多个平衡，但在所研究的条件下，对于Zn(II)只检测到一种配合物。
