Dinuclear organogold(I) complexes bearing uracil moieties: chirality of Au(I)-Au(I) axis and self-assembling
Dinuclear organogold(I) complexes bearing uracil moieties: chirality of Au(I)-Au(I) axis and self-assembling
复制标题
带有尿嘧啶部分的双核有机金(I)配合物：Au(I)-Au(I)轴的手性和自组装
DOI：
10.1039/c5ce00221d
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发表时间：
2015
期刊：
影响因子：
3.1
通讯作者：
and Toshikazu Hirao
中科院分区：
文献类型：
--
作者：
Yuki Sakamoto;Toshiyuki Moriuchi;and Toshikazu Hirao
双核有机金（I）配合物与作为有机金属化合物的桥连双膦配体和作为核碱基的尿嘧啶衍生物的缀合被证明提供生物有机金属缀合物。双核有机金（I）-尿嘧啶共轭物的单晶X-射线结构测定揭示了金（I）和尿嘧啶部分在固态下的组装性质。以Xantphos为桥连双膦配体的（U 6 Au）2（μ-Xantphos）（U 6 = 6-乙炔基-1-辛基尿嘧啶）的晶体结构揭示了分子内亲金性Au（I）-Au（I）相互作用的存在。基于Au（I）-Au（I）轴的R-和S-对映体存在于晶胞中，它们通过尿嘧啶部分之间的分子间氢键交替连接以形成氢键组装体。在双核有机金（I）配合物（U 5 Au）2（μ-Xantphos）（U 5 = 5-乙炔基-1-辛基尿嘧啶）的情况下，发现两种对映体通过5-乙炔基-尿嘧啶部分之间的π-π相互作用分别形成纯手性RR和SS二聚体。在晶体堆积中，每个二聚体通过尿嘧啶部分之间的分子间氢键交替组装以形成氢键组装体。如所预期的，利用（R）-BINAP作为具有轴向手性的桥接双膦配体诱导了Au（I）-Au（I）轴的手性。双核有机金（I）与（R）-BINAP（U6 Au）2（μ-R-BINAP）配合物的晶体结构证实了Au（I）-Au（I）轴的轴向手性，形成R，R-对映体，其中每个分子通过尿嘧啶部分之间的分子间氢键排列，形成螺旋分子排列。
The conjugation of dinuclear organogold(I) complexes with a bridging diphosphine ligand as an organometallic compound and the uracil derivative as a nucleobase was demonstrated to afford bioorganometallic conjugates. Single-crystal X-ray structure determination of the dinuclear organogold(I)–uracil conjugates revealed the assembly properties of gold(I) and the uracil moieties in the solid state. The crystal structure of (U6Au)2(μ-Xantphos) (U6 = 6-ethynyl-1-octyluracil) with Xantphos as the bridging diphosphine ligand revealed the presence of an intramolecular aurophilic Au(I)–Au(I) interaction. R- and S-enantiomers based on the Au(I)–Au(I) axis exist in the unit cell, which are connected alternately to form the hydrogen-bonded assembly through intermolecular hydrogen bonds between the uracil moieties. In the case of the dinuclear organogold(I) complex (U5Au)2(μ-Xantphos) (U5 = 5-ethynyl-1-octyluracil), both enantiomers were found to form homochiral RR and SS dimers, respectively, through π–π interactions between 5-ethynyl-uracil moieties. In the crystal packing, each dimer is assembled alternately to form the hydrogen-bonded assembly through intermolecular hydrogen bonds between the uracil moieties. As expected, the utilization of (R)-BINAP as a bridging diphosphine ligand with axial chirality induced the chirality of the Au(I)–Au(I) axis. The crystal structure of the dinuclear organogold(I) complex with (R)-BINAP (U6Au)2(μ-R-BINAP) confirmed the axial chirality of the Au(I)–Au(I) axis, forming a R,R-enantiomer, wherein each molecule is arranged through intermolecular hydrogen bonds between the uracil moieties to form a helical molecular arrangement.