Syntheses and structures of dinuclear gold(I) dithiophosphonate complexes and the reaction of the dithiophosphonate complexes with phosphines: diverse coordination types.
Syntheses and structures of dinuclear gold(I) dithiophosphonate complexes and the reaction of the dithiophosphonate complexes with phosphines: diverse coordination types.
复制标题
双核金(I)二硫代磷酸盐配合物的合成和结构以及二硫代磷酸盐配合物与膦的反应：多种配位类型。
DOI：
10.1021/ic034114y
复制
发表时间：
2003
期刊：
影响因子：
--
通讯作者：
FacklerJr,JohnP
中科院分区：
文献类型：
--
作者：
Maspero,Angelo;Kani,Ibrahim;Mohamed,AhmedA;Omary,MohammadA;Staples,RichardJ;FacklerJr,JohnP
双核二硫代磷酸金 (I) 络合物，[Au2(dtp)2] (1)，其中 dtp = [S2P(R)(OR‘)]-，其中 R =p-C6H4OCH3；合成了R‘=c-C5H9，并研究了其与膦配体PPh3和Ph2P(CH2)nPPh2(n= 1−4)的反应。化合物1含有两个由阴离子二硫代膦酸酯配体同桥联的金原子，形成椅形八元环配合物。 1与二膦配体反应后，形成双核开环配合物Au2(dppm)(dtp)2(2)、Au2(dppe)(dtp)2(3)、Au2(dppp)(dtp)2(4)、Au2(dppb)(dtp)2(5)（dppm = 二苯基膦甲烷；dppe = 二苯基膦乙烷；dppp =二苯基膦基丙烷；dppb =二苯基膦基丁烷）。与 dppm 的反应取决于化学计量。因此，当1与2当量的dppm反应时，形成离子络合物[Au2(dppm)2(dtp)]dtp。该 dtp 抗衡离子与四氟硼酸根交换，得到 [Au2(dppm)2(dtp)]BF4，其结晶得到两种可相互转化的异构体：6-黄色和7-白色。 1 与 PPh3 反应得到四配位单核复合物 [Au(dtp)(PPh3)2] (8)。 1−8的分子结构经X射线晶体学证实，并显示出多种配位模式和几何形状。 1 及其与 dppm (2,6,7) 的反应产物的晶体结构显示出 2.95−3.10 Å 的短分子内 Au·Au 亲金键相互作用，但没有可辨别的分子间相互作用。然而，1 与长链 Ph2P(CH2)nPPh2 配体（n= 2−4）的反应产物表现出缺乏分子内和分子间 Au·Au 相互作用的结构。
The dinuclear gold(I) dithiophosphonate complex, [Au2(dtp)2] (1), where dtp = [S2P(R)(OR‘)]-with R =p-C6H4OCH3; R‘=c-C5H9, has been synthesized and its reaction studied with the phosphine ligands PPh3and Ph2P(CH2)nPPh2(n= 1−4). Compound1contains two gold atoms homobridged by the anionic dithiophosphonate ligand, forming an eight-membered ring complex in a chair form. After the reaction of1with diphosphine ligands, the dinuclear open-ring complexes Au2(dppm)(dtp)2(2), Au2(dppe)(dtp)2(3), Au2(dppp)(dtp)2(4), Au2(dppb)(dtp)2(5) were formed (dppm = diphenylphosphinomethane; dppe = diphenylphosphinoethane; dppp = diphenylphosphinopropane; dppb = diphenylphosphinobutane). The reaction with dppm is stoichiometry-dependent. Thus, when1reacts with 2 equiv of dppm, the ionic complex [Au2(dppm)2(dtp)]dtp forms. This dtp counterion was exchanged with tetrafluoroborate to yield [Au2(dppm)2(dtp)]BF4, the crystallization of which afforded two interconvertible isomers,6-yellow and7-white. Reaction of1with PPh3affords the tetracoordinate mononuclear complex [Au(dtp)(PPh3)2] (8). The molecular structures of1−8were confirmed by X-ray crystallography and show multiple coordination modes and geometries. The crystal structures of1and its reaction products with dppm (2,6,7) show short intramolecular Au···Au aurophilic bonding interactions of 2.95−3.10 Å while no intermolecular interactions were discernible. However, reaction products of1with longer-chain Ph2P(CH2)nPPh2ligands,n= 2−4, exhibit structures that lack both intra- and intermolecular Au···Au interactions.