Synthesis of gold phosphido complexes derived from bis(secondary) phosphines. structure of tetrameric [Au(MesP(CH(2))(3)PMes)Au](4).
Synthesis of gold phosphido complexes derived from bis(secondary) phosphines. structure of tetrameric [Au(MesP(CH(2))(3)PMes)Au](4).
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由双（仲）膦衍生的金磷配合物的合成。
DOI：
10.1021/ic100219j
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发表时间：
2010
影响因子：
4.6
通讯作者：
A. Rheingold
中科院分区：
文献类型：
--
作者：
Elizabeth M. Lane;Timothy W. Chapp;R. Hughes;David S. Glueck;B. Feland;G. Bernard;R. Wasylishen;A. Rheingold
处理2当量Au（THT）Cl（THT =四氢噻吩）与双（仲）膦HP（R）约为PH（R）（接头近似=（CH（2））（3），R = Mes = 2，4，6-Me（3）C（6）H（2）（1），R = Is = 2，4，6-（i-Pr）（3）C（6）H（2）（2），R = Ph（4）;近似=（CH（2））（2），R = Is（3）; HP（R）近似PH（R）= 1，1 ′-（eta（5）-C（5）H（4）PHPh）（2）Fe（5）），得到双核配合物（AuCl）（2）（μ-HP（R）近似PH（R））（6-10）。用氨水进行脱卤化氢反应，得到磷配合物[（Au）（2）（μ-P（R）约P（R））]（n）（11-15）。二茂铁基和苯基膦基衍生物15和14是不溶的;后者的特征在于固态（31）P NMR光谱。Isitylphosphido配合物12和13产生了广泛的，不明确的NMR光谱。然而，均三甲苯基磷并配合物11以单一产物形式形成，其通过多核溶液核磁共振光谱、固态（31）P核磁共振光谱和元素分析进行表征。质谱分析表明，这种材料含有8个金原子（n = 4）。根据（1）H NMR谱提出的结构，含有磷原子的扭曲立方体，通过X射线晶体结构测定得到证实。NMR光谱，包括通过（1）H NMR DOSY测量11的流体动力学半径，表明该结构在溶液中保持。密度泛函理论（DFT）的结构计算11也在很好的协议与固态结构。
Treatment of 2 equiv of Au(THT)Cl (THT = tetrahydrothiophene) with the bis(secondary) phosphines HP(R) approximately PH(R) (linker approximately = (CH(2))(3), R = Mes = 2,4,6-Me(3)C(6)H(2) (1), R = Is = 2,4,6-(i-Pr)(3)C(6)H(2) (2), R = Ph (4); approximately = (CH(2))(2), R = Is (3); HP(R) approximately PH(R) = 1,1'-(eta(5)-C(5)H(4)PHPh)(2)Fe (5)), gave the dinuclear complexes (AuCl)(2)(mu-HP(R) approximately PH(R)) (6-10). Dehydrohalogenation with aqueous ammonia gave the phosphido complexes [(Au)(2)(mu-P(R) approximately P(R))](n) (11-15). Ferrocenyl- and phenylphosphido derivatives 15 and 14 were insoluble; the latter was characterized by solid-state (31)P NMR spectroscopy. Isitylphosphido complexes 12 and 13 gave rise to broad, ill-defined NMR spectra. However, mesitylphosphido complex 11 was formed as a single product, which was characterized by multinuclear solution NMR spectroscopy, solid-state (31)P NMR spectroscopy, and elemental analyses. Mass spectrometry suggested that this material contained eight gold atoms (n = 4). A structure proposed on the basis of the (1)H NMR spectra, containing a distorted cube of phosphorus atoms, was confirmed by X-ray crystallographic structure determination. NMR spectroscopy, including measurement of the hydrodynamic radius of 11 by (1)H NMR DOSY, suggested that this structure was maintained in solution. Density functional theory (DFT) structural calculations on 11 were also in good agreement with the solid-state structure.