Structure of [Rh2(CO)2(.mu.-Cl)((C6H5)2PCH2P(C6H5)2)2][BF4]. A binuclear "A-frame" complex showing the open "active" site
Structure of [Rh2(CO)2(.mu.-Cl)((C6H5)2PCH2P(C6H5)2)2][BF4]. A binuclear "A-frame" complex showing the open "active" site
复制标题
[Rh2(CO)2(μ-Cl)((C6H5)2PCH2P(C6H5)2)2][BF4]的结构。
DOI：
10.1021/ic50200a013
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发表时间：
1979
期刊：
影响因子：
--
通讯作者：
S. Dwight
中科院分区：
文献类型：
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作者：
M. Cowie;S. Dwight
配合物[Rt^ COMq-ClXCQHsXPC^ PCCeHsXX][BF_4]的结构经X射线晶体学测定，证实它是一个“A-框架”型物种。结构参数在大多数方面与密切相关的物种[Rl^CCOXGu-SXHsQHsXPCHíPtQHsXX]相似，显著差异在于桥接两个金属中心的“活性”位点更容易被本络合物中的小分子攻击。标题配合物在丙酮溶液中结晶，空间群为C_1P ~ 1，仅含PF ~（6-）和B（C_6H_5）~（4-）。有证据表明，BF 4-阴离子是HF从玻璃中浸出硼的结果。约化后的晶胞尺寸为a= 13.044（1）A，B= 14.962（2）A，c= 12.800（2）A，a= 96.20（1），ε = 92.56（1），y= 86.42（1），Z= 2。基于5729个独特的、观察到的反射，通过全矩阵、最小二乘技术将结构细化到R= 0.046和Rn = 0.064的一致性指数。相关测量参数为：Rh-P（av）= 2.321（2）A，Rh-C= 1.794（7）和1.807（7）A，Rh-Cl= 2.380（2）和2.406（2）A，CO= 1.184（8）和1.202（8）A，Rh-Rh= 3.1520（8）A，C-Rh-Cl= 170.9（2）和172.6（3），Rh-Cl-Rh= 82.38（5）。
The structure of the complex [Rt^ COMq-ClXCQHsXPC^ PCCeHsXX][BF4] has been determined by X-ray crystallography, verifying that it is an “A-frame” type species. The structural parameters are similar inmost aspects to those of the closely related species [Rl^ CCOXGu-SXÍQHsXPCHíPtQHsXX], with the significant difference that the “active” site, bridging the two metal centers, is more open to attack by small molecules in the present complex. The title complex crystallizes in the space group C¡ lP\from an acetone solution containing as the only anions PF6~ and B (C6H5) 4~. Evidence suggests that theBF4 “anion results from the leaching of boron from the glass by HF. Thereduced unit cell has dimensions a= 13.044 (1) A, b= 14.962 (2) A, c= 12.800 (2) A, a= 96.20 (1), ß= 92.56 (1), and y= 86.42 (1) with Z= 2. On the basis of 5729 unique, observed reflections the structure was refined by full-matrix, least-squares techniques to agreement indices of R= 0.046 and R „= 0.064. Some relevant metrical parameters are Rh-P (av)= 2.321 (2) A, Rh-C= 1.794 (7) and 1.807 (7) A, Rh-Cl= 2.380 (2) and 2.406 (2) A, CO= 1.184 (8) and 1.202 (8) A, Rh-Rh= 3.1520 (8) A, C-Rh-Cl= 170.9 (2) and 172.6 (3), and Rh-Cl-Rh= 82.38 (5).