化学学报 ›› 1987, Vol. 45 ›› Issue (8): 754-759. 上一篇    下一篇

研究论文

过渡金属卡宾配合物V.铼的阳离子卡拜配合物与邻-碳硼烷双锂盐的反应及其产物π-环戊二烯基二羰基[(1-碳硼烷基)(苯基)卡宾]铼的晶体结构

陈家碧;雷桂馨;徐筱杰;唐有祺   

  1. 中国科学院上海有机化学研究所;北京大学化学系
  • 发布日期:1987-08-15

Transition metal carbene complexes V. Reaction of the cationic carbyne complex of rhenium with 1,2-dilithiocarborane and crystal structure of \p\-cyclopentadienyl-dicarbonyl[(1-carboranyl)(phenyl)carbene]rhenium, [\p\-C5h5(CO)2ReC(C2HB10H10)C6H5]

CHEN JIABI;LEI GUIXIN;XU XIAOJIE;TANG YOUQI   

  • Published:1987-08-15

铼的阳离子卡拜配合物,[π-C5H5(CO)2ReCC6H5]BBr4(1),在THF中低温下与1,2-碳硼烷双锂盐反应,生成π-环戊二烯基二羰基[(1-碳硼烷基)(苯基)卡宾]铼[π-C5H5(CO)2ReC(C2HB10H10)-C6H5](2)及π-环戊二烯羧基[(1-碳硼烷基甲酰基)(苯基卡拜)铼[π-C5H5(CO)(COC2HB10H10)-ReCC6H5](3),和1与邻-碳硼烷单锂盐反应所生成的产物完全相同.2的分子结构已由单晶X-射线结构分析证实.属于单斜晶系,空间群为P21/n,晶胞参数:a=14.043(8)埃,b=8.302(6)埃,c=17.926(11)埃,β=93.96(5).晶胞中有四个分子.其结构已用重原子法解出并用块矩阵最小二乘法修正,最后的偏离因子R=0.076.同时也讨论了可能的反应机制.

关键词: 晶体结构测定, X射线衍射分析, 环戊二烯 P, 环戊二烯 P, 羰基络合物, 羰基络合物, 碳烯, 单晶, 空间效应, 碳硼烷类

The cationic carbyne complex of rhenium, [p-C5H5(CO)2ReCC6H5]BBr4, reacts in THF with 1,2-dilithiocarborane at low temperature to give (p-cyclopentadienyl)dicarbonyl[(1-carboranyl)(phenyl)carbene]rhenium, [p-C5H5(CO)2ReC(C2HB10H10)(C6H5)] (I), and (p-cyclopentadienyl)carbonyl(1-carboranylformacyl)(phenylcarbyne)rhen ium, [p-C5H5(CO)(COC2HB10H10)ReCC6H5], which are identical with the products from the reaction with 1-lithiocarborane. The mol. structure of I has been confirmed by its single crystal x-ray structure determination A possible reaction mechanism is discussed.

Key words: CRYSTAL STRUCTURE DETERMINATION, X-RAY DIFFRACTION ANALYSIS, CYCLOPENTADIENE P, CYCLOPENTADIENE P, CARBONYL COMPLEX, CARBONYL COMPLEX, CARBENE, SINGLE CRYSTALS, STERIC EFFECT, CARBORANES

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