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铼的阳离子卡拜络合物,[π-C_5H_5(CO)_2—R_(?)CC_6H_5]BBr4(Ⅰ),在THF中低温下与邻-碳硼烷基锂反应,碳硼烷基阴离子加成到卡拜碳和羰基碳原子上生成两个新奇的铼的卡宾和卡拜络合物,π-环戊二烯基二羰基[(1-碳硼烷基)(苯基)卡宾]铼[π-C_5H_5(CO)_2ReC(C_2HB_(10)H_(10))C_6H_5](Ⅱ)和π-环戊二烯基羰基(1-碳硼烷基甲酰基)(苯基卡拜)铼[π-C_5H_5(CO)(COC_2HB_(10)H_(10))ReCC_6H_51(Ⅲ)。这表明在阳离子卡拜络合物Ⅰ中有两个亲电中心。络合物Ⅲ在溶液中室温下逐渐转变为络合物Ⅱ。Ⅱ和Ⅲ是通过元素分析和红外、核磁共振光谱及质谱分析,最后通过X射线单晶结构分析鉴定的。本文还讨论了上述反应的可能机制。
Rhenium cationic caculate complex, [π-C_5H_5 (CO) _2-R_ (?) CC_6H_5] BBr4 (Ⅰ) is reacted with ortho-carboborane at low temperature in THF, Carbocyclic and carbazole complexes that generate two novel rheniums upon carbazole and carbonyl carbon atoms, π-cyclopentadienyl dicarbonyl [(1-carboborane) (phenyl) carbene] rhenium [π-C_5H_5 (CO) _2ReC (C_2HB_ (10) H_ (10)) C_6H_5] (Ⅱ) and π-cyclopentadienylcarbonyl π-C_5H_5 (CO) (COC_2HB_ (10) H_ (10)) ReCC_6H_51 (Ⅲ). This indicates that there are two electrophilic centers in the cationic Carbazole complex I. Complex III is gradually converted to Complex II in solution at room temperature. Ⅱ and Ⅲ were identified by elemental analysis, IR, 1H NMR and MS, and finally by X-ray single crystal structure analysis. This article also discusses the possible mechanism of the above reaction.