二氯卡宾与四苯基环戊二烯酮脱氧反应产物的晶体和分子结构

STUDIES ON CRYSTAL STRUCTURE OF REACTION PRODUCT OF DICHLOROCARBENE WITH TETRAPHENYLCYCLOPENTADIENON

本文报道了二氯卡宾 (由一溴二氯苯基甲基汞产生 )与四苯基环戊二烯酮 (TPCP)脱氧反应产物的晶体与分子结构 ,并就其结构特征讨论了反应机理和产物的关系。二氯卡宾与TPCP脱氧反应的产物为偕二氯环戊二烯 (1,1 二氯四苯基环戊二烯 ) ,属于正交晶系 ,空间点群为P2 12 12 1,晶胞参数a =0 .85 83(2 ) ,b =1.15 6 2(3) ,c =2 .2 5 6 5 (5 )nm ,v =2 .2 39(2 )nm3 ,Mr=430 .39,Dx =1.30g/cm3 。最终偏差因子R =0 .0 6 1,Rw =0 .0 6 5。

The crystal structure of the deoxygenating reaction product 1,1 dichlorotetraphenylcyclopentadienone of phenyl (bromodichloromethyl) mercury with tetraphenylcyclopentadienone (TPCP) is reported.The crystal belongs to quadratic,space group P2 12 12 1,with unit cell of a=0.8583(2),b=1.1562(3),c=2.2565(5)nm,V=2.239(2)nm 3,Z=4,Mr=439.39,Dx=1.30g/cm 3,μ=3.02cm -1 ,F(000)=912.The final deviation factor has coverage with R=0.061 and Rw=0.065 for 1332 observed independent reflections.These observed results support the previously proposed mechanism for the carbene reaction of this type in which the structural characteristics of the incipient carbonyl ylide intermediate is suggested to play a key role in choosing different competitive pathways.