新型η3-苄基环戊二烯镍络合物的合成及其晶体结构

Synthesis and Crystal Structure of a Novel η~3-benzyl Cyclopentadienyl Nickel Complex

二茂镍与1,1-二苯基(三甲基硅基)甲基锂反应合成了一个新的η3-苄基环戊二烯基镍络合物——(η5-环戊二烯)[7-苯基-7-(三甲基)硅基-1,2,7-η3-苄基]镍(1),其结构经NMR,MS,元素分析和单晶X-射线衍射表征。1属单斜晶系,空间群C12/c1,晶胞参数a=19.2180(6),b=16.6330(5),c=14.3880(4),α=90.00°,β=123.91°,γ=90.00°,V=3816.73(20)3,Z=8。晶体结构数据显示1包含η3-苄基并具有18价电子构型。反应产物除1外还分离出了四苯乙烯和其他几种有机镍络合物,四苯乙烯的存在证明在反应过程中发生了C-Si键断裂。

A novel η3-benzyl cyclopentadienyl nickel complex,（η5-cyclopentadienyl）[7-phenyl-7-（trimethyl）silyl-1,2,7-η3-benzyl]nickel（1）,was synthesized by the reaction of nickelocene with 1,1-diphenyl（trimethylsilyl）methyl lithium.The structure was characterized by NMR,MS,elemental analysis and single crystal X-ray diffraction.1 belongs to monoclinic system,space group C1 2/c 1 with a=19.218 0（6）,b=16.633 0（5）,c=14.388 0（4）,α=90.00°,β=123.91°,γ=90.00°,V=3 816.73（20）3,Z=8.The results showed that 1 possessed 18 valence electron configuration which contains η3-benzyl group.Tetraphenyl ethylene and other organonickel clusters were also isolated from the products.Mechanism of the reaction was discussed.Formation of tetraphenyl ethylene in the reaction proved the dissociation of C-Si bond.