四羰基二(五甲二硅基环戊二烯基)二钼的合成及反应  

Synthesis and Reactions of Tetracarbonyl Bis(pentamethyldisi-lanylcyclopentadienyl) Di-Molybdenum

作　　者：邝代治 周秀中[2] 

机构地区：[1]衡阳师范专科学校化学系,衡阳421008 [2]南开大学化学系,天津300071

出　　处：《化学学报》1994年第9期853-857,共5页Acta Chimica Sinica

基　　金：南开大学元素有机化学所国家重点实验室资助的课题.

摘　　要：五甲二硅基环戊二烯与Mo(CO)_6在甲苯中加热回流9h,生成[η-Me_5Si_2C_5H_4Mo(CO)_3]_2(1),1的甲苯溶液进一步加热则发生脱羰而生成(?)(2),2分别与Ph_3P,HC≡CH及PhC≡CH反应,生成加成产物:(η-Me_5Si_2C_5H_4)(CO)_2Mo-(PPh_3)Mo(CO)_2(PPh_3)(C_5H_4Si_2Me_5-η)(3),[η-Me_5Si_2C_5H_4Mo(CO_2)]_2(μ-HC≡CH(4)及[η-Me_5Si_2C_5H_4Mo(CO)_2]_2(μ—PhCCH)(5).以元素分析,IR和~1H NMR谱表征了它们的结构,并用X射线衍射测定了4的晶体结构.4的晶体属单斜晶系,空间群P2_1/α,晶胞数据:α=1.3139(2),b=0.7350(1),c=3.5247(9)nm;β=92.87(2)°,V=3.3996nm^3,Z=4,D_c=1.41g·cm^(-3).The toluene solution of pentamethyldisilanyl cyclopentadiene and Mo(CO)6 was heated at reflux for 9h to yield the dimolybdenum complex [η-Me5Si2C5H4Mo(CO)3]2(l). 1 was converted into the title compound (η-Me5Si2C5H4) (CO)2Mo= Mo(CO)2 (C5H4Si2Me5-η) (2) by thermal decarbonylation. 2 reacted respectively with Ph3P, HC≡CH and PhC≡CH afforded the addition products:[η-Me5Si2C5H4Mo(CO)2PPh3] 2(3), [η-Me5Si2C5H4)(CO)2Mo]2(μ-HC≡CH) (4) and [(η-Me5Si2C5H4)(CO)2Mo]2(μ-PhC≡CH) (5). Their structures were characterized by elemental analyses, IR and 1H NMR spectra, the crystal structure of 4 was determined by X-ray diffraction. The crystals are monoclinic, space group P21 / a with a =1.3139(2), b = 0.7350(1),c = 3.5247(9)nm;β = 92.87(2)°, V=3.3996nm3, Z=4, Dc= 1.41g ·cm-3.

关 键 词：羰基 硅基 环戊二烯基 钼 合成 

分 类 号：O627.63[理学—有机化学]