对苯二甲酰双环戊二烯基锡钼(钨)异多核金属配合物的合成与晶体结构  

Synthesis and Crystal Structure of Terephthaloyl Bridging Cyclopentadienyl M-Sn(Ⅳ) Bonded Heteromultimetallic Complexes

作　　者：唐良富[1] 柴建方[1] 赵书斌[1] 王积涛[1] 曹秀英[2] 

机构地区：[1]南开大学化学系,天津300071 [2]天津市科学技术信息研究所,天津300074

出　　处：《化学学报》2002年第7期1298-1302,共5页Acta Chimica Sinica

基　　金：国家自然科学基金 (No .2 0 172 0 2 9;2 9972 0 2 6 )资助项目

摘　　要：通过对苯二甲酰双环戊二烯基三羰基钼 (钨 )负离子与有机锡的反应 ,合成了一系列的对苯二甲酰双环戊二烯基锡钼 (钨 )异多核金属配合物 ,并用IR ,1HNMR和元素分析对其进行了表征 .结果表明 ,环戊二烯上的拉电子取代基极大地减弱金属负离子的亲核性 ,对苯二甲酰双环戊二烯基三羰基钼 (钨 )负离子与R2 SnCl2 (R =Ph ,Me ,Et)反应时 ,仅有一个氯原子被金属负离子所取代 .用X射线单晶衍射测定了化合物 {p [(Ph3 Sn) (CO) 3 MoC5H4 C(O) ]2 C6H4 }的晶体结构 .该晶体为单斜晶系 ,空间群为C2 /c,晶胞参数为 :a =3 42 0 9(10 )nm ,b=1 132 9(3)nm ,c=1 42 14(4 )nm ,β =10 4 46 6 (5 )° ,V =5 334 (3)nm3 ,Z =4,R =0 0 33.A series of heteromultimetallic complexes have been synthesized by the reaction of the dianions {p-[(CO) 3MC 5H 4C(O)] 2C 6H 4} 2- (M= Mo, W) with R nSnCl 4-n (R=Ph, Me, Et; n= 2, 3) in 1∶2 or 1∶1 ratio, and characterized by elemental analysis, 1H NMR and IR spectroscopy.The electron-withdrawing groups on the cyclopentadienyl rings greatly decrease the nucleophilicity of the metallic anions.Thus, only one chlorine atom on tin compound was replaced by the metallic anion when the dianions reacted with SnR 2Cl 2.The crystal structure of {p-[(Ph 3Sn)(CO) 3MoC 5H 4C(O)] 2C 6H 4} was determined by X-ray structure analysis, which is monoclinic, space group C2/c with unit cell parameters: a=3.4209(10) nm, b=1.1329(3) nm, c=1.4214(4) nm, β=104.466(5)°, V=5.334(3) nm 3, Z=4, R=0.033. The central metal of Mo adopts a 3∶4 piano stool structure, and two SnMo units are in trans- position of the bridging phenyl group.

关 键 词：对苯二甲酰双环戊二烯基 合成 杂多核金属化合物 晶体结构 锡 钼 钨 

分 类 号：O641.4[理学—物理化学]