烯烃配位的过渡金属卡宾配合物的研究——ⅩⅥ.四氟苯并双环[2.2.2]辛三烯三羰基铁的新奇开环反应——新型螯合双烯丙基二羰基铁配合物的合成和结构  

Studies on Olefin-Coordinating Transition Metal Carbene Complexes——ⅩⅥ. An Unusual Ring-Opening Reaction of Tetrafluorobenzobicyclo-[2.2.2] octatriene (triearbonyl) iron——Synthesis and Structure of New Type of Chelated Diallyl Dicarbonyliron

作　　者：陈家碧[1] 殷建国[1] 徐维铧[1] 来鲁华[2] 张泽莹[2] 邵美成[2] 

机构地区：[1]中国科学院上海有机化学研究所 [2]北京大学物理化学研究所

出　　处：《化学学报》1990年第2期195-203,共9页Acta Chimica Sinica

基　　金：中国科学院科学基金;国家自然科学基金

摘　　要：四氟苯并双环[2.2.2]辛三烯三羰基铁(C_(12)H_6F_4)-Fe(CO)_3(1)与芳基锂试剂ArLi(Ar=C_6H_5ο-,m-,ρ-CH_3C_6H_4、ρ-CH_3OC_6H_4、ρ-ClC_6H_4),在低温下反应,生成的酰羰基锂盐中间体用三乙基氧铃一四氟硼酸盐(Et_3OBF_4)在水溶液中于O℃进行烷基化时,双环烯烃配体开环,生成组成为(C_(12)H_6F_4)(CO)_2FeC(OC_2H_5)Ar的螯合双烯丙基二羰基铁配合物(2—7)。配合物5的晶体属单斜晶系,晶胞参数为:a=16.870(4),b=13.707(4),c=19.361(4)A,β=107.92(2)°,v=4259(1)A^3,z=8,空间群为C_(2h)~6—C2/c,最后的偏离因子R=O.0409,R_w=O.0391。Reaction of tetrafluorobenzobicyclo [2.2.2] octatriene (tricarbonyl) iron (C_(12)H_6F_4). Fe(CO)_3 (1) with aryllithium reagents, ArLi (Ar=C_6H_5; o-, m-, p-CH_3C_6H_4; p-CH_3C(?)H_4; p-ClC_6H_4) in ether at low tempenature, and subsequent alkylation of the formed acylmetalates with Et_3OBF_4 in aqueous solution at 0℃ led to the novel ringopening reaction of the bicyolodiene ligand to give the chelated diallyl dicarbonyliron complexes 2—7 with the compositions of (C_(12)H_6F_4)(CO)_2FeC(OC_2H_5)Ar. The single crystals of the complex 5 belong to monoclinic system, with a=16.870 (4) , b=13.707(4) c=19.361(4)(?), β=107.92(2), V=4259(1)(?)~3, Z=8, D_c=l.51g/cm^3, and with space group C_(?)~6-C2/c. The final discrepancy indices are R=0.0409 and R_w=0.0391.

关 键 词：铁配合物 螯合双烯丙基 二羰基铁 

分 类 号：O614.811[理学—无机化学]