新型硅基桥连双(环戊二烯基)四羰基二铁类配合物的合成  

Synthesis of Novel Silyl-bridged Bis(cyclopentadienyl)Tetracarbonyldiiron Complexes

作　　者：谷广娜 王俊岭[1] 冯书晓[1] 马军营[1] GU Guang-na;WANG Jun-ling;FENG Shu-xiao;MA Jun-ying(College of Chemical Engineering and Pharmaceutics,Henan University of Science and Technology,Luoyang 471023,China)

机构地区：[1]河南科技大学化工与制药学院,河南洛阳471023

出　　处：《合成化学》2020年第5期421-425,共5页Chinese Journal of Synthetic Chemistry

基　　金：河南省自然科学基金资助项目(182300410353);河南省高等学校重点科研项目(20A430012);河南科技大学青年基金资助项目(2015QN002);河南科技大学博士科研启动基金资助项目(13480048)。

摘　　要：以六甲基二硅烷为原料,经氯代、格式反应和锂化反应制得双(环戊二烯基)配体(C5H5)2MeSiSiMe2R(3a^3c),将该配体分别与五羰基铁在对二甲苯中回流反应,合成了3种新型的硅基桥连双(环戊二烯基)四羰基二铁类配合物[η^5,η^5-C5H4MeSi(SiMe2R)C5H4]Fe2(CO)2(μ-CO)2[R=p-C6H4CH3(4a),R=p-C6H4OCH3(4b),R=CH2C6H5(4c)],其结构经1H NMR,13C NMR,IR和元素分析表征。并用X-射线单晶衍射法确定了配合物4b的分子结构。结果表明:4b(CCDC:1942618)属单斜晶系,Cc空间群,晶胞参数a=18.591(3)A,b=10.3080(10)A,c=14.136(2)A,α=90°,β=117.262(6)°,γ=90°,V=2408.1(6)A^3,Z=4,F(000)=1152,Dc=1.546 g·cm^-3,μ=1.338 mm^-1,R1=0.0351,wR2=0.0754。The bis(cyclopentadienyl)ligands,(C5H5)2MeSiSiMe2R(3 a^3 c),were prepared by chlorination,Grignard reaction and lithiation reaction using hexamethyldisilane as starting materials.Then three new silyl-bridged bis(cyclopentadienyl)tetracarbonyldiiron complexes[η^5,η^5-C5H4MeSi(SiMe2R)C5H4]Fe2(CO)2(μ-CO)2[R=p-C6H4CH3(4 a),R=p-C6H4OCH3(4 b),R=CH2C6H5(4 c)]were synthesized by the reactions of 3 a^3 c with Fe(CO)5 in refluxing p-xylene.The molecular structures of 4 a^4 c were characterized by 1H NMR,13C NMR,IR and elemental analysis.The crystal structure of complex 4 b was determined by X-ray diffraction.The result showed that 4 b(CCDC:1942618)belonged to monoclinic,space group Cc,with crystal cell parameters of a=18.591(3)A,b=10.3080(10)A,c=14.136(2)A,α=90°,β=117.262(6)°,γ=90°,V=2408.1(6)A^3,Z=4,F(000)=1152,Dc=1.546 g·cm^-3,μ=1.338 mm^-1,R1=0.0351,wR2=0.0754.

关 键 词：桥连环戊二烯 羰基铁化合物 硅基桥 配合物 晶体结构 合成 

分 类 号：O627.8[理学—有机化学] O626[理学—化学]