1,3-二(三甲基硅基)-2-叔丁基锂与铁(Ⅱ)、钴(Ⅱ)、镍(Ⅱ)、钛(Ⅳ)的反应及结构

Reaction and Crystal Structures of 1,3-bis(trimethylsilyl)-2-t-butyl-aza-allyl-Lithium with Iron(Ⅱ), Cobalt(Ⅱ), Nickel(Ⅱ), Titanium(Ⅳ)

1,3-二(三甲基硅基)-2-叔丁基锂与氯化镍或四氯化钛反应合成了内消旋的1,3-二(三甲基硅基)-2-叔丁基偶联化合物(1);与氯化钴和氯化亚铁反应分别生成了二配位的1,3-二(三甲基硅基)-2-叔丁基钴和铁配合物(2,3)。用NMR,元素分析和X-射线衍射对其单晶的结构进行了分析,结果表明:化合物1属三斜晶系;化合物2和3均属单斜晶系,配合物2中心钴为六配位畸变的八面体构型。配合物3与2结构相类似。

Aza-allyl lithium [LiN（R）C（Bu）CHR]2 （R=SiMe3）reacted with NiCl2 or TiCh to produce a coupling meso-compound [N（SiMe3）C（Bu）CH（SiMe3）]2 （1）, or with COCl2, FeCl2 （mole ratio 2：1） to produce complex 1,3-bis （trimethylsilyl）-2-t-butyl-aza-allyl cobalt（Ⅱ） （2） and 1,3-bis（trimethylsilyl）-2-t-butyl-aza-allyl iron（Ⅱ） （3） respectively. Compounds 1, 2 and 3 were characterized by elemental analysis, H and 13C NMR spectra and X-ray single crystal diffraction. The results show that the compound 1 belongs to the triclinic space group P1. A centro-symmetric dimer aggregation is observed with the two moiety positioned in trans manner. The complex 2 belongs to the monoclinic space group C2/c. The molecular structure of 2 is rigorous centro-symmetry. The six coordination atoms of two 1-aza-allyl ligands organize the distorted octahedral field of central cobalt atom. The structure of 3 is similar to complex 2. CCDC： 219193, 1; 219194, 2; 219195, 3.