氮硅取代的氮杂烯丙基锂、铁(Ⅱ)和钴(Ⅱ)的合成及结构(英文)

本文以(Me2)NCH2C6H4CHSiMe2(NMe2)]Li(TMEDA)与叔丁腈为原料按1∶1加成得到氮杂烯丙基的锂化合物{(Me2)NCH2C6H4}CHC(tBu)NSiMe2(NMe2)Li(TMEDA)]即1。然后用乙醚或四氢呋喃作溶剂化合物1和二氯化亚铁或二氯化钴按2∶1反应得到氮杂烯丙基铁或钴的化合物分别为2和3。通式为M{(Me2)NCH2C6H4}CHC(tBu)NSiMe2(NMe2)]2(M=Fe(2),Co(3))。化合物1,2和3的结构分别用1H NMR,13C NMR,元素分析和X-射线单晶衍射技术进行了表征。晶体结构表明化合物2和3结构类似,都是以金属为对称中心的硅桥联的端基氮配位的氮杂烯丙基化合物。

Synthesis and Structure of N-Silyl-Substituted the Lithium, Iron(Ⅱ) and Cobalt(Ⅱ) 1-Azaally Complexes

The N-silyl-Ni-(2-((dimethylamino)methyl)benzyl)-N,N,l,l-tetramethylsilanamiolithium 1-azaally compound {(Me2)NCH2C6H4}CHC(tBu)NSiMe2(NMe2)Li(TMEDA)] (1) was synthesized by interaction of (Me2)NCH2C6H4 CHSiMe2(NMe2)]Li(TMEDA) with one equivalent of tertbutyronitrile (tBuCN). The derivative iron(Ⅱ) and cobalt(II) compounds were produced by the treatment of 1 with FeCl2 or CoCl2 in tetrahydrofuran or diethylether at zero temperature, respectively, with the general formula M{(Me2)NCH2C6H4}CHC(tBu)NSiMe2(NMe2)]2 (M=Fe (2), Co (3)). The 1-azaally complexes 1,2 and 3 were also characterized by X-ray single crystal diffraction and NMR analysis. Structural analyses of 2 and 3 reveal that their molecular structures are very similar. The structure of the centrosymmetric crystalline Fe(Ⅱ) or Co (Ⅱ) is unusually within the present series of homoleptic metal (Ⅱ) 1-azaallyls in that it is an k1-enamido metal complex. CCDC: 771795, 1; 771796, 2; 771797, 3.