Cheng Yanxiang, Doyle David J, Hitchcock Peter B, Lappert Michael F
The Chemistry Department, University of Sussex, Brighton, UK BN1 9QJ.
Dalton Trans. 2006 Oct 7(37):4449-60. doi: 10.1039/b607782j. Epub 2006 Aug 3.
The synthesis of the following crystalline complexes is described: [Li(L)(thf)2] (), [Li(L)(tmeda)] (), [MCl2(L)] [M=Al (), Ga ()], [In(Cl)(L)(micro-Cl)2Li(OEt2)2] (), [In(Cl)(L){N(H)C6H3Pri(2)-2,6}] (), [In(L){N(H)C6H3Pri(2)-2,6}2] (), [{In(Cl)(L)(micro-OH)}2] (), [L(Cl)In-In(Cl)(L)] () (the thf-solvate, the solvate-free and the hexane-solvate), [{In(Cl)L}2(micro-S)] () and [InCl2(L)(tmeda)] () ([L]-=[{N(C6H3Pri(2)-2,6)C(H)}2CPh]-). From H(L) (), via Li(L) in Et2O, and thf, tmeda, AlCl3, GaCl3 or InCl3 there was obtained , , , or , respectively in excellent yield. Compound was the precursor for each of , and [{InCl3(tmeda)2{micro-(OSnMe2)2}}] () by treatment with one () or two () equivalents of K[N(H)(C6H3Pri(2)-2,6)], successively Li[N(SiMe3)(C6H3Pri(2)-2,6)] and moist air (), Na in thf (), tmeda (), or successively tmeda and Me3SnSnMe3 (). Crystals of (with an equivalent of In) and were obtained from InCl or thermolysis of [In(Cl)(L){N(SiMe3)(C6H3Pri(2)-2,6)}] () {prepared in situ from and Li[N(SiMe3)(C6H3Pri(2)-2,6)] in Et2O}, respectively. Compound was obtained from a thf solution of and sulfur. X-Ray data for crystalline , , , , , and are presented. The M(L) moiety in each (not the L-free ) has the monoanionic L ligated to the metal in the N,N'-chelating mode. The MN1C1C2C3N2 six-membered M(L) ring is pi-delocalised and has the half-chair (, and ) or boat (, and ) conformation.
[Li(L)(thf)₂]()、[Li(L)(tmeda)]()、[MCl₂(L)] [M = Al()、Ga()]、[In(Cl)(L)(μ-Cl)₂Li(OEt₂)₂]()、[In(Cl)(L){N(H)C₆H₃Pri₂-2,6}]()、[In(L){N(H)C₆H₃Pri₂-2,6}₂]()、[{In(Cl)(L)(μ-OH)}₂]()、[L(Cl)In-In(Cl)(L)]()(四氢呋喃溶剂化物、无溶剂化物和己烷溶剂化物)、[{In(Cl)L}₂(μ-S)]()和[InCl₂(L)(tmeda)]()([L] = [{N(C₆H₃Pri₂-2,6)C(H)}₂CPh])。由H(L)(),通过在Et₂O中生成Li(L),并加入四氢呋喃、tmeda、AlCl₃、GaCl₃或InCl₃,分别以优异的产率得到了、、、或。化合物是、和[{InCl₃(tmeda)₂{μ-(OSnMe₂)₂}}]()的前体,通过用一()或两()当量的K[N(H)(C₆H₃Pri₂-2,6)]、依次用Li[N(SiMe₃)(C₆H₃Pri₂-2,6)]和潮湿空气()、在四氢呋喃中的Na()、tmeda()或依次用tmeda和Me₃SnSnMe₃处理得到。(含当量In)和的晶体分别由InCl或[In(Cl)(L){N(SiMe₃)(C₆H₃Pri₂-2,6)}]()的热分解得到{由和Li[N(SiMe₃)(C₆H₃Pri₂-2,6)]在Et₂O中原位制备}。化合物由和硫的四氢呋喃溶液得到。给出了晶体、、、、、和的X射线数据。每个(不含无L的)中的M(L)部分具有以N,N'-螯合模式与金属相连的单阴离子L。MN₁C₁C₂C₃N₂六元M(L)环是π离域的,具有半椅式(、和)或船式(、和)构象。