Synthesis of Zirconium, Hafnium, and Tantalum Complexes with Sterically Demanding Hydrazide Ligands
作者:Jean-Sébastien M. Lehn、Saba Javed、David M. Hoffman
DOI:10.1021/ic061483w
日期:2007.2.1
M(N(Et)NMe2)4 (M = Zr or Hf), MCl(N(R)NMe2)3 (M = Zr, R = i-Pr or t-Bu; M = Hf, R = t-Bu), and TaCl3(N(i-Pr)NMe2)2. The X-ray crystal structures of [LiN(i-Pr)NMe2]4, [LiN(t-Bu)NMe2.THF]2, ZrCl(N(R)NMe2)3 (R = i-Pr or t-Bu), and TaCl3(N(i-Pr)NMe2)2 were determined. The structural analyses revealed that the hydrazide ligands in ZrCl(N(R)NMe2)3 (R = i-Pr or t-Bu) and TaCl3(N(i-Pr)NMe2)2 are eta2 coordinated.
通过和t-BuN(H)N(H)Me中间体为主要成分,在由t-BuN(H)NMe2,t组成的90:5:5混合物中合成了笨重的肼t-BuN(H)NMe2 -BuN(Me)N(H)Me和t-BuN(Me)NMe2。使混合物与正丁基锂反应,然后进行蒸馏和分步结晶,导致分离出配体前体LiN(t-Bu)NMe2。酰化锂LiN(R)NMe2与金属氯化物反应得到酰肼配合物M(N(Et)NMe2)4(M = Zr或Hf),MCl(N(R)NMe2)3(M = Zr, R = i-Pr或t-Bu; M = Hf,R = t-Bu)和TaCl 3(N(i-Pr)NMe 2)2。[LiN(i-Pr)NMe2] 4,[LiN(t-Bu)NMe2.THF] 2,ZrCl(N(R)NMe2)3(R = i-Pr或t-Bu)的X射线晶体结构),然后确定TaCl3(N(i-Pr)NMe2)2。结构分析表明ZrCl(N(R)NMe2)3(R