Treatment of the potentially chelating bis-carbene, 1,2-ethylene-3,3′-di-tert-butyl-diimidazole-2,2′-diylidene, EtIBut, with [MH3(NMe3)], M = Al, Ga, In, in a 1 ∶ 1 or 1 ∶ 2 stoichiometery led to good yields of the metal rich 2 ∶ 1 adducts, [(MH3)2(μ-EtIBut)]. These complexes have been spectroscopically characterised and the X-ray crystal structures of two (M = Al or In) obtained. In contrast, the 1 ∶ 1 or 1 ∶ 2 reactions of EtIBut with MX3, M = In or Tl, X = Br or Cl, led to the 1 ∶ 1 adducts, [MX3(EtIBut)]. The X-ray crystal structure of one of these, [InBr3(EtIBut)], shows the ligand to act in a chelating mode, taking up equatorial positions of an trigonal bipyramid. The reactions of EtIBut with MCl3, M = Al or Ga, led to decomposition
and in the aluminium reaction the major product of the decomposition process was the bis-imidazolium salt, [EtIButH2][Cl]2, which has also been crystallographically characterised. Several related reactions are described.
用[
MH3(NMe3)]处理具有潜在螯合作用的双烯烃--1,2-
乙烯-3,3′-二叔丁基二
咪唑-2,2′-二亚基,EtIBut、M = Al、Ga、In,按 1 ∶ 1 或 1 ∶ 2 的
化学计量,可以得到富含
金属的 2 ∶ 1 加合物[(
MH3)2(μ-EtIBut)]。对这些复合物进行了光谱表征,并获得了其中两种(M = Al 或 In)的 X 射线晶体结构。与此相反,EtIBut 与 MX3(M = In 或 Tl,X = Br 或 Cl)的 1 ∶ 1 或 1 ∶ 2 反应会产生 1 ∶ 1 加合物 [MX3(EtIBut)]。其中一种加合物[InBr3(EtIBut)]的 X 射线晶体结构显示,
配体以螯合方式发挥作用,占据了三叉二棱柱的赤道位置。EtIBut 与 MCl3(M = Al 或 Ga)的反应导致分解,在铝反应中,分解过程的主要产物是
双咪唑盐 [EtIButH2][Cl]2,该产物也已通过晶体学鉴定。本文介绍了几个相关的反应。