Dalton Trans. 2014 Mar 21;43(11):4593-602. doi: 10.1039/c4dt90024c.
Neutral Zr(IV) and Hf(IV) dimethyl complexes stabilized by unsymmetrical dianionic {N,C,N'} pincer ligands have been prepared from their corresponding bis-amido complexes upon treatment with AlMe₃. Their structure consists of a central ó-bonded aryl donor group (C) capable of forming robust M-C bonds with the metal center, enforced by the synergic effect of both the coordination of peripheral donor groups (N) and the chelating rigid structure of the {N,C,N} ligand framework. Such a combination translates into systems having a unique balance between stability and reactivity. These Zr(IV) and Hf(IV) dimethyl complexes were converted in situ into cationic species [M(IV){N⁻,C⁻,N}Me][B(C₆F₅)₄] which are active catalysts for the room temperature (r.t.) intramolecular hydroamination/cyclization of primary and secondary aminoalkenes as well as for the high temperature ethylene-1-octene copolymerizations.
通过三甲基铝处理，从相应的双酰胺配合物制备了由非对称二阴离子{N,C,N'}钳形配体稳定的中性 Zr(IV)和 Hf(IV)二甲基配合物。它们的结构由一个中心的σ键合芳基供体基团（C）组成，能够与金属中心形成坚固的 M-C 键，这是外围供体基团（N）的配位和{ N,C,N}配体框架的螯合刚性结构的协同效应共同作用的结果。这种组合转化为在稳定性和反应性之间具有独特平衡的系统。这些 Zr(IV)和 Hf(IV)二甲基配合物原位转化为阳离子物种[M(IV){N⁻,C⁻,N}Me][B(C₆F₅)₄]，它们是室温（r.t.）下伯胺和仲胺烯烃的分子内氢胺化/环化以及高温乙烯-1-辛烯共聚的活性催化剂。
