Ruiz Javier, García Lucía, Vivanco Marilín, Sol Daniel, García-Granda Santiago
Departamento de Química Orgánica e Inorgánica, Facultad de Química, Universidad de Oviedo, 33006 Oviedo, Spain.
Dalton Trans. 2017 Aug 8;46(31):10387-10398. doi: 10.1039/c7dt02049j.
A variety of half-sandwich iron(ii) complexes with diprotic acyclic diaminocarbene ligands (pADCs) have been obtained by reaction of the cationic complexes [Fe(Cp)(CO)(CNR)] and [Fe(Cp)(CO)(CNR)] with methylamine, and their acid-base behaviour was studied, revealing an easy reversible deprotonation reaction of both N-H moieties of the carbene ligands. The deprotonation process is frequently followed by a nucleophilic attack of the nitrogen atom on a vicinal carbonyl or isocyanide ligand, affording the corresponding metallacycles. Metalation of one or two N-H groups of the pADC ligands can be accomplished by reaction of the carbene complexes with either [AuCl(PPh)] or [Ru(p-cym)Cl] in the presence of KOH or LiHMDS as deprotonating agents. A number of Fe(ii)/Au(i) and Fe(ii)/Ru(ii) heterometallic complexes have been prepared in this way, some of them formally containing unique metalla-N-heterocyclic carbene ligands.
通过阳离子配合物[Fe(Cp)(CO)(CNR)]和[Fe(Cp)(CO)(CNR)]与甲胺反应，已获得了多种含有双质子无环二氨基卡宾配体（pADC）的半夹心铁（II）配合物，并对其酸碱行为进行了研究，结果表明卡宾配体的两个N-H部分都容易发生可逆的去质子化反应。去质子化过程之后，氮原子经常会对邻位羰基或异氰化物配体进行亲核攻击，从而生成相应的金属环。在作为去质子化剂的KOH或LiHMDS存在下，卡宾配合物与[AuCl(PPh)]或[Ru(p-cym)Cl]反应，可以实现pADC配体中一个或两个N-H基团的金属化。通过这种方式制备了许多Fe（II）/Au（I）和Fe（II）/Ru（II）异金属配合物，其中一些形式上含有独特的金属-N-杂环卡宾配体。
