Álvarez-Miguel Lucía, Del Carmen-Rodríguez Clara, Valle María, Álvarez Celedonio M, Martín-Álvarez José M, García-Rodríguez Raúl, Miguel Daniel
SOSCATCOM Group, Departamento de Química Orgánica y Química Inorgánica, Facultad de Farmacia and Instituto de Investigación Química "Andrés M. del Río" (IQAR) Universidad de Alcalá Campus Universitario, 28871 Alcalá de Henares, Madrid, Spain.
GIR MIOMET/IU CINQUIMA/Química Inorgánica, Facultad de Ciencias Universidad de Valladolid, 47011, Valladolid, Spain.
Dalton Trans. 2024 Sep 18;53(36):15101-15112. doi: 10.1039/d4dt01915f.
A library of new neutral and cationic Ni(II) complexes containing isocyanide ligands and mono- or dialkyl-dithiophosphate have been easily prepared and fully characterized. The synthesis of the neutral complexes unfolds through the alkyl transfer from one alkyldithiophosphate leaving group coordinated to the Ni(II) complex. The alkyl transfer is controlled by steric factors and is highly solvent-dependent. These complexes shown to constitute excellent precursors to obtain new families of air stable Ni(II)-based acyclic diaminocarbene complexes (Ni(II)-ADCs) by nucleophilic attack with various alkyl-substituted amines. Remarkably, the ADC is only produced at one of the isocyanide ligands, keeping the other isocyanide unreacted. This was subsequently exploited to prepare the unprecedented neutral and cationic dinuclear Ni(II) complexes containing a bridging bis-carbene ligand using piperazine.
一个包含异腈配体和单烷基或二烷基二硫代磷酸酯的新型中性和阳离子镍（II）配合物库已被轻松制备并全面表征。中性配合物的合成是通过从与镍（II）配合物配位的一个烷基二硫代磷酸离去基团进行烷基转移来实现的。烷基转移受空间因素控制且高度依赖溶剂。这些配合物被证明是通过与各种烷基取代胺进行亲核进攻来获得新型空气稳定的基于镍（II）的无环二氨基卡宾配合物（Ni（II）-ADC）的优异前体。值得注意的是，ADC仅在其中一个异腈配体处产生，而另一个异腈未反应。随后利用这一点，使用哌嗪制备了前所未有的含有桥连双卡宾配体的中性和阳离子双核镍（II）配合物。
