Synthesis and reactivity of air stable Ni(II) complexes with isocyanides and dialkyldithiophosphate ligands: alkyl transfer and acyclic diaminocarbene formation

A library of new neutral and cationic Ni(II) complexes containing isocyanide ligands and mono- or dialkyl-dithiophosphate have been prepared and fully characterized. They are subsequently shown to constitute excellent precursors to obtain new families of air stable Ni(II)-based acyclic diaminocarbene (Ni-ADCs) complexes by nucleophilic attack with various alkyl-substituted amines. Remarkably, the ADC is only produced at one of the isocyanide ligands. This was subsequently exploited to obtain an unpredecented dinuclear complex containing a bridging bis-carbene ligand using piperazine.