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

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.