10.1039/b814806f
The research focuses on the synthesis and characterization of cationic and neutral NiII complexes containing the non-innocent PNPtBu pincer ligand. The study aims to explore the formation of alkyl and thiolate species using the non-innocent character of the PNPtBu backbone. Starting with the dicationic complex 1, Ni(PNPtBu)(NCMe)2, the researchers prepared a series of dicationic and monocationic NiII complexes. Key chemicals used in the process include tert-butyl isocyanide, azide, benzylmercaptan, thiophenol, and various nickel and phosphorus-containing compounds. The research concludes that complex 1 serves as a versatile building block for the synthesis of well-defined mononuclear NiII species, such as the rare mononuclear monothiolate complexes 7 and 8. The non-innocent nature of the PNPtBu ligand leads to significant electronic changes, which were investigated for both dication 3 and monocation 6, featuring a tert-butyl isocyanide co-ligand. DFT calculations supported the assignment of the deprotonated PN-PtBu ligand as a monoamido fragment, and the study also provided access to new neutral Ni-complexes with Ph, Me, or H as co-ligands, offering potential applications in catalytic reactions.
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