It is known that nickel(II) generally prefers to have square planer geometry, however, by designing a tridentate ligand with significant steric bulk the geometry can be manipulated and this can potentially lead to unusual interactions and reactivity. We designed and synthesized a novel tridentate NCN-pincer ligand that incorporated an aryl bromide scaffold and two phosphinimine donors where the phosphorus atoms were decorated with phenyl and cyclohexyl moieties (LBr). This ligand was metallated with nickel(0) bis(cyclooctadiene) via an oxidative addition (LNiBr). Reaction of the LNiBr with silver trifluoromethanesulfonate (AgOTf) leads loss of the bromide and formation of a unique, potentially T-shaped, Ni(II) complex ([LNi]OTf). However, investigations are looking into the possibility that the 4th coordinate site is occupied by an intramolecular, d-agostic interaction with a phenyl C-H. The complexes have been characterized by single crystal X-ray diffraction, 1H and 13C NMRs, cyclic voltammetry, and electronic absorption spectroscopy.

Synthesis and characterization of a nickel(II) diphosphinimino NCN-pincer complex that may contain an agostic interaction

2019 Spring National Meeting

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