Synthesis, Characterization, and Catalytic Reactivity of {CoNO}⁸ PCP Pincer Complexes

The reaction of coordinatively unsaturated Co(II) PCP pincer complexes with nitric oxide leads to the formation of new, air-stable, diamagnetic mono nitrosyl compounds. The synthesis and characterization of five- and four-coordinate Co(III) and Co(I) nitrosyl pincer complexes based on three different ligand scaffolds is described. Passing NO through a solution of [Co(PCP^NMe-iPr)Cl], [Co(PCP^O-iPr)Cl] or [Co(PCP^CH2-iPr)Br] led to the formation of the low-spin complex [Co(PCP-iPr)(NO)X] with a strongly bent NO ligand. Treatment of the latter species with (X = Cl, Br) AgBF₄ led to chloride abstraction and formation of cationic square-planar Co(I) complexes of the type [Co(PCP-iPr)(NO)]⁺ featuring a linear NO group. This reaction could be viewed as a formal two electron reduction of the metal center by the NO radical from Co(III) to Co(I), if NO is counted as NO⁺. Hence, these systems can be described as {CoNO}⁸ according to the Enemark-Feltham convention. X-ray structures, spectroscopic and electrochemical data of all nitrosyl complexes are presented. Preliminary studies show that [Co(PCP^NMe-iPr)(NO)]⁺ catalyzes efficiently the reductive hydroboration of nitriles with pinacolborane (HBpin) forming an intermediate {CoNO}⁸ hydride species.