Exploring the Effect of Pincer Rigidity on Oxidative Addition Reactions with Cobalt(I) Complexes.

Cobalt complexes containing the 2,6-diaminopyridine-substituted PNP pincer ( iPr P NMe NP = 2,6-( i Pr 2 PNMe) 2 (C 5 H 3 N)) were synthesized. A combination of solid-state structures and investigation of the cobalt(I)/(II) redox potential established a relatively rigid and electron-donating chelating ligand as compared to iPr PNP ( iPr PNP = 2,6-( i Pr 2 PCH 2 ) 2 (C 5 H 3 N)). Based on a buried volume analysis, the two pincer ligands are sterically indistinguishable. Nearly planar, diamagnetic, four-coordinate complexes were observed independent of the field strength (chloride, alkyl, aryl) of the fourth ligand completing the coordination sphere of the metal. Computational studies supported a higher barrier for C-H oxidative addition, largely a result of the increased rigidity of the pincer. The increased oxidative addition barrier resulted in stabilization of ( iPr P NMe NP)Co(I) complexes, enabling the characterization of the cobalt boryl and the cobalt hydride dimer by X-ray crystallography. Moreover, ( iPr P NMe NP)CoMe served as an efficient precatalyst for alkene hydroboration likely because of the reduced propensity to undergo oxidative addition, demonstrating that reactivity and catalytic performance can be tuned by rigidity of pincer ligands.