Concerted aryl-sulfur reductive elimination from PNP pincer-supported Co(iii) and subsequent Co(i)/Co(iii) comproportionation.

This report discloses a combined experimental and computational study aimed at understanding C-S reductive elimination from Co(iii) supported by a diarylamido/bis(phosphine) PNP pincer ligand. Divalent (PNP)Co-aryl complexes could be easily oxidized to five-coordinate Co(iii) derivatives, and anion metathesis provided five-coordinate (PNP)Co(Ar)(SAr') complexes of Co(iii). In contrast to their previously described (POCOP)Co(Ar)(SAr') analogs, but similarly to the (PNP)Rh(Ar)(SAr') and (POCOP)Rh(Ar)(SAr') analogs, (PNP)Co(Ar)(SAr') undergo C-S reductive elimination with the formation of the desired diarylsulfide product ArSAr'. DFT studies and experimental observations are consistent with a concerted process. However, in contrast to the Rh analogs, the immediate product of such reductive elimination, the unobserved Co(i) complex (PNP)Co, un-dergoes rapid comproportionation with the (PNP)Co(Ar)(SAr') starting material to give Co(ii) compounds (PNP)Co-Ar and (PNP)Co-SAr'.