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Abstract
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'.
Highlights
The present report details our efforts in the synthesis of ve-coordinate CoIII-aryl/thiolate complexes supported by the PNP ligand, their propensity to undergo concerted C–S reductive elimination (RE), and the subsequent comproportionation reactivity that again diverges from the Rh system
High-spin Co(II) compounds tend to produce 1H NMR spectra that are broadened beyond useful interpretation
(PNP)Co complexes in the +1, +2, and +3 oxidations states relevant to potential cross-coupling reactions were prepared and fully characterized
Summary
Scheme 1 C–S reductive coupling observed for the (POCOP) Rh(Ph)(SPh) and (PNP)Rh(Ph)(SPh) complexes The present report details our efforts in the synthesis of ve-coordinate CoIII-aryl/thiolate complexes supported by the PNP ligand, their propensity to undergo concerted C–S RE, and the subsequent comproportionation reactivity that again diverges from the Rh system.
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