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

Bryan J Foley, Chandra Mouli Palit, Nattamai Bhuvanesh, Jia Zhou, Oleg V Ozerov

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Article in Chemical science, 2020. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 1 paper.

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1 citing paper in PubMed.

Reaction Pathways and Redox States in α-Selective Cobalt-Catalyzed Hydroborations of Alkynes.Angewandte Chemie (International ed. in English) · 2020
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5 authors.

Bryan J FoleyDepartment of Chemistry , Texas A&M University , 3255 TAMU , College Station , Texas 77842 , USA . Email: ozerov@chem.tamu.edu.ORCID 0000-0003-0570-769X

Chandra Mouli PalitDepartment of Chemistry , Texas A&M University , 3255 TAMU , College Station , Texas 77842 , USA . Email: ozerov@chem.tamu.edu.

Nattamai BhuvaneshDepartment of Chemistry , Texas A&M University , 3255 TAMU , College Station , Texas 77842 , USA . Email: ozerov@chem.tamu.edu.

Jia ZhouSchool of Science , Harbin Institute of Technology , Shenzhen 518055 , China . Email: jiazhou@hit.edu.cn.ORCID 0000-0001-5418-5141

Oleg V OzerovDepartment of Chemistry , Texas A&M University , 3255 TAMU , College Station , Texas 77842 , USA . Email: ozerov@chem.tamu.edu.ORCID 0000-0002-5627-1120

Funding

No grant is acknowledged in the PubMed record.

6 · The paper itself

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'.

Identifiers

PMID32953010

DOI10.1039/d0sc01813a

PMCPMC7480512

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