A P−P Bond as a Redox Reservoir and an Active Reaction Site. (8th October 2018)

• Record Type: Journal Article
• Authors: Kim, Yeong‐Eun; Lee, Yunho
• Is Part Of: Angewandte Chemie. Volume 130:Number 43(2018)
• Page Start: 14355
• Page End: 14359
• Publication Date: 2018-10-08
• Subjects: Cabonylierung -- Metall-Ligand-Kooperation -- Metallradikaloide -- Nickel -- Phosphorkomplexe; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201809122
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: The carbonylation of a nickel(II) anilido species2 led to the formation of a dinickel(0)–CO complex (P2 P‐PP2 ){Ni(CO)}2 3 with a P−P bond along with isocyanate generation. In this reaction, the central phosphide moiety of an anionic PPP ligand (PPP − = − P[2‐P i Pr2 C6 H4 ]2 ) acts as a single‐electron donor to form a P radical. Alternatively, 3 can be synthesized from the reduction of (PPP)NiCl (1 ) in the presence of CO; thus, the reaction proceeds by radical coupling of a . P−Ni 0 −CO species. The reverse reaction occurred to generate1 when3 was treated with AgCl. Since the P−P bond is light‐sensitive, its homolysis is possible and was explored by EPR spectroscopy and DFT analysis. Finally, various bond‐activation reactions of3 occurred under visible‐light conditions, thus indicating that a P−P bond can act as an active reaction site.