A P-P Bond as a Redox Reservoir and an Active Reaction Site

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The carbonylation of a nickel(II) anilido species 2 led to the formation of a dinickel(0)-CO complex (P2P-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-(PPr2C6H4)-Pr-i](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 generate 1 when 3 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 of 3 occurred under visible-light conditions, thus indicating that a P-P bond can act as an active reaction site.
Publisher
WILEY-V C H VERLAG GMBH
Issue Date
2018-10
Language
English
Article Type
Article
Keywords

PERSISTENT PHOSPHINYL RADICALS; MEDIATED FORMATION; CRYSTAL-STRUCTURE; IMIDO COMPLEXES; LIGANDS; INTERCONVERSION; DIPHOSPHINE; GENERATION; MECHANISM; O-2

Citation

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, v.57, no.43, pp.14159 - 14163

ISSN
1433-7851
DOI
10.1002/anie.201809122
URI
http://hdl.handle.net/10203/246557
Appears in Collection
CH-Journal Papers(저널논문)
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