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- W2592913013 abstract "Abstract Redox non‐innocent ligands have recently emerged as interesting tools to obtain new reactivity with a wide variety of metals. However, gold has almost been neglected in this respect. Here, we report mechanistic investigations related to a rare example of ligand‐based redox chemistry in the coordination sphere of gold. The dinuclear metal‐centered mixed‐valent Au I –Au III complex 1 , supported by monoanionic diarylamido‐diphosphine ligand PNP Pr and with three chlorido ligands overall, undergoes a complex series of reactions upon halide abstraction by silver salt or Lewis acids such as gallium trichloride. Formation of the ultimate Au I –Au I complex 2 requires the intermediacy of Au I –Au I dimers 5 and 7 as well as the unique Au III –Au III complex 6 , both of which are interconverted in a feedback loop. Finally, unprecedented ortho ‐selective C−H activation of the redox‐active PNP ligand results in the carbazolyldiphosphine derivative PN*P Pr via ligand‐to‐metal two‐electron transfer. This work demonstrates that the redox‐chemistry of gold may be significantly expanded and modified when using a reactive ligand scaffold." @default.
- W2592913013 created "2017-03-16" @default.
- W2592913013 creator A5005123295 @default.
- W2592913013 creator A5015653296 @default.
- W2592913013 creator A5067333596 @default.
- W2592913013 date "2017-04-03" @default.
- W2592913013 modified "2023-09-26" @default.
- W2592913013 title "Controlled Interconversion of a Dinuclear Au Species Supported by a Redox‐Active Bridging PNP Ligand Facilitates Ligand‐to‐Gold Electron Transfer" @default.
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- W2592913013 doi "https://doi.org/10.1002/chem.201700360" @default.
- W2592913013 hasPubMedCentralId "https://www.ncbi.nlm.nih.gov/pmc/articles/5413818" @default.
- W2592913013 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/28248000" @default.
- W2592913013 hasPublicationYear "2017" @default.
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