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RESEARCH PRODUCT
Carbon–Phosphorus Coupling from C^N Cyclometalated Au III Complexes
Wim T. KloosterDidier BourissouSophie R. ThomasAngela CasiniAngela CasiniRiccardo BonsignoreRobert Leyshon JenkinsSimon J. ColesGiampaolo Baronesubject
Organometallic Chemistrygold(III) cyclometalataled compoundsDenticitygold(III) cyclometalated compoundschemistry.chemical_element010402 general chemistry01 natural sciencesMedicinal chemistryDFTCatalysisReductive eliminationchemistry.chemical_compoundcross-couplingcarbon-phosphorous bond[CHIM]Chemical SciencesReactivity (chemistry)Phosphonium010405 organic chemistryPhosphorusCommunicationOrganic Chemistryreductive eliminationGeneral ChemistryBond formationcross- couplingCommunications0104 chemical sciences3. Good healthddc:gold(III) cyclometalataled compoundchemistrySettore CHIM/03 - Chimica Generale E Inorganicadensity functional calculationscarbon–phosphorous bondCarbondescription
Abstract With the aim of exploiting new organometallic species for cross‐coupling reactions, we report here on the AuIII‐mediated Caryl−P bond formation occurring upon reaction of C^N cyclometalated AuIII complexes with phosphines. The [Au(C^N)Cl2] complex 1 featuring the bidentate 2‐benzoylpyridine (CCON) scaffold was found to react with PTA (1,3,5‐triaza‐7‐phosphaadamantane) under mild conditions, including in water, to afford the corresponding phosphonium 5 through C−P reductive elimination. A mechanism is proposed for the title reaction based on in situ 31P{1H} NMR and HR‐ESI‐MS analyses combined with DFT calculations. The C−P coupling has been generalized to other C^N cyclometalated AuIII complexes and other tertiary phosphines. Overall, this work provides new insights into the reactivity of cyclometalated AuIII compounds and establishes initial structure–activity relationships to develop AuIII‐mediated C−P cross‐coupling reactions.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2020-04-01 |