LabLichtenberg (@lablichtenberg.bsky.social)

#Bismuth meets platinum (#1): diaryl bismuth cations undergo oxidative aryl transfer to Pt(0)! Attempts to trap the low-valent Bi intermediate yielded a Pt radical complex. Now out in the p-block special issue of #Organometallics, @pubs.acs.org: pubs.acs.org/doi/10.1021/... Congrats to the team!

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Reactivity of Diaryl Bismuth Cations toward a Platinum(0) Complex: Oxidative Aryl Transfer Reactions of three aryl-substituted bismuth cations, [BiPh2(SbF6)], [BiMes2(SbF6)], and [BiDipp2(SbF6)], with the Pt0 complex Pt(PCy3)2 have been investigated (Mes = 2,4,6-trimethyl-phenyl; Dipp = 2,6-di-iso-propyl-phenyl; Cy = cyclohexyl). Unexpectedly, and in contrast with the reactivity of the recently reported methyl analogue [BiMe2(SbF6)], the formation of isolable metal-only Lewis pairs [(Cy3P)2Pt→BiAr2(SbF6)] is not observed (Ar = aryl). Instead, an unprecedented bismuth-to-platinum oxidative aryl transfer is witnessed to give the PtII complexes [PtAr(PCy3)2(SbF6)], along with the suggested bismuthinidene intermediates BiAr. Attempts to trap these fleeting intermediates with an ortho-quinone led to a PtII semiquinone radical complex. https://pubs.acs.org/doi/10.1021/acs.organomet.5c00441