Kumar, VikasGonnade, Rajesh G.Yıldız, Cem BurakMajumbar, Moumita2021-12-072021-12-0720211433-7851https:/dx.doi.org/10.1002/anie.202111339https://hdl.handle.net/20.500.12451/8870Upon stabilization by 5,6-bis(diisopropylphosphino)acenaphthene to form compound 1, the fugitive antimony (I) cation exhibited nucleophilic behavior towards coinage metals. Compound 1 was strategically synthesized at room temperature from SbCl3, the bis(phosphine), and trimethylsilyl trifluoromethanesulfonate taken in a 1:2:3 ratio, whereby the bis(phosphine) plays the dual role of a reductant and a supporting ligand. The generation of 1 involves two-electron oxidation of the ligand to form a P?P bonded diphosphonium dication. Compound 1 was separated from this dication to give both products in pure form in moderate yields. Despite the overall positive charge, the SbI site in 1 was found to bind to metal centers, forming complexes with AuI, AgI and CuI. Compound 1 reduced CuII to CuI and formed a coordination complex with the resulting CuI species. The effects of the electron-rich bis(phosphine) and the constrained peri geometry in stabilizing and enhancing the nucleophilicity of 1 have been rationalized through computational studies.eninfo:eu-repo/semantics/embargoedAccessAntimony(I) CationCoordination ModesNucleophilicityPhosphine LigandsReductionArticle6048255222552910.1002/anie.20211133934505340Q1WOS:000709822100001Q1