Stabilization of the elusive antimony(I) cation and Its coordination complexes with transition metals
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Dosyalar
Tarih
2021
Dergi Başlığı
Dergi ISSN
Cilt Başlığı
Yayıncı
John Wiley and Sons Inc
Erişim Hakkı
info:eu-repo/semantics/embargoedAccess
Özet
Upon 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.
Açıklama
Anahtar Kelimeler
Antimony(I) Cation, Coordination Modes, Nucleophilicity, Phosphine Ligands, Reduction
Kaynak
Angewandte Chemie - International Edition
WoS Q Değeri
Q1
Scopus Q Değeri
Q1
Cilt
60
Sayı
48
