Stabilization of the elusive antimony(I) cation and its coordination complexes with transition metals
| Title | Stabilization of the elusive antimony(I) cation and its coordination complexes with transition metals |
| Publication Type | Journal Article |
| Year of Publication | 2021 |
| Authors | Kumar, V, Gonnade, RG, Yildiz, CB, Majumdar, M |
| Journal | Angewandte Chemie-International Edition |
| Volume | 60 |
| Issue | 48 |
| Pagination | 25522-25529 |
| Date Published | NOV |
| Type of Article | Article |
| ISSN | 1433-7851 |
| Keywords | antimony(I) cation, coordination modes, nucleophilicity, phosphine ligands, reduction |
| Abstract | 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 Sb-I site in 1 was found to bind to metal centers, forming complexes with Au-I, Ag-I and Cu-I. Compound 1 reduced Cu-II to Cu-I and formed a coordination complex with the resulting Cu-I 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. |
| DOI | 10.1002/anie.202111339 |
| Type of Journal (Indian or Foreign) | Foreign |
| Impact Factor (IF) | 15.336 |
Divison category:
Physical and Materials Chemistry