Upon the intriguing stereoselective formation of organobismuth(V) complexes

Barucki, Hubert; Coles, Simon J.; Costello, James F.; Hursthouse, Michael B.

Abstract

The preparation of triphenyl-bismuth(v) 3a-k and antimony(v) 4e-k bis-carboxy ester complexes is described. A range of studies in solution suggest that the diastereoselective formation of (RR,SS)-3a-j is governed by the thermodynamic stability of rapidly interconverting epimeric species. Diastereoselectivity is absent in the case of the corresponding Sb complexes, leading to the conclusion that a combination of both ligand-ligand (steric) and metal-ligand (hyperconjugative) interactions govern stereoselectivity. The formation of homochiral complexes (RR,SS)-3a-j is rationalised using a simple model, invoking for the first time a palindromic BiPh3 propeller moiety, which correlates the chirality of the trans axial carboxy-ester ligands. The X-ray crystal structures of both hetero- and homochiral diastereoisomeric antimony complexes (4h and 4i, respectively) are presented in support of this model.

Citation

Barucki, H., Coles, S. J., Costello, J. F., & Hursthouse, M. B. (2003). Upon the intriguing stereoselective formation of organobismuth(V) complexes. Chemistry - A European Journal, 9(12), 2877-2884. https://doi.org/10.1002/chem.200304852

• Journal Article Type: Article
• Publication Date: Jun 16, 2003
• Journal: Chemistry - A European Journal
• Print ISSN: 0947-6539
• Publisher: Wiley
• Peer Reviewed: Peer Reviewed
• Volume: 9
• Issue: 12
• Pages: 2877-2884
• DOI: https://doi.org/10.1002/chem.200304852
• Keywords: antimony, bismuth, diastereoselectivity, hyperconjugation, propellers
• Public URL: https://uwe-repository.worktribe.com/output/1069346
• Publisher URL: http://dx.doi.org/10.1002/chem.200304852