DFT studies of the σ-donor/π-acceptor properties of [SnCB10H11]– and its relationship to [SnCl3]–, CO, PF3, [SnB11H11]2–, SnC2B9H11, and related SnC2BnHn+2 compounds

Fox, Mark A.; Marder, Todd B.; Wesemann, Lars

Abstract

The 1,2-carbastanna-closo-dodecaborate, [SnCB10H11]–, was found via DFT calculations to have intermediate σ-donor/π-acceptor properties between those of [SnB11H11]2– and 3,1,2-SnC2B9H11, and quite similar HOMO and LUMO energies and shapes to those of [SnCl3]–, which is a stronger σ-donor and weaker π-acceptor than CO or PF3. The non-carbon containing cluster [SnB11H11]2– is shown to be a very strong donor, whereas the dicarbon cluster 3,1,2-SnC2B9H11 is a poor σ-donor but good Lewis acid, consistent with experimental results. Thus, these systems can be tuned across a very wide range via isolobal replacement of [BH]– for CH vertices. The higher negative charge in the non-carbon-containing systems, as well as the fact that boron is more electropositive than carbon, contribute to the increased energies of both HOMO and LUMO in the stannaboranes compared to the stannacarboranes, explaining their relative donor and acceptor properties.Key words: DFT calculations, tin, borane cluster.

Citation

Fox, M. A., Marder, T. B., & Wesemann, L. (2009). DFT studies of the σ-donor/π-acceptor properties of [SnCB10H11]– and its relationship to [SnCl3]–, CO, PF3, [SnB11H11]2–, SnC2B9H11, and related SnC2BnHn+2 compounds. Canadian Journal of Chemistry, 87(1), 63-71. https://doi.org/10.1139/v08-081

• Journal Article Type: Article
• Publication Date: Jan 1, 2009
• Deposit Date: Dec 14, 2011
• Publicly Available Date: May 6, 2015
• Journal: Canadian Journal of Chemistry
• Print ISSN: 0008-4042
• Electronic ISSN: 1480-3291
• Publisher: Canadian Science Publishing
• Peer Reviewed: Peer Reviewed
• Volume: 87
• Issue: 1
• Pages: 63-71
• DOI: https://doi.org/10.1139/v08-081
• Public URL: https://durham-repository.worktribe.com/output/1532895