Intra- and inter-molecular carboranyl C-H center dot center dot center dot N hydrogen bonds in pyridyl-containing ortho-carboranes

Alekseyeva, E.S.; Batsanov, A.S.; Boyd, L.A.; Fox, M.A.; Hibbert, T.G.; Howard, J.A.K.; MacBride, J.A.H.; Mackinnon, A.; Wade, K.

Abstract

Four C-substituted derivatives of ortho-carborane, 1-R-1,2-C2B10H11, where R = 2'-pyridyl (1), 2'-picolyl (2), 5'-bromo-2'-pyridyl (3) or 3'-pyridyl (4) have been prepared using adaptations of standard procedures, and structurally characterised by single crystal X-ray diffraction studies in an exploration of C-H...N hydrogen bonding effects involving their carborane CH units. Calculations at the MP2/6-31G* level of theory were used to assess the strength of the hydrogen bonding detected, and calculated NMR shifts at the GIAO-B3LYP/6-311G* level were compared with measured C-H shifts to show that intramolecular C-H...N hydrogen bonding persisted in solution in the case of compound 1. The value of IR C-H stretching frequencies for probing hydrogen bonding in these systems was also studied. An unsuccessful attempt to convert compound 3 into a macrocyclic species (C2B10H10C5H3N)(3) in which three ortho-carborane units are linked through 2,5-disubstituted pyridine rings is also described.

Citation

Alekseyeva, E., Batsanov, A., Boyd, L., Fox, M., Hibbert, T., Howard, J., …Wade, K. (2003). Intra- and inter-molecular carboranyl C-H center dot center dot center dot N hydrogen bonds in pyridyl-containing ortho-carboranes. Dalton Transactions, 475-482

• Journal Article Type: Article
• Publication Date: 2003-02
• Journal: Dalton Transactions
• Print ISSN: 1477-9226
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• Issue: 3
• Pages: 475-482