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Trends in ortho-carboranes 1-X-2-R-1,2-C2B10H10 (R = Ph, Me) bearing an exo-CN-bonded substituent group (X = NO, N=NR ' or NHR '')

Fox, M.A.; Peace, R.J.; Clegg, W.; Elsegood, M.R.J.; Wade, K.

Trends in ortho-carboranes 1-X-2-R-1,2-C2B10H10 (R = Ph, Me) bearing an exo-CN-bonded substituent group (X = NO, N=NR ' or NHR '') Thumbnail


Authors

R.J. Peace

W. Clegg

M.R.J. Elsegood

K. Wade



Abstract

The preparation and crystal structures of four ortho-carboranyl-nitrogen compounds, PhCboNdouble bond; length as m-dashN(C6H4Me-4) (1), PhCboNHNH(C6H4Me-4) (2), MeCboNHNHPh (3) and PhCboNHOH (4) (Cbo = 1,2-C2B10H10; nitrogen groups at cage carbon C1, Ph or Me at C2), the last as a 1,4-dioxane solvate, are reported. Comparisons of their structures with those of other ortho-carboranyl-nitrogen systems studied earlier reveal further correlations between their cage C–C and exo-C–N bond distances and bond orders. Substituent orientations and bond distances (cage C1–C2, exo-C1–N) in RCboNHR′′ systems (R = Ph or Me at C2) are consistent with dative π-bonding from a nitrogen lone pair into the cage carbon p-AO otherwise responsible for cage C1–C2 σ bonding. Their C1–C2 bond distances are remarkably sensitive to the planar (sp2) or pyramidal (sp3) nature of the NHR′′ group. The Ndouble bond; length as m-dashO and Ndouble bond; length as m-dashNR′ residues in RCboX prefer to be orientated in plane with the cage C1–C2 in contrast to the RCboNHR′′ systems. Correlations between their cage C–C and exo-C–N bond distances and the 11B NMR chemical shifts of their antipodal boron atoms reflect the π-bonding characteristics of the nitrogen substituent.

Citation

Fox, M., Peace, R., Clegg, W., Elsegood, M., & Wade, K. (2009). Trends in ortho-carboranes 1-X-2-R-1,2-C2B10H10 (R = Ph, Me) bearing an exo-CN-bonded substituent group (X = NO, N=NR ' or NHR ''). Polyhedron, 28(12), 2359-2370. https://doi.org/10.1016/j.poly.2009.04.041

Journal Article Type Article
Publication Date Aug 1, 2009
Deposit Date Dec 14, 2011
Publicly Available Date Mar 28, 2024
Journal Polyhedron
Print ISSN 0277-5387
Publisher Elsevier
Peer Reviewed Peer Reviewed
Volume 28
Issue 12
Pages 2359-2370
DOI https://doi.org/10.1016/j.poly.2009.04.041
Keywords Carborane, Amine, Nitroso, Benzene, Cluster, π-Bonding.

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Copyright Statement
NOTICE: this is the author’s version of a work that was accepted for publication in Polyhedron. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Polyhedron, 28, 212, 2009, 10.1016/j.poly.2009.04.041




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