New synthetic and structural studies on nitroso-ortho-carboranes RCB10H10CNO and bis(ortho-carboranyl)amines (RCB10H10C)(2)NH (R = Ph or Me)

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

doi:10.1016/j.poly.2008.12.014

New synthetic and structural studies on nitroso-ortho-carboranes RCB10H10CNO and bis(ortho-carboranyl)amines (RCB10H10C)(2)NH (R = Ph or Me)

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

Authors

Dr Mark Fox m.a.fox@durham.ac.uk
Assistant Professor

J.A.H. MacBride

R.J. Peace

W. Clegg

M.R.J. Elsegood

K. Wade

Abstract

Improved procedures are reported for the preparation of nitroso-carboranes RCb°NO (Cb° = 1,2-C2B10H10; R = Ph, Me at cage carbon C2) in 44–77% yield, and of dicarboranylamines (RCb°)2NH in 55–65% yield by reactions between the lithio-carboranes, RCb°Li and nitrosyl chloride, NOCl, in cold mixtures of diethyl ether and either pentane (for RCb°NO) or dimethoxyethane (for (RCb°)2NH). Deprotonation of the amines by KOtBu in toluene in the presence of 18-crown-6, (CH2CH2O)6, affords the salts [K(18-crown-6)]+[(RCb°)2N]−. X-ray crystal structures of PhCb°NO, (PhCb°)2NH, (MeCb°)2NH and [K(18-crown-6)]+[(PhCb°)2N]− are described, and the bonding implications of their cage C…C distances (1.68, 1.80, 1.75 and 1.99 Å, respectively) are discussed. These species provide further striking examples of the remarkable capacity of the ortho-carborane cage to act as a sensitive indicator of the π-donor characteristics of ligands attached to its cage carbon atoms.

Citation

Fox, M., MacBride, J., Peace, R., Clegg, W., Elsegood, M., & Wade, K. (2009). New synthetic and structural studies on nitroso-ortho-carboranes RCB10H10CNO and bis(ortho-carboranyl)amines (RCB10H10C)(2)NH (R = Ph or Me). Polyhedron, 28(4), 789-795. https://doi.org/10.1016/j.poly.2008.12.014

Journal Article Type	Article
Publication Date	Mar 1, 2009
Deposit Date	Dec 14, 2011
Publicly Available Date	Jul 3, 2014
Journal	Polyhedron
Print ISSN	0277-5387
Publisher	Elsevier
Peer Reviewed	Peer Reviewed
Volume	28
Issue	4
Pages	789-795
DOI	https://doi.org/10.1016/j.poly.2008.12.014
Keywords	Ortho-Carborane, π-Bond, Amine group, Nitroso group, Crystal structure, Clusters.

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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, 4, 2009, 10.1016/j.poly.2008.12.014