J. Kahlert
Crystal structures of the carborane dianions, [1,4-(PhCB10H10C)2C6H4]2- and [1,4-(PhCB10H10C)2C6F4]2-, and the stabilizing role of the para-phenylene unit on unusual 2n+3 SE clusters
Kahlert, J.; Stammler, H.-J.; Neumann, B.; Harder, R.A.; Weber, L.; Fox, M.A
Authors
Abstract
While carboranes with 2 n+2 and 2 n+4 (n=number of skeletal atoms) skeletal electrons (SE) are widely known, little has been reported on carboranes with odd SE numbers. Electrochemical measurements on two-cage assemblies, where two C-phenyl-ortho-carboranyl groups are linked by a para-phenylene or a para-tetrafluorophenylene bridge, revealed two well separated and reversible two-electron reduction waves indicating formation of stable dianions and tetraanions. The salts of the dianions were isolated by reduction with sodium metal and their unusual structures were determined by X-ray crystallography. The diamagnetic dianions contain two 2 n+3 SE clusters where each cluster has a notably long carborane C–carborane C distance of ca 2.4 Å. The π conjugation within the phenylene bridge plays an important role in the stabilization of these carboranes with odd SE counts.
Citation
Kahlert, J., Stammler, H., Neumann, B., Harder, R., Weber, L., & Fox, M. (2014). Crystal structures of the carborane dianions, [1,4-(PhCB10H10C)2C6H4]2- and [1,4-(PhCB10H10C)2C6F4]2-, and the stabilizing role of the para-phenylene unit on unusual 2n+3 SE clusters. Angewandte Chemie International Edition, 53(14), 3702-3705. https://doi.org/10.1002/anie.201310718
Journal Article Type | Article |
---|---|
Acceptance Date | Dec 10, 2013 |
Online Publication Date | Feb 26, 2014 |
Publication Date | Apr 1, 2014 |
Deposit Date | Jan 9, 2014 |
Publicly Available Date | Mar 19, 2014 |
Journal | Angewandte Chemie International Edition |
Print ISSN | 1433-7851 |
Electronic ISSN | 1521-3773 |
Publisher | Wiley |
Peer Reviewed | Peer Reviewed |
Volume | 53 |
Issue | 14 |
Pages | 3702-3705 |
DOI | https://doi.org/10.1002/anie.201310718 |
Keywords | Carborane, Conjugation, Electrochemistry, Phenylene, Quinoidal structures. |
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Advance online version © 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co.
KGaA. This is an open access article under the terms of the Creative
Commons Attribution License, which permits use, distribution and
reproduction in any medium, provided the original work is properly
cited.
Published Journal Article (Final published version)
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Publisher Licence URL
http://creativecommons.org/licenses/by/4.0/
Copyright Statement
Final published version
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