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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

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 Thumbnail


Authors

J. Kahlert

H.-J. Stammler

B. Neumann

R.A. Harder

L. Weber



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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Publisher Licence URL
http://creativecommons.org/licenses/by/4.0/

Copyright Statement
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.





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