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 2n+3 Skeletal Electron Clusters

Kahlert J, Stammler H-G, Neumann B, Harder RA, Weber L, Fox MA (2014)
Angewandte Chemie - International Edition in English 53(14): 3702-3705.

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While carboranes with 2n+2 and 2n+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 2n+3 SE clusters where each cluster has a notably long carboraneC-carboraneC distance of ca 2.4 angstrom. The conjugation within the phenylene bridge plays an important role in the stabilization of these carboranes with odd SE counts.
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Kahlert J, Stammler H-G, Neumann B, Harder RA, Weber L, Fox MA. 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 2n+3 Skeletal Electron Clusters. Angewandte Chemie - International Edition in English. 2014;53(14):3702-3705.
Kahlert, J., Stammler, H. - G., Neumann, B., Harder, R. A., Weber, L., & Fox, M. A. (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 2n+3 Skeletal Electron Clusters. Angewandte Chemie - International Edition in English, 53(14), 3702-3705.
Kahlert, J., Stammler, H. - G., Neumann, B., Harder, R. A., Weber, L., and Fox, M. A. (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 2n+3 Skeletal Electron Clusters. Angewandte Chemie - International Edition in English 53, 3702-3705.
Kahlert, J., et al., 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 2n+3 Skeletal Electron Clusters. Angewandte Chemie - International Edition in English, 53(14), p 3702-3705.
J. Kahlert, et al., “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 2n+3 Skeletal Electron Clusters”, Angewandte Chemie - International Edition in English, vol. 53, 2014, pp. 3702-3705.
Kahlert, J., Stammler, H.-G., 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 2n+3 Skeletal Electron Clusters. Angewandte Chemie - International Edition in English. 53, 3702-3705 (2014).
Kahlert, Jan, Stammler, Hans-Georg, Neumann, Beate, Harder, Rachel A., Weber, Lothar, and Fox, Mark 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 2n+3 Skeletal Electron Clusters”. Angewandte Chemie - International Edition in English 53.14 (2014): 3702-3705.
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Negatively charged metallacarborane redox couples with both members stable to air.
Lupu M, Zaulet A, Teixidor F, Ruiz E, Vinas C., Chemistry 21(18), 2015
PMID: 25788451

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Alekseyeva ES, Fox MA, Howard JAK, MacBride JAH, Wade K., 2003

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