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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 2n+3 skeletal electron clusters.

Kahlert J, Stammler HG, Neumann B, Harder RA, Weber L, Fox MA - Angew. Chem. Int. Ed. Engl. (2014)

Bottom Line: 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.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.

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Affiliation: Fakultät für Chemie der Universität Bielefeld, 33615 Bielefeld (Germany).

No MeSH data available.


Molecular structures of the dianions [3]2− and [4]2− in the crystals. The tris(dimethoxyethane)sodium cations and hydrogen atoms are omitted for clarity.
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fig04: Molecular structures of the dianions [3]2− and [4]2− in the crystals. The tris(dimethoxyethane)sodium cations and hydrogen atoms are omitted for clarity.

Mentions: Diphenyl-ortho-carborane, 1,2-Ph2-1,2-C2B10H10 (1; Scheme 1), shows two one-electron reduction waves indicating the presence of a stable radical anion [1]− with a 2 n+3 SE count.10 Spectroelectrochemical experiments, EPR measurements and calculations on the radical anion [1]− suggest that the free electron is delocalized within the carborane cluster and the carborane C1═C2 bond is lengthened to 2.39 Å in [1]− compared to 1.76 Å in 1 at B3LYP/6-31G*.11 The phenyl groups remain little changed on going from 1 to [1]−.


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 HG, Neumann B, Harder RA, Weber L, Fox MA - Angew. Chem. Int. Ed. Engl. (2014)

Molecular structures of the dianions [3]2− and [4]2− in the crystals. The tris(dimethoxyethane)sodium cations and hydrogen atoms are omitted for clarity.
© Copyright Policy
Related In: Results  -  Collection

Show All Figures
getmorefigures.php?uid=PMC4257503&req=5

fig04: Molecular structures of the dianions [3]2− and [4]2− in the crystals. The tris(dimethoxyethane)sodium cations and hydrogen atoms are omitted for clarity.
Mentions: Diphenyl-ortho-carborane, 1,2-Ph2-1,2-C2B10H10 (1; Scheme 1), shows two one-electron reduction waves indicating the presence of a stable radical anion [1]− with a 2 n+3 SE count.10 Spectroelectrochemical experiments, EPR measurements and calculations on the radical anion [1]− suggest that the free electron is delocalized within the carborane cluster and the carborane C1═C2 bond is lengthened to 2.39 Å in [1]− compared to 1.76 Å in 1 at B3LYP/6-31G*.11 The phenyl groups remain little changed on going from 1 to [1]−.

Bottom Line: 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.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.

View Article: PubMed Central - PubMed

Affiliation: Fakultät für Chemie der Universität Bielefeld, 33615 Bielefeld (Germany).

No MeSH data available.