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Updated: Jul 3, 2025

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework
Published on: April 9, 2018
Synthesis and cluster structure distortions of biscarborane dithiol, thioether, and disulfide
Jared R Riffle1, Tyler M Hemingway1, Mark D Smith1
1Department of Chemistry and Biochemistry, University of South Carolina, 631 Sumter St, Columbia, South Carolina 29208, USA. peryshkov@sc.edu.
Abstract:
The synthesis and structural characterization of the first sulfur-containing derivatives of the C,C-biscarborane {ortho-C2B10}2 cluster - thiol, thioether, and disulfide - are reported. The biscarboranyl dithiol (1-HS-C2B10H10)2 exhibits an exceedingly long intracluster carbon-carbon bond length of 1.858(3) Å, which is attributed to the extensive interaction between the lone pairs of the thiol groups and the unoccupied molecular orbital of the carborane cluster. The structures of the doubly deprotonated biscarboranyl dithiolate anion (1-S-C2B10H10)22- with various counter cations feature an even longer carbon-carbon bond length of 2.062(10) Å within the cluster along with a short carbon-sulfur bond of 1.660(7) Å, both indicative of significant delocalization of electron density from the sulfur atoms into the cluster.
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