@article {140, title = {Thermal isomerizations of monothiolated carboranes (HS)C2B10H11 and the solid-state investigation of 9-(HS)-1,2-C2B10H11 and 9-(HS)-1,7-C2B10H11}, journal = {Journal of Organometallic Chemistry}, volume = {798}, year = {2015}, month = {12/2015}, pages = {132-140}, type = {Full article}, chapter = {132}, abstract = {

At 300-500 C, three C-thiolated closo-dicarbadodecaborane isomers 1-(HS)-1,2-C2B10H11 (1-o), 1-(HS)-1,7-C2B10H11 (1-m), and 1-(HS)-1,12-C2B10H11 (1-p), and two B-thiolated isomers 9-(HS)-1,7-C2B10H11 (9-m) and 9-(HS)-1,2-C2B10H11 (9-o) show two types of reaction: first, removal of an SH group from the closo-dicarbadodecaborane skeleton, and second, skeletal isomerizations from ortho to meta to para that lead to new isomers. A previously unreported SH skip from carbon-to-boron is also observed. The effect of the thiol group on the skeletal rearrangement is discussed. The isomerisation products are assigned on the basis of correlation of their computationally obtained dipole moments with their gas-chromatographic retention times. Computational results on molecular energies for the mono-thiolated species show good agreement between the calculated relative stabilities and the incidence and relative quantities of the isomerization products. Two of the starting B-thiolated isomers, 9-o and 9-m, were characterized using single-crystal X-ray diffraction analyses and their crystallographic packings as well as some selected structural parameters are discussed. All starting compounds were characterized using multinuclear NMR spectroscopy.

}, keywords = {carborane, Carboranethiol, closo-dicarbadodecaborane thiol, closo-dicarbadodecaboranes, Cluster, Dipole, Isomer, Isomerisation, Thermal Stability}, doi = {10.1016/j.jorganchem.2015.06.020}, url = {http://www.sciencedirect.com/science/article/pii/S0022328X15300462}, author = {Tomas Base and Jan Machacek and Zuzana Hajkova and Jens Langecker and John D Kennedy and Michael J Carr} }