@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}, year = {2015}, 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} } @article {119, title = {Decaborane Thiols as Building Blocks for Self-Assembled Monolayers on Metal Surfaces}, journal = {Inorganic Chemistry}, volume = {51}, year = {2012}, chapter = {1685}, abstract = {

Three nido-decaborane thiol cluster compounds, [1-(HS)-nido-B10H13] 1, [2-(HS)-nido-B10H13] 2, and [1,2-(HS)2-nido-B10H12] 3 have been characterized using NMR spectroscopy, single-crystal X-ray diffraction analysis, and quantum-chemical calculations. In the solid state, 1, 2, and 3 feature weak intermolecular hydrogen bonding between the sulfur atom and the relatively positive bridging hydrogen atoms on the open face of an adjacent cluster. Density functional theory (DFT) calculations show that the value of the interaction energy is approximately proportional to the number of hydrogen atoms involved in the interaction and that these values are consistent with a related bridging-hydrogen atom interaction calculated for a B18H22 C6H6 solvate. Self-assembled monolayers (SAMs) of 1, 2, and 3 on gold and silver surfaces have been prepared and characterized using X-ray photoelectron spectroscopy. The variations in the measured sulfur binding energies, as thiolates on the surface, correlate with the (CC2) calculated atomic charge for the relevant boron vertices and for the associated sulfur substituents for the parent B10H13(SH) compounds. The calculated charges also correlate with the measured and DFT-calculated thiol 1H chemical shifts. Wetting-angle measurements indicate that the hydrophilic open face of the cluster is directed upward from the substrate surface, allowing the bridging hydrogen atoms to exhibit a similar reactivity to that of the bulk compound. Thus, [PtMe2(PMe2Ph)2] reacts with the exposed and acidic B }, doi = {10.1021/ic202000b}, author = {Jonathan Bould and Jan Machacek and Michael G S Londesborough and Ramon Macias and John D Kennedy and Zdenek Bastl and Patrik Rupper and Tomas Base} } @article {123, title = {Reversible Capture of Small Molecules On Bimetallaborane Clusters: Synthesis, Structural Characterization, and Photophysical Aspects}, journal = {Inorganic Chemistry}, volume = {50}, year = {2011}, chapter = {7511}, doi = {10.1021/ic200374k}, url = {http://pubs.acs.org/doi/abs/10.1021\%2Fic200374k}, author = {Jonathan Bould and Tomas Base and Michael G S Londesborough and Luis A Oro and Ramon Macias and John D Kennedy and Pavel Kubat and Marcel Fuciman and Tomas Polivka and Kamil Lang} } @article {124, title = {An Experimental Solution to the "Missing Hydrogens" Question Surrounding the Macropolyhedral 19-Vertex Boron Hydride Monoanion [B19H22](-), a Simplification of Its Synthesis, and Its Use As an Intermediate in the First Example of syn-B18H22 to anti-B18H22}, journal = {Inorganic Chemistry}, volume = {49}, year = {2010}, chapter = {4092}, doi = {10.1021/IC901976y}, url = {http://pubs.acs.org/doi/abs/10.1021/ic901976y}, author = {Michael G S Londesborough and Jonathan Bould and Tomas Base and Drahomir Hnyk and Mario Bakardjiev and Josef Holub and Ivana Cisarova and John D Kennedy} }