TY - JOUR T1 - Icosahedral Carbaboranes with Peripheral Hydrogen– Chalcogenide Groups: Structures from Gas Electron Diffraction and Chemical Shielding in Solution JF - Chemistry A European Journal Y1 - 2019 A1 - Tomas Base A1 - Josef Holub A1 - Jindrich Fanfrlik A1 - Drahomir Hnyk A1 - Paul L Lane A1 - Derek A Wann A1 - Yury V Vishnevskiy A1 - Denis Tikhonov A1 - Christian G Reuter A1 - Norbert W Mitzel KW - carborane-diselenol KW - carborane-dithiol KW - gass phase electron diffraction KW - GPE KW - sturcture AB -

Hydrochalcogeno carbaboranes: Icosahedral carbaboranes with thiol and selenol groups were prepared and their structures determined by gas electron diffraction augmented by ab initio calculated data (see figure). A method for quantifying the experimental contribution to the structural parameters was developed and tested. Comparison of NMR chemical shifts in solution with quantum‐chemically calculated values allowed further structural information to be retrieved.

VL - 25 UR - https://onlinelibrary.wiley.com/doi/10.1002/chem.201805145 IS - 9 ER - TY - JOUR T1 - The gaseous structure of closo-9,12-(SH)2-1,2-C2B10H10, a modifier of gold surfaces, as determined using electron diffraction and computational methods JF - Dalton Transactions Y1 - 2013 A1 - Derek A Wann A1 - Paul D Lane A1 - Heather E Robertson A1 - Tomas Base A1 - Drahomir Hnyk AB -

The molecular structure of closo-9,12-(SH)2-1,2-C2B10H10 has been determined by the concerted use of quantum chemical calculations and gas electron diffraction (GED). For the purposes of GED, the architecture of the carbaborane cage was simplified to allow it to have C2v symmetry, while the positioning of the thiol groups means that the molecule had overall C1 symmetry. The accuracy of the experimental structure, as well as that calculated at the MP2(full)/6-311++G(3df,3pd) level, has been gauged by comparison of experimental 11B NMR chemical shifts with those calculated using gauge-invariant atomic orbitals (GIAO) methods. The inclusion of electron correlation in the magnetic property calculations (GIAO-MP2) gave superior results to those carried out using GIAO-HF. The electronic structure of this derivative, with respect to its directional interaction with a metal surface, is outlined.

VL - 42 UR - http://pubs.rsc.org/en/results?artrefjournalname=dalton%20trans.&artrefstartpage=12015&artrefvolumeyear=2013&fcategory=journal ER -