Icosahedral Carbaboranes with Peripheral Hydrogen–Chalcogenide Groups: Structures from Gas Electron Diffraction and Chemical Shielding in Solution

TY - JOUR

T1 - Icosahedral Carbaboranes with Peripheral Hydrogen–Chalcogenide Groups

T2 - Structures from Gas Electron Diffraction and Chemical Shielding in Solution

AU - Baše, Tomáš

AU - Holub, Josef

AU - Fanfrlík, Jindřich

AU - Hnyk, Drahomír

AU - Lane, Paul D.

AU - Wann, Derek A.

AU - Vishnevskiy, Yury V.

AU - Tikhonov, Denis

AU - Reuter, Christian G.

AU - Mitzel, Norbert W.

N1 - © 2018 WILEY‐VCH Verlag GmbH & Co. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details.

PY - 2019/2/11

Y1 - 2019/2/11

N2 - Carbaboranes 1,2-(EH)2-closo-1,2-C2B10H10 (E=S, Se) were prepared, in the case of E=Se for the first time. Their semi-experimental equilibrium molecular structures were established by the concerted use of quantum-chemical calculations and gas electron diffraction. A method was developed and implemented to quantify the contribution of experimental data to each refined structural parameter. The accuracy of the experimental structures and those calculated at the MP2 level of theory were gauged by comparison of experimental 11B NMR chemical shifts with quantum-chemically computed values; the inclusion of electron correlation (GIAO-MP2) provided superior results. For the purpose of geometrical prediction, the remaining group 16 elements were considered, and the icosahedral structures for E=O and Te were also computed; for E=O the same theoretical approach was used as for E=S, and for E=Te a description similar to that for E=Se was employed.

AB - Carbaboranes 1,2-(EH)2-closo-1,2-C2B10H10 (E=S, Se) were prepared, in the case of E=Se for the first time. Their semi-experimental equilibrium molecular structures were established by the concerted use of quantum-chemical calculations and gas electron diffraction. A method was developed and implemented to quantify the contribution of experimental data to each refined structural parameter. The accuracy of the experimental structures and those calculated at the MP2 level of theory were gauged by comparison of experimental 11B NMR chemical shifts with quantum-chemically computed values; the inclusion of electron correlation (GIAO-MP2) provided superior results. For the purpose of geometrical prediction, the remaining group 16 elements were considered, and the icosahedral structures for E=O and Te were also computed; for E=O the same theoretical approach was used as for E=S, and for E=Te a description similar to that for E=Se was employed.

KW - ab initio calculations

KW - carboranes

KW - electron diffraction

KW - selenols

KW - thiols

UR - http://www.scopus.com/inward/record.url?scp=85060176331&partnerID=8YFLogxK

U2 - 10.1002/chem.201805145

DO - 10.1002/chem.201805145

M3 - Article

C2 - 30489662

SN - 0947-6539

VL - 25

SP - 2313

EP - 2321

JO - Chemistry : A European Journal

JF - Chemistry : A European Journal

IS - 9

ER -