Thermal isomerizations of monothiolated carboranes (HS)C2B10H11 and the solidstate investigation of 9-(HS)-1,2-C2B10H11 and 9-(HS)-1,7-C2B10H11

0445984 - ÚACH 2016 RIV CH eng J - Journal Article
Baše, Tomáš - Macháček, Jan - Hájková, Zuzana - Langecker, Jens - Kennedy, John David - Carr, MJ.
Thermal isomerizations of monothiolated carboranes (HS)C2B10H11 and the solidstate investigation of 9-(HS)-1,2-C2B10H11 and 9-(HS)-1,7-C2B10H11.
Journal of Organometallic Chemistry. Roč. 798, č. 1 (2015), s. 132-140. ISSN 0022-328X. E-ISSN 1872-8561
R&D Projects: GA ČR GAP205/10/0348
Institutional support: RVO:61388980
Keywords : Carboranethiol * Isomerisation * Thermal Stability * Closo-dicarbadodecaboranes * Closo-dicarbadodecaborane thiol
Subject RIV: CA - Inorganic Chemistry
Impact factor: 2.336, year: 2015

At 300-500 ºC, 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 closodicarbadodecaborane 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 Bthiolated 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.
Permanent Link: http://hdl.handle.net/11104/0254437


Research data: CCDC, CCDC