An unexpected rearrangement of carbon vertexes in the tricarbollide series. Asymmetrical 7-aryl-nido-7,8,9-C3B8H11 derivatives

0456958 - ÚACH 2016 RIV CH eng J - Článek v odborném periodiku
Bakardjiev, Mario - Holub, Josef - Hnyk, Drahomír - Štíbr, Bohumil - Růžičková, Z. - Růžička, A.
An unexpected rearrangement of carbon vertexes in the tricarbollide series. Asymmetrical 7-aryl-nido-7,8,9-C3B8H11 derivatives.
Journal of Organometallic Chemistry. Roč. 805, MAR (2016), s. 117-121. ISSN 0022-328X. E-ISSN 1872-8561
Grant CEP: GA ČR(CZ) GAP207/11/0705
Institucionální podpora: RVO:61388980
Klíčová slova: Boron hydrides * Carboranes * NMR spectroscopy
Kód oboru RIV: CA - Anorganická chemie
Impakt faktor: 2.184, rok: 2016

Thermal rearrangement of the Na+[8-R-nido-7,8,9-C3B8H10]¯ salts (R = Ph, p-tol, and 2-naph = 2-napthhyl), followed by protonation with conc. H2SO4, proceeds via an unexpected 8 → 7 rearrangement of the cluster RC unit under the formation of the neutral 7-R-nido-7,8,9-C3B8H11 tricarbollides. A C-vertex swing mechanism, involving an unstable 2,7,8-intermediate, was proposed for this rearrangement and substantiated via MP2/6-31G*calculations. Removal of the bridging hydrogen from 7-R-nido-7,8,9-C3B8H11 with Et3N leads to the Et3NH+ salts of the corresponding [7-R-nido-7,8,9-C3B8H10]¯ anions. All the compounds isolated were characterized by multinuclear (11B, 1H, and 13C) NMR spectroscopy and the structures of the simplest 7-Me derivatives were optimized at the MP2/6-31G*level of theory, the structures being verified by GIAO-MP2 computations. The structure of the starting 8-(p-tol)-nido-7,8,9-C3B8H11 was determined by an X-ray diffraction study.
Trvalý link: http://hdl.handle.net/11104/0257455


Vědecká data: CCDC