Synthesis of the first 11-vertex arachno-dicarbathiaborane anion, [1,6,7-C2SB8H11](-). Theoretical refinement of its structure

0163491 - UACH-T 20033039 RIV GB eng J - Článek v odborném periodiku
Janoušek, Zbyněk - Holub, Josef - Hnyk, Drahomír - Londesborough, Michael Geoffrey Stephen - Shoemaker, R. K.
Synthesis of the first 11-vertex arachno-dicarbathiaborane anion, [1,6,7-C2SB8H11](-). Theoretical refinement of its structure.
Polyhedron. Roč. 22, č. 27 (2003), s. 3541-3545. ISSN 0277-5387. E-ISSN 1873-3719
Grant CEP: GA MŠMT LN00A028
Výzkumný záměr: CEZ:AV0Z4032918
Klíčová slova: boranes * heteroboranes * NMR spectroscopy
Kód oboru RIV: CA - Anorganická chemie
Impakt faktor: 1.584, rok: 2003

The addition of elemental sulphur to the 10-vertex nido dicarborane [6,9-C(2)B(8)H10](2-)(2) engenders the new 11-vertex species [1,6,7-C2SB8H11](-) (2), which has been structurally characterised using the ab initio/GIAO/NMR method and by deductions made from observations on its reaction chemistry. These combined studies revealed 2 to adopt a structure that is formally derived from the hypothetical parent [closo-B13H13](2-) anion by removal of two adjacent six-coordinate and five-coordinate vertices. Since the GIAO calculations of B-11 and C-13 chemical shifts, employing the RMP2/6-31G* geometry, showed an excellent agreement with the experimental findings, in particular those for delta(B-11) and delta(C-13) that were computed at the GIAO-RMP2/II' level, the RMP2/6-31G* parameters can be deemed a good representation of the molecular structure of 2 in solution. The other possible structural alternatives of 2 could be ruled out on the basis of geometrical, energetic, and NMR criteria.
Trvalý link: http://hdl.handle.net/11104/0060724