New route to 1-thia-closo-dodecaborane(11), closo-1-SB11H11, and its halogenation reactions. The effect of the halogen on the dipole moments and the NMR spectra and the importance of spin-orbit coupling for the B-11 chemical shifts

0040393 - ÚACH 2007 RIV GB eng J - Journal Article
Macháček, Jan - Plešek, Jaromír - Holub, Josef - Hnyk, Drahomír - Všetečka, V. - Císařová, I. - Kaupp, M. - Štíbr, Bohumil
New route to 1-thia-closo-dodecaborane(11), closo-1-SB11H11, and its halogenation reactions. The effect of the halogen on the dipole moments and the NMR spectra and the importance of spin-orbit coupling for the B-11 chemical shifts.
[Nová cesta k 1-thia-closo-dodecaborane(11) a jeho halogenační reakce. Vliv halogenu na dipólmomenty a NMR spektra. Důležitost spin-orbitálního kaplingu a NMR posuny.]
Dalton Transactions. -, č. 8 (2006), s. 1024-1029. ISSN 1477-9226. E-ISSN 1477-9234
R&D Projects: GA MŠMT(CZ) LC523
Grant - others:DFG(DE) KA1187/5-1
Institutional research plan: CEZ:AV0Z40320502
Keywords : magnetic-resonance spectroscopy * phosphadicarbaboranes * density-functional theory
Subject RIV: CA - Inorganic Chemistry
Impact factor: 3.012, year: 2006

Reaction between nido-B10H14 (1) and elemental sulfur in CHCl3, in the presence of Et3N at room temperature, followed by treatment with Et3N center dot BH3 at 170-190 degrees C, resulted in the isolation of closo-1-SB11H11 (2) in 50 percent yield. Selected electrophilic halogenation reactions of compound 2 led to the isolation of a series of monoltalogenated derivatives of general constitution. Experimental B-11 chemical shifts generally show acceptable agreement with theoretical values calculated by GIAO methods, but spin-orbit coupling must be included for nuclei bearing heavy-atom substituents such as Br or I.

Byla vypracována nová cesta přípravy 1-SB11H11 a zkoumány jeho halogenační reakce.
Permanent Link: http://hdl.handle.net/11104/0134122