Syntheses and chemistry of hypervalent cyclo-R4Sb4, cyclo-(RSbE)n[R = 2-(Me2NCH2)C6H4, E = O, S] and precursors.

Autor: Opris LM; Facultatea de Chimie si Inginerie Chimica, Universitatea Babes-Bolyai, Cluj-Napoca, Romania., Silvestru A, Silvestru C, Breunig HJ, Lork E
Jazyk: angličtina
Zdroj: Dalton transactions (Cambridge, England : 2003) [Dalton Trans] 2004 Nov 07 (21), pp. 3575-85. Date of Electronic Publication: 2004 Sep 28.
DOI: 10.1039/B409866H
Abstrakt: The cyclostibane R(4)Sb(4)(1)(R = 2-(Me(2)NCH(2))C(6)H(4)) was synthesized by reduction of RSbCl(2) with Mg in THF or with Na in liquid NH(3). The reaction of 1 with [W(CO)(5)(THF)] gives the stibinidene complex RSb[W(CO)(5)](2)(2). RSbCl(2) and (RSbCl)(2)E [E = O (6), E = S (8)] react with KOH or Na(2)S in toluene/water to give the heterocycles (RSbE)(n)[E = O, n= 3 (3); E = S, n= 2 (4)]. The chalcogeno-bridged compounds of the type (RSbCl)(2)E [E = O (6), E = S (8)] were synthesized by reaction of RSbCl(2) with KOH or Na(2)S in toluene/water, but also by reaction of RSbCl(2) with the heterocycles (RSbE)(n). The compounds (RSbI)(2)O (7) and (RSbBr)(2)S (9) were prepared via halogen-exchange reactions between (RSbCl)(2)E and NaI (E = O) or KBr (E = S) or by reactions between RSbI(2) and KOH or RSbBr(2) and Na(2)S. The reaction of cyclo-(RSbS)(2) with W(CO)(5)(THF) in THF results in trapping of the cis isomer in cyclo-(RSbS)(2)[W(CO)(5)](5). The solution behaviour of the compounds was investigated by (1)H and (13)C NMR spectroscopy. The molecular structures of compounds 1-7 and 9 were determined by single-crystal X-ray diffraction.
Databáze: MEDLINE