Sabahittin Gülec

Strukturen von [Me4Sb]2[MeSbI4]MeSbI2, und [Me4Sb]I. Darstellung von Me3Sb · MeSbI2 und farbwechsel bei Me4Sb2 · Me2SbBr

Abstract The crystal structures of the complex [Me 4 Sb] 2 [MeSbI 4 ] ( 1 ) and its precursors MeSbI 2 ( 2 ) and [Me 4 Sb]I ( 3 ) are reported. In 1 there are tetrahedral cations and square pyramidal anions with Sb-I distances of 290–320 pm. The structure of 2 contains MeSbI 2 molecules. They associate via iodine bridges to form linear chains with alternating short and long Sb-I distances. The coordination around antimony is distorted tetragonal pyramidal. The tetrahedral coordination of the ions in 3 results in the formation of a wurtzite type structure with antimony-iodine distances of 406 and 435 pm. The novel adducts Me 3 Sb·Me 2 SbI 2 ( 4 ) and Me 2 SbSbMe 2 ·Me 2 SbBr ( 5 ) are formed by reaction of the components. They decompose easily with formation of antimony(V) compounds. Crystals of 5 are yellow but become reversibly black on cooling.

(Me3Sn)2SbSb(SnMe3)2, 1∞-verknüpfte SbSb-Hanteln in einem thermochromen Distiban mit Schweratomgerüst

Abstract Single crystals of the thermochromic distibane (Me 3 Sn) 4 Sb 2 ( 1 ) are obtained by irradiation of (Me 3 Sn) 3 Sb with sunlight. The crystal structure of 1 is reported as linear chains of distibane molecules in trans conformation with Sb ⋯ Sb contacts of 389 ppm. Diffuse reflexion spectra of 1 in the solid state and in solution demonstrate thermochromic effect. The Raman spectrum of solid 1 exhibits strong absorption at 162 cm −1 for ν(Sb 2 ).

Reactions of Cyclostibanes or Distibanes with Diselenides or Ditellurides

Abstract Reactions of (MesSb)4 or (EtSb)x with (MeSe)2, (PhSe)2, (MeTe)2, (PhTe)2 or (p-TolTe)2 were studied in C6D6 in sealed NMR tubes. Products of the type Mes2 SbER (E = Se, Te; R = Me, Ph, p-Tol) and (p-TolTe)2 SbMes or Et (SbER)2 (E = Se, Te; R = Me, Ph, p-Tol) were obtained. EtSb(TePh)2 was synthesized as red crystals. The telluro stibanes Me2 SbTePh and Et2 SbTePh were prepared from Me4 Sb2 or Et4 Sb2 and (PhTe)2.

Alkylantimondichloride und -bromide

Abstract MeSbCl 2 is formed by the exchange reaction of equimolar amounts of Me 2 SbCl with SbCl 3 . Alkylantimony dibromides of the type RSbBr 2 with R = Me, Et, n-Pr, n-Bu are obtained by dismutation of the corresponding dialkylantimony bromides with SbBr 3 . Exchange as well as redox reactions occur in the R 3 Sb and SbX 3 , or R 3 Sb and RSbX 2 (R = Me, Et; X = Cl, Br) system. Ethylantimony dibromide can also be synthesized by elimination of EtBr from Et 2 SbBr 3 . The 1 H NMR spectra of the alkylantimony dihalides in CDCl 3 and C 6 D 6 exhibit major solvent effects.

NEUE DARSTELLUNG, SCHWEFELINSERTION UND HYDROLYSE DER PHENYL(TRIMETHYLSILYL)STIBANE

Abstract Reaction of Mg and Me3,SbCl with Ph2,SbCl or PhSbCl2, gives Ph2,SbSiMe3, (1) or PhSb(SiMe3)2, (2). Sulfur inserts into 1 to give Ph2,SbSSiMe3, (3). Products of action of S8 on 2 are 3, PhSb(SSiMe3,)2, (4), (Me3,Si)2,S, and Sb2S3. Hydrolysis or methanolysis of 1, or 2 give Ph2,SbH2 (5), or PhSbH2, (6) respectively. Die Reaktion von Mg und Me3SiCl mit Ph2SbCl oder PhSbCl2 fuhrt zu Ph2,SbSiMe3 (1) oder PhSb(SiMe3,)2, (2). Schwefel insertiert in 1 unter Bildung von Ph2,SbSSiMe3, (3). Produkte der Reaktion von S8, mit 2 sind 3, PhSb(SSiMe3,)2, (4), (Me3,Si)2,S und Sb2S3. Durch Hydrolyse oder Methanolyse von 1 oder 2 entstehen Ph2SbH (5) oder PhSbH2 (6).

Equilibria in Organo Antimony Ring Chemistry

Abstract Reactions of ethyl antimony and n-propyl antimony rings give equilibria with the mixed substituted derivatives R(n-m)R′mSbn (n = 4, m=1-3; n=5, m=1-4; R=Et, R′= n-Pr). The equilibrium constant K = [(EtSb)4]5/[(EtSb)5]4 has been determined as K = 9.10−8 mol/l. Air oxidation of p-TolSb(SiMeo3)2 gives yellow crystals of p-tolylantimony. In solution (p-TolSb)5 is the most abundant of p-tolyl antimony rings.

Exchange reactions of distibines

Abstract Distibines of the type R 2 SbSbR′ 2 with R = CH 3 , R′ = C 2 H 5 ( 1 ), R = CH 3 , R′= n -C 3 H 7 ( 2 ), R = CH 3 , R′= C 6 H 5 ( 3 ), R = C 2 H 5 , R′= C 6 H 5 ( 4 ), R = n -C 3 H 7 , R′ = C 6 H 5 ( 5 ), and R = CH 3 , R′ = 2,4,6-(CH 3 ) 2 C 6 H 2 ( 6 ) are formed in equilibria by exchange reactions of the respective distibines of the type R 4 Sb 2 and R′ 4 Sb 2 .

The Molecular Structures and Conformational Preferences of Simple Molecules Containing Bonds Between a Trivalent Group 15 and a Divalent Group 16 Element: The Molecular Structures of Dimethyl(methylthio)stibane and Dimethyl(methylseleno)stibane, (CH3)2SbECH3 E = S or Se, by Gas Electron Diffraction

Gas electron diffraction data of (CH3)2SbECH3 E = S or Se, show that the predominant conformer is one where the dihedral angle defined by the E–C bond, the Sb–E bond and the presumed direction of the lone pair at the Sb atom falls in the range –45 to +45°. The Sb–S and Sb–Se bond distances are 241.4(8) and 255.5(3) pm, respectively.

Darstellung von Dichalkogenostibanen des Typs RSb(ER′)2 (R = CH3, C2H5; E = S, Se; R = CH3, C6H5)/ Preparation of Dichalcogenostibanes of the Type RSb(ER′)2 (R = CH3, C2H5; E = S, Se; R′ = CH3, C6H5 )

Abstract Dichalcogenostibanes of the type RSb(ER′)2 (R = CH3 ,C2H5; E = S. Se; R′ = CH3. C6H5) and trialkylstibanes R3Sb have been prepared by redistribution reactions of stibanes of the type R2SbER′.