Beiträge zur Chemie der Silicium‐Schwefel‐Verbindungen. XXXIII. Die Struktur des Bis(triphenylsilyl)sulfids

Abstract

Bis(triphenylsilyl)sulfid (1) wurde durch Kondensation von Triphenylsilanthiol erhalten. Die Verbindung ist bemerkenswert stabil gegen Hydrolyse. 1 kristallisiert monoklin [P21/n (Nr. 14); a = 1707,8 pm; b = 1454,6 pm; c = 1225,0 pm; β = 97,27°; Z = 4; 4470 hkl; R = 0,053]. Das Molekül ist gewinkelt mit einem Bindungswinkel SiSSi = 112,0°. Die Abstände SiS bzw. SiC betragen im Mittel 215,2 pm bzw. 187,4 pm. Die Einzelheiten der Struktur werden im Zusammenhang diskutiert.

Dicoordinate Copper(I) Silanechalcogenolates

“…Trends in the Cu−E−Si bond angles for complexes 1 − 3 closely parallel those for the Si−E−Si bond angles of (Ph 3 Si) 2 E. Thus, for (Ph 3 Si) 2 E, θ(Si−E−Si) varies in the series E = O (180°), S [111.94(8)°], Se [110.51(2)°] . In addition, the unique bonding in the Cu−O−Si fragment of 1 is manifested not only by its linear geometry but also in some extremely short Cu−O and Si−O bond distances.…”

Synthesis and Structure of a S4Si4 Cage Compound

“…At the sulfur atoms of 1 an average bond angle of 87.8° was found, and the mean Si−S bond length amounts to 2.150 Å. This is comparable with the Si−S bond length in bis(triphenylsilyl) sulfide (2.153 Å) and only marginally shorter than the bond length in decamethyl-7-thiahexasilanorbornane (2.169 Å). , The angles between the two Si−S bonds at the silicon atoms average to 104.2°. In contrast to N 4 S 4 , where the electropositive sulfur atoms have a tetrahedral symmetry and the electronegative nitrogen atoms form a square plane, in compound 1 the inverse arrangement is found with the sulfur atoms in a plane like that in As 4 S 4 .…”

Salts of Tris(pentafluoroethyl)silylchalcogenolates [Si(C2F5)3E]− with E = S, Se, and Te: Synthesis, Structure, and Reactivity

“…The Si–S distance in 1a [197.8(1) pm] is significantly shortened compared to the Si–S bond lengths in alkyl-substituted silylthiolates (⌀ = 205 pm) ,, but virtually identical with the Si–S bond length in [Cl 3 SiS] − [197.5(1) pm]. , In comparison, the Si–S bonds in bis-silyl-substituted sulfides range from 214 to 216 pm − and SiS double bonds are about 195 pm long. − The same effect was observed for the Si–Se distances [212.3(1) pm compared to 220.0(1) pm in [Me 2 Pyr]­[SiMe 3 Se]] and the Si–Te bond lengths [234.7(1) pm compared to 242.1(1) pm in [K­(18-crown-6)·THF]­[SiPh 3 Te]] in the corresponding [Si­(C 2 F 5 ) 3 Se] − ( 1b ) and [Si­(C 2 F 5 ) 3 Te] − ( 1c ) ions. Along with the previously discussed NMR spectroscopic observations, this points to a stronger Si–E bond and a concomitant stabilization of the C 2 F 5 -substituted silyl chalcogenolates compared to common alkyl and aryl derivatives.…”