(CH₃)₂SBr₂ – einige Reaktionen und Strukturen

Abstract

(CH3)2SBr2 (1) ist ein (8‐S‐3 + 10‐Br‐2) Donor‐Akzeptor‐Komplex und reagiert mit (CH3)2S(O)NSi(CH3)3 zu [(CH3)2S(O)NS(CH3)2]+Br− (2), mit SbBr3 zu (CH3)2SBr+SbBr4− (3). 1 kristallisiert monoklin (P21/c) mit a = 733,8, b = 734,2, c = 1132,7 pm, β = 92,8° und Z = 4. 2 kristallisiert orthorhombisch in der Raumgruppe Pnma mit a = 967,2, b = 793,3, c = 1168,3 pm und Z = 4. Die SBr‐ und BrBr‐Kraftkonstanten von 1 werden mit denen von S2Br2 und 3 bzw. Br2 verglichen. Die NMR‐ und Massenspektren von 1 und 2 werden kurz diskutiert.

Trapping of a Thiolate→Dibromine Charge‐Transfer Adduct by a Macrocyclic Dinickel Complex and Its Conversion into an Arenesulfenyl Bromide Derivative

“…[18] The band at 336 cm À1 is assumed to be the stretching vibration of the S À Br bond. This frequency is similar to those reported for Me 2 S À Br + (346 cm À1 ) [10] and S 2 Br 2 (357 cm À1 ). [19] The shift of the S À Br stretch from 292 cm À1 in 2 to 336 cm À1 in 4 is in good agreement with the stronger (covalent) SÀBr bonding interaction in 4.…”

“…In the thioether-Br 2 CT adduct (CH 3 ) 2 SBr 2 these modes occur at 211 and 289 cm À1 , respectively. [10] The large shift of the BrÀBr stretching vibration away from that of the uncomplexed Br 2 molecule (301 cm À1 ) [17] is in agreement with a decrease of the Br À Br bond order and the CT nature of 2. Complex 4 displays two Raman bands at 156 and 180 cm À1 attributable to the n s (BrBr) and n as (BrBr) stretching modes of the tribromide ions.…”

“…The SÀBr distance is significantly longer than the value of approximately 2.18 predicted for a covalent SÀ Br single bond [9] and is within the range of SÀBr distances reported for bromine thioether CT adducts (2.3-2.4 ). [10,11] The Ni À S1 bond lengths are also affected, on average these lengthen by 0.11 relative to 1.To our knowledge, no dibromine adduct of a nickel thiolate complex has been reported to date. However, a iodine adduct of a square-planar nickel thiolate complex…”

Telluranes: potential synthons for charge-transfer complexes (involving hypervalent Te–I bonds) and serendipitous synthesis of the first triphenyl methyl phosphonium salts containing [C4H8TeI4]2− and [TeI6]2−anions

“…Two distinct structural motifs are possible: R 2 YX 2 could be a charge transfer (CT) complex R 2 Y-X-X or it may correspond to W trigonal bipyramidal (TBP) structure. For example Me 2 SBr 2 is a CT complex Me 2 S-Br-Br [2] while Me 2 SeBr 2 [3] and Me 2 TeBr 2 [4] adopt WTBP structure. Me 2 SI 2 [1], Me 2 SeI 2 [3] are CT complexes and Me 2 TeI 2 [5,6] corresponds to WTBP structure.…”

Interpretation der Schwingungsspektren von (CH3)2SO2, (CH3)2SO(NH) und (CH3)2S(NH)2 unter Verwendung eines Kopplungsstufenverfahrens

“…Normal Coordinate Analysis of (CH 3 ) 2 SO 2 , (CH 3 ) 2 SO(NH), and (CH 3 ) 2 S(NH) 2 using the Method of Stepwise Coupling Abstract. The qualitative assignment of the vibrational spectra of (CH 3 ) 2 SO 2 (1), (CH 3 ) 2 SO(NH) (2 a), and (CH 3 ) 2 S(NH) 2 (3 a) and of the C and N deuterated derivatives of 2 a and 3 a is used in a normal coordinate analysis by the method of stepwise coupling. The force constants and the energy distributions are calculated in symmetry coordinates using a generalized valence force field.…”