Formation of T-Shaped versus Charge-Transfer Molecular Adducts in the Reactions Between Bis(thiocarbonyl) Donors and Br2and I2

The reactions of 4,5,6,7-tetrathiocino-[1,2-b:3,4-b’]-1,3,8,10-tetrasubstituted-diimidazolyl-2,9-dithiones (R2,R’2-todit; 1: R=R’=Et; 2: R=R’=Ph; 3: R=Et, R’=Ph) with Br2 exclusively afforded 1:1 and 1:2 “Tshaped” adducts, as established by FTRaman spectroscopy and single-crystal X-ray diffraction in the case of complex 1·2Br2. On the other hand, the reactions of compounds 1–3 with molecular I2 provided charge-transfer (CT)“spoke” adducts, among which the solvated species 3·2I2·ACHTUNGTRENUNG(1�x)I2·xCH2Cl2 (x=0.94) and (3)2·7I2·xCH2Cl2, (x=0.66) were structurally characterized. The nature of all of the reaction products was elucidated based on elemental analysis and FT-Raman spectroscopy and supported by theoretical calculations at the DFT level.