title: Formation of T-shaped versus charge-transfer molecular adducts in the reactions between bis(thiocarbonyl) donors and Br2 and I2.
abstract: The reactions of 4,5,6,7-tetrathiocino-[1,2-b:3,4-b']-1,3,8,10-tetrasubstituted-diimidazolyl-2,9-dithiones (R(2),R'(2)-todit; 1: R=R'=Et; 2: R=R'=Ph; 3: R=Et, R'=Ph) with Br(2) exclusively afforded 1:1 and 1:2 "T-shaped" adducts, as established by FT-Raman spectroscopy and single-crystal X-ray diffraction in the case of complex 1·2Br(2). On the other hand, the reactions of compounds 1-3 with molecular I(2) provided charge-transfer (CT) "spoke" adducts, among which the solvated species 3·2I(2)·(1-x)I(2)·xCH(2)Cl(2) (x=0.94) and (3)(2)·7I(2)·xCH(2)Cl(2), (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.
authors.affiliation: Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, S.S. 554 bivio per Sestu, 09042 Monserrato, Cagliari, Italy.
authors.forename: Annalisa
authors.initials: A
authors.lastname: Mancini
authors.forename: M Carla
authors.initials: MC
authors.lastname: Aragoni
authors.forename: Neil
authors.initials: N
authors.lastname: Bricklebank
authors.forename: Carlo
authors.initials: C
authors.lastname: Castellano
authors.forename: Francesco
authors.initials: F
authors.lastname: Demartin
authors.forename: Francesco
authors.initials: F
authors.lastname: Isaia
authors.forename: Vito
authors.initials: V
authors.lastname: Lippolis
authors.forename: Anna
authors.initials: A
authors.lastname: Pintus
authors.forename: Massimiliano
authors.initials: M
authors.lastname: Arca