The octanuclear iodine‐chlorine interhalides [I4Cl4]2− and [I3Cl5]2− were prepared in two steps. Firstly, addition of ICl to the triaminocyclopropenium chloride salt [C3(NEt2)3]Cl forms the trihalide ICl2− salt, secondly, addition of half an equivalent of I2 or ICl, respectively, gave the desired products upon crystallization at low temperature. The non‐stoichiometric octahalide [I3.6Cl4.4]2− was obtained after heating a CH2Cl2 solution of the ICl2− salt to reflux for 2 hours followed crystallization. [I4Cl4]2− is best described as two ICl2− anions bridged by I2, whereas [I3Cl5]2− is best described as an [I2Cl3]− pentahalide with a weak halogen bond to an ICl2− trihalide. The octahalides were characterized by X‐ray crystallography, computational studies, Raman and Far‐IR spectroscopies, as well as by TGA and melting point.

Rational Synthesis, Structures and Properties of the IonicL iquid Binary Iodine-BromineO ctahalideS eries [I n Br 8À Àn ] 2À À (n = 0, 2, 3, 4) Abstract: As eries of octanuclear iodine-bromine interhalides [I n Br 8Àn ] 2À (n = 0, 2, 3, 4) were prepareds ystematically in two steps. Firstly,a ddition of ad ihalogen (Br 2 or IBr) to the triaminocyclopropenium bromide salt [C 3 (NEt 2 ) 3 ]Br forms the corresponding trihalide salt with Br 3 À or IBr 2 À anions, respectively.S econdly, additiont oB r 3 À of half an equivalent of Br 2 gives the octabromine polyhalide [Br 8 ] 2À ,w hereas addition to IBr 2 À of half an equivalent of Br 2 ,I Br or I 2 gives the corresponding interhalides:[ I 2 Br 6 ] 2À ,[ I 3 Br 5 ] 2À ,a nd [I 4 Br 4 ] 2À ,r espectively.T he four octahalides were characterized by X-ray crystallography,c omputationals tudies, Ramana nd Far-IR spectroscopies, as well as by TGA and melting point. All of the salts werefound to be ionic liquids.Scheme1.The iodine-bromine interhalide family.[a] M.

The solid-state structure of a discrete chloride monohydrate species, [Cl(H 2 O)] − , is reported for the first time. It was isolated as a salt of the tris(dipropylamino)cyclopropenium cation and has been structurally characterized by X-ray and neutron diffraction. Infrared (IR), far-infrared, and Raman spectroscopic studies were also carried out. Additionally, the D 2 O and HDO isotopomers were investigated. Of the six fundamental vibrational modes, only the out-of-plane bend ν 3 was not observed as it forms an IR-and Raman-inactive local mode phonon.

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A discrete dichloride tetrahydrate cluster, [Cl 2 (H 2 O) 4 ] 2À , was obtained as a salt of the bis(diphenylamino)diethylamino cyclopropenium cation [C 3 (NPh 2 ) 2 (NEt 2 )] + and characterized by single-crystal X-ray diffraction and infrared spectroscopy. This chloride-chloride ion-pair cluster consists of a [Cl 2 (H 2 O) 2 ] 2À square with opposite edges bridged by water molecules to give a chair-like structure of the non-hydrogen atoms. The solid-state structure is essentially the same as the calculated gasphase structure. Infrared spectra were also collected on the deuterium analogue [Cl 2 (D 2 O) 4 ] 2À . Computational studies were carried out on gas-phase [Cl 2 (H 2 O) 4 ] 2À to confirm the infrared band assignments in the solid state. The structure and infrared spectrum are consistent with the discrete nature of the cluster.[a] M.