ABSTRACT
The solid-state structure of a discrete chloride monohydrate species, [Cl(H2O)]-, 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 D2O and HDO isotopomers were investigated. Of the six fundamental vibrational modes, only the out-of-plane bend ν3 was not observed as it forms an IR- and Raman-inactive local mode phonon.
ABSTRACT
A discrete dichloride tetrahydrate cluster, [Cl2 (H2 O)4 ]2- , was obtained as a salt of the bis(diphenylamino)diethylamino cyclopropenium cation [C3 (NPh2 )2 (NEt2 )]+ and characterized by single-crystal X-ray diffraction and infrared spectroscopy. This chloride-chloride ion-pair cluster consists of a [Cl2 (H2 O)2 ]2- 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 gas-phase structure. Infrared spectra were also collected on the deuterium analogue [Cl2 (D2 O)4 ]2- . Computational studies were carried out on gas-phase [Cl2 (H2 O)4 ]2- to confirm the infrared band assignments in the solid state. The structure and infrared spectrum are consistent with the discrete nature of the cluster.
ABSTRACT
A series of five ternary octanuclear iodine-bromine-chlorine interhalides, [I2 Br2 Cl4 ]2- (1), [I3 BrCl4 ]2- (2), [I4 Br2 Cl2 ]2- (3), [I2 Br4 Cl2 ]2- (4) and [I3 Br3 Cl2 ]2- (5), have been rationally constructed in two steps. Firstly, addition of a dihalogen (ICl or IBr) to the triaminocyclopropenium chloride salt [C3 (NEt2 )3 ]Cl forms the corresponding trihalide salt with [ICl2 ]- or [BrICl]- anions, respectively. Secondly, addition of a half-equivalent of a second dihalogen, followed by crystallization at low temperature, gives the corresponding octahalide: addition of Br2 and IBr to [ICl2 ]- gives 1 and 2, respectively, whereas addition of I2 , Br2 and IBr to [BrICl]- gives 3, 4 and 5, respectively. The five octahalides were characterized by X-ray crystallography and far-IR spectroscopy.
ABSTRACT
A series of octanuclear iodine-bromine interhalides [In Br8-n ]2- (n=0, 2, 3, 4) were prepared systematically in two steps. Firstly, addition of a dihalogen (Br2 or IBr) to the triaminocyclopropenium bromide salt [C3 (NEt2 )3 ]Br forms the corresponding trihalide salt with Br3 - or IBr2 - anions, respectively. Secondly, addition to Br3 - of half an equivalent of Br2 gives the octabromine polyhalide [Br8 ]2- , whereas addition to IBr2 - of half an equivalent of Br2 , IBr or I2 gives the corresponding interhalides: [I2 Br6 ]2- , [I3 Br5 ]2- , and [I4 Br4 ]2- , respectively. The four octahalides were characterized by X-ray crystallography, computational studies, Raman and Far-IR spectroscopies, as well as by TGA and melting point. All of the salts were found to be ionic liquids.
ABSTRACT
The octanuclear iodine-chlorine interhalides [I4 Cl4 ]2- and [I3 Cl5 ]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 [I3.6 Cl4.4 ]2- was obtained after heating a CH2 Cl2 solution of the ICl2 - salt to reflux for 2â hours followed crystallization. [I4 Cl4 ]2- is best described as two ICl2 - anions bridged by I2 , whereas [I3 Cl5 ]2- is best described as an [I2 Cl3 ]- 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.
