A theoretical investigation of the structure of (Cl2F)+ and protonated ClF

Elemental Chlorine and Chlorine Fluoride: Theoretical and Experimental Proton Affinity and the Gas Phase Chemistry of Cl2H + and FClH+ Ions

“…For protonated chlorine fluoride both [ClFH] + and [FClH] + are minima, the latter one being the global minimum, whereas the [FHCl] + structure converges to the [FClH] + one. The only previous theoretical analysis of the [H, F, Cl] + system is an ab initio study performed in 1979 in the framework of the restricted Hartree−Fock theory utilizing the 4-31G basis set . Its results differ from ours in that the stability order of protomers FClH + and ClFH + is reversed, the latter ion being found to be more stable than the former one by ca.…”

“…For the protonation of Cl 2 we considered as starting geometries both a [ClClH] + structure with the proton interacting only with one chlorine atom and a [ClHCl] + structure with the proton 6 Its results differ from ours in that the stability order of protomers FClH + and ClFH + is reversed, the latter ion being found to be more stable than the former one by ca. 36 kcal mol -1 .…”

“…The higher basicity of Cl than of F in halogen and interhalogen molecules, a trend hardly surprising on intuitive grounds, but not always supported by theoretical results, 6 is consistent with the basicity order F 2 , ClF < Cl 2 , defined by the PA scale: F 2 , 79, 22 ClF, 121.0; Cl 2 , 131.4 kcal mol -1 , whose most salient feature is the remarkably large ∆PA increase, over 40 kcal mol -1 , following replacement of one of the F atoms of the F 2 molecule with a Cl atom.…”

Gaseous Trihalogen Cations. Formation, Structure and Reactivity of Cl3+ and Cl2F+ Ions from a Joint ab Initio and FT-ICR Study

“…Decades of experimental and theoretical work have yielded a rich harvest of information on homo- and hetero-trihalogen cations, in particular Cl 3 + and Cl 2 F + , whose interest stems, inter alia, from their role in electrophilic halogenation. − The structure of Cl 2 F + has been the focus of a lively controversy fueled by conflicting evidence on the relative stability of the [Cl−Cl−F] + and [Cl−F−Cl] + isomers. − The Cl 3 + and Cl 2 F + cations have been characterized in the solid state by the spectroscopic study of their AsF 6 - salts, but are unstable in solution, even in superacid media. , In striking contrast with the wealth of information gathered in condensed phases, very little is known on gaseous trihalogen cations, except for the detection of Cl 3 + as a secondary, unreactive product reported in a study on the reactions of rare gas ions with Cl 2…”

Gaseous Cl3+ and Cl2F+ cations. a joint mass spectrometric and theoretical study

“…236 kcal mol À1 for H°f (Cl 3 ). The Cl 2 F ion (2) has been the subject of a lively controversy concerning the relative stability of its isomeric forms, [Cl-Cl-F] and [Cl-F-Cl] 3,4,[9][10][11] In general, the Cl 2 F ion has been thought of as the product from the interaction between ClF and Cl , because ClF and AsF 5 (or BF 3 ) were used for the synthesis of its salts. 3,4 This investigation prepared Cl 2 F by the reaction of Cl 2 /XeF 2 in CI mode, according to the oxidative fluorination process XeF Cl 2 À3Xe 2 3…”