A combined experimental and theoretical approach has been used to study intermolecular chalcogen bonding. Specifically, the chalcogen bonding occurring between halide anions and CS2 molecules has been investigated using both anion photoelectron spectroscopy and high‐level CCSD(T) calculations. The relative strength of the chalcogen bond has been determined computationally using the complex dissociation energies as well as experimentally using the electron stabilisation energies. The anion complexes featured dissociation energies on the order of 47 kJ/mol to 37 kJ/mol, decreasing with increasing halide size. Additionally, the corresponding neutral complexes have been examined computationally, and show three loosely‐bound structural motifs and a molecular radical.
The anion photoelectron spectra of Cl−⋅⋅⋅CD3CDO, Cl−⋅⋅⋅(CD3CDO)2, Br−⋅⋅⋅CH3CHO, and I−⋅⋅⋅CH3CHO are presented with electron stabilisation energies of 0.55, 0.93, 0.48, and 0.40 eV, respectively. Optimised geometries of the singly solvated species featured the halide appended to the CH3CHO molecule in‐line with the electropositive portion of the C=O bond and having binding energies between 45 and 52 kJ mol−1. The doubly solvated Cl−⋅⋅⋅(CH3CHO)2 species features asymmetric solvation upon the addition of a second CH3CHO molecule. Theoretical detachment energies were found to be in excellent agreement with experiment, with comparisons drawn between other halide complexes with simple carbonyl molecules.
Halide-formic acid complexes have been studied utilising a combined experimental and theoretical approach. Formic acid exists as two conformers, distinguished by the relative rotation about the C-OH bond. Computational investigation...
The Cover Feature shows an archetypal chalcogen bond stabilising the dimer complex between carbon disulfide and a halide anion (artwork: Christian and Elham Haakansson). Laser light is utilised to detach electrons from the complex in order to discern chalcogen binding energy in combination with high‐level ab initio calculations. More information can be found in the Communication by Duncan A. Wild and co‐workers.
Mass spectrometry and anion photoelectron spectroscopy have been used to study the gas-phase S N 2 reaction involving Br À and CH 3 I. The anion photoelectron spectra associated with the reaction intermediates of this S N 2 reaction are presented. Highlevel CCSD(T) calculations have been utilised to investigate the reaction intermediates that may form as a result of the S N 2 reaction along various different reaction pathways, including back-side attack and front-side attack. In addition, simulated vertical detachment energies of each reaction intermediate have been calculated to rationalise the photoelectron spectra.
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