Friedel-Crafts Type Methylation with Dimethylhalonium Salts

The dimethylchloronium salt [Me2Cl][Al(OTeF5)(4)] is used to methylate electron-deficient aromatic systems in Friedel-Crafts type reactions as shown by the synthesis ofN-methylated cations, such as [MeNC5F5](+), [MeNC5F4I](+), and [MeN3C3F3](+). To gain a better understanding of such fundamental Friedel-Crafts reactions, the role of the dimethylchloronium cation has been evaluated by quantum-chemical calculations

(Noble Gas)n-NC+ Molecular Ions in Noble Gas Matrices: Matrix Infrared Spectra and Electronic Structure Calculations

An investigation of pulsed-laser-ablated Zn, Cd and Hg metal atom reactions with HCN under excess argon during co-deposition with laser-ablated Hg atoms from a dental amalgam target also provided Hg emissions capable of photoionization of the CN photo-dissociation product. A new band at 1933.4 cm−1 in the region of the CN and CN+ gas-phase fundamental absorptions that appeared upon annealing the matrix to 20 K after sample deposition, and disappeared upon UV photolysis is assigned to (Ar)nCN+, our key finding. It is not possible to determine the n coefficient exactly, but structure calculations suggest that one, two, three or four argon atoms can solvate the CN+ cation in an argon matrix with C−N absorptions calculated (B3LYP) to be between 2317.2 and 2319.8 cm−1. Similar bands were observed in solid krypton at 1920.5, in solid xenon at 1935.4 and in solid neon at 1947.8 cm−1. H13CN reagent gave an 1892.3 absorption with shift instead, and a 12/13 isotopic frequency ratio–nearly the same as found for 13CN+ itself in the gas phase and in the argon matrix. The CN+ molecular ion serves as a useful infrared probe to examine Ng clusters. The following ion reactions are believed to occur here: the first step upon sample deposition is assisted by a focused pulsed YAG laser, and the second step occurs on sample annealing: (Ar)2++CN→Ar+CN+→(Ar)nCN+

Novel synthetic pathway for the production of phosgene

Chloride ions are efficient catalysts for the synthesis of phosgene from carbon monoxide and elemental chlorine at room temperature and atmospheric pressure. Control experiments rule out a radical mechanism and highlight the role of triethylmethylammonium trichloride, [NEt3Me][Cl3], as active species. In the catalytic reaction, commercially available [NEt3Me]Cl reacts with Cl2 to form [NEt3Me][Cl3], enabling the insertion of CO into an activated Cl─Cl bond with a calculated energy barrier of 56.9 to 77.6 kJ mol−1. As [NEt3Me]Cl is also a useful chlorine storage medium, it could serve as a catalyst for phosgene production and as chlorine storage in a combined industrial process