ISSN 1990-7931, Russian Journal of Physical Chemistry B, 2013, Vol. 7, No. 6, pp. 717–720. © Pleiades Publishing, Ltd., 2013. Original Russian Text © O.I. Gromov, A.V. Terekhin, A.V. Lobanov, E.N. Golubeva, 2013, published in Khimicheskaya Fizika, 2013, Vol. 32, No. 11, pp. 51–54. 717 1. INTRODUCTION Copper chloride complexes used to catalyze pro- cesses involving chlorinated hydrocarbons, such as the addition of carbon tetrachloride at double bonds (Kharasch reaction) [1], reaction of exchange of a chlo- rine atom in a organochlorine compound for hydrogen of an aliphatic hydrocarbon (C–Cl bond metathesis) [2, 3], isomerization of allyl halides [4], and living radi- cal polymerization [5]. In particular, quaternary ammonium tetrachlorocuprates ([R 4 N] + ) 2 [Cu II Cl 4 ] 2– are precursors of catalysts of one-electron redox reac- tions involving polychlorinated hydrocarbons [6]. The available kinetic data suggest that copper(II) organic compounds may act as intermediates in these reac- tions [7, 8]. Similar organocopper complexes are formed by the photolysis of quaternary ammonium tetrachlorocu- prates [R 4 N + ] 2 [CuC ] (R 4 N + is the cation of tributyl- benzyl- or tetrahexylammonium) in glassy (2-chloro- butane) and crystallizable (chloroform, chlorobenzene) noncomplexing solvents [9]. EPR measurements also show the formation of organic radicals. It was demon- strated that the photolysis produces two new copper complexes, designated by the authors of [10] as 1-Cu and 2-Cu. When the samples were heated to 100–105 K, 2-Cu was found to quantitatively transform into 1-Cu. At these same temperatures, the EPR spectrum of alkyl radicals was observed to disappear. As a result, an individual EPR spectrum of the 1-Cu complex was recorded, which made it possible to reliably determine the parameters of this compound: g 1 = 2.082 ± 0.003, g 2 = 2.033 ± 0.001, g 3 = 2.024 ± 0.001, А( 63 Cu) 1 = (4.1 ± 0.2) mT, А( 63 Cu) 2 = (3.8 ± 0.1) mT, and А( 63 Cu) 3 = (11.0 ± 0.2) mT [11]. Quantum-chemical l 4 2 – calculations showed that this product has the compo- sition CuCl 2 R' [12, 13]. An analysis of the absorption spectra of the photolysis products of (NR 4 ) 2 CuCl 4 in the visible and UV ranges, as well as the results of quantum-chemical calculations, suggested that the second photolysis product has the composition CuCl 3 R' – [13]. The CuCl 3 R' – compound is characterized by the following parameters of the spin Hamiltonian: g 1 = 2.005, g 2 = 2.084, g 3 = 2.112, А( 63 Cu) 1 = 22 mT, А( 63 Cu) 2 = 8 mT, and А( 63 Cu) 3 = 7 mT [14]. The following scheme for the formation and inter- conversion of the photolysis products of quaternary ammonium tetrachlorocuprates was proposed [13, 15]: where R = –C 6 H 13 , R' = (–C 6 H 12 )N + (C 6 H 13 ); in a frozen solvent matrix, CuCl 3 R' – and CuCl 2 R' are lost at 100 and 110 K, respectively. The aim of the present work was to extend the tem- perature and concentration ranges of the existence of the photolysis products by reducing their diffusion mobility by means of attaching to an Aerosil surface in order to obtain additional data on the stability and reactivity of these compounds. 2 NR CuCl NR R' CuCl HCl, 2 2 4 4 4 3 * ( ) ( )( ) + - + - → + 3 NR R' CuCl NR CuCl R 2 4 3 4 ' ( )( ) ( ) , + - + -   →   [ ] 3 2 NR CuCl R CuCl R' NR Cl 4 4 ' ( ) ( ) , + - + -   → +   [ ] 2 CuCl R' R' R' R' CuCl 2 , - + → - + [ ] 2 2 CuCl R' R' R' 2CuCl 2 , - → - + Photochemical Transformations of Quaternary Ammonium Tetrachlorocuprates on an Aerosil Surface O. I. Gromov*, A. V. Terekhin, A. V. Lobanov, and E. N. Golubeva Faculty of Chemistry, Moscow State University, Moscow, Russia *e-mail: aalchm@gmail.ru Received January 15, 2013 Abstract—EPR measurements show that the products of photolysis of quaternary ammonium tetrachloro- cuprates with 405-nm light in a solvent frozen at 77 K and on an aerosil surface are identical. As compared to matrix isolation at low temperature, immobilization on an aerosil surface makes it possible to extend the tem- perature range of existence of copper(II) organic products of photolysis by at least 50 K. Keywords: EPR, photolysis products of quaternary ammonium tetrachlorocuprates, light wavelength, aerosil DOI: 10.1134/S1990793113060031 STRUCTURE OF CHEMICAL COMPOUNDS. SPECTROSCOPY