title: Photochemistry of Dithiocarbamate Cu(S2CNEt2)2Complex in CHCl3. Transient Species and TD-DFT Calculations.
abstract: Nanosecond laser flash photolysis was used to study the mechanism of photochemical transformations of the diethyldithiocarbamate Cu(II) complex (Cu(dtc)2, where dtc-≡-S2CNEt2anion) in chloroform solutions. The electron transfer from the excited Cu(dtc)2complex to a solvent molecule leads to the appearance of the primary intermediate, the [ClCu(dtc)(dtcCHCl2)] complex, where a dtcCHCl2molecule is coordinated with a copper ion via one sulfur atom. In the fast reaction (k = 2.1 × 109M-1s-1) with Cu(dtc)2, this complex forms a long-lived dimer [ClCu(dtc)(dtcCHCl2)Cu(dtc)2]. This intermediate decays during several seconds (k = 5.6 × 10-2s-1) into the final product, i.e., a diamagnetic dimer [ClCu(dtc)Cu(dtc)2]. To determine the structure of intermediate complexes the quantum chemical calculations were carried out using DFT, TD-DFT, and PCM (Polarizable Continuum Model) methods.
authors.affiliation: Voevodsky Institute of Chemical Kinetics and Combustion SB RAS , 630090 Novosibirsk, Russia.|Novosibirsk State University , 630090 Novosibirsk, Russia.
authors.forename: Aleksey I
authors.initials: AI
authors.lastname: Solovyev
authors.affiliation: Voevodsky Institute of Chemical Kinetics and Combustion SB RAS , 630090 Novosibirsk, Russia.|Novosibirsk State University , 630090 Novosibirsk, Russia.
authors.forename: Victor F
authors.initials: VF
authors.lastname: Plyusnin
authors.affiliation: Novosibirsk State University , 630090 Novosibirsk, Russia.|Boreskov Institute of Catalysis SB RAS , 630090 Novosibirsk, Russia.
authors.forename: Aleksandr A
authors.initials: AA
authors.lastname: Shubin
authors.affiliation: Voevodsky Institute of Chemical Kinetics and Combustion SB RAS , 630090 Novosibirsk, Russia.
authors.forename: Vjacheslav P
authors.initials: VP
authors.lastname: Grivin
authors.affiliation: Novosibirsk State University , 630090 Novosibirsk, Russia.|Nikolaev Institute of Inorganic Chemistry SB RAS , 630090 Novosibirsk, Russia.
authors.forename: Stanislav V
authors.initials: SV
authors.lastname: Larionov