1 research outputs found
Photochemistry of Dithiocarbamate Cu(S<sub>2</sub>CNEt<sub>2</sub>)<sub>2</sub> Complex in CHCl<sub>3</sub>. Transient Species and TD-DFT Calculations
Nanosecond laser
flash photolysis was used to study the mechanism
of photochemical transformations of the diethyldithiocarbamate CuÂ(II)
complex (CuÂ(dtc)<sub>2</sub>, where dtc<sup>–</sup> ≡ <sup>–</sup>S<sub>2</sub>CNEt<sub>2</sub> anion) in chloroform
solutions. The electron transfer from the excited CuÂ(dtc)<sub>2</sub> complex to a solvent molecule leads to the appearance of the primary
intermediate, the [ClCuÂ(dtc)Â(dtcCHCl<sub>2</sub>)] complex, where
a dtcCHCl<sub>2</sub> molecule is coordinated with a copper ion via
one sulfur atom. In the fast reaction (<i>k</i> = 2.1 ×
10<sup>9</sup> M<sup>–1</sup> s<sup>–1</sup>) with CuÂ(dtc)<sub>2</sub>, this complex forms a long-lived dimer [ClCuÂ(dtc)Â(dtcCHCl<sub>2</sub>)ÂCuÂ(dtc)<sub>2</sub>]. This intermediate decays during several
seconds (<i>k</i> = 5.6 × 10<sup>–2</sup> s<sup>–1</sup>) into the final product, i.e., a diamagnetic dimer
[ClCuÂ(dtc)ÂCuÂ(dtc)<sub>2</sub>]. To determine the structure of intermediate
complexes the quantum chemical calculations were carried out using
DFT, TD-DFT, and PCM (Polarizable Continuum Model) methods