title: Photochemistry of dithiocarbamate Cu(II) complex in CCl4.
abstract: Laser pulse photolysis was used to study the nature and reactions of intermediates in the photochemistry of the flat dithiocarbamate complex Cu(Et(2)dtc)(2) in CCl(4). A nanosecond laser pulse (355 nm) is shown to induce intermediate absorption bands of bivalent copper complex whose coordination sphere contains a dithiocarbamate radical Et(2)dtc(•) and a chloride ion at the axial position ([(Et(2)dtc)Cu(Et(2)dtc(•))Cl(a)]). At room temperature during some microseconds after the laser pulse, this intermediate interacts with the initial complex to form presumably a dimer [Cu(2)(Et(2)dtc)(3)(Et(2)dtc(•))Cl]. The latter vanishes in the second-order reaction. Analysis of kinetic and spectral features gives the arguments for the formation of a cluster [Cu(2)(Et(2)dtc)(3)Cl-tds-Cu(2)(Et(2)dtc)(3)Cl], which produces a new absorption band at 345 nm. The cluster decomposes in ∼5 ms into final products, a binuclear complex [Cu(2)(Et(2)dtc)(3)Cl] and tetraethylthiuramdisulfide (Et(4)tds).
authors.affiliation: Institute of Chemical Kinetics and Combustion SB RAS, 630090 Novosibirsk, Russia. plyusnin@kinetics.nsc.ru
authors.forename: Victor F
authors.initials: VF
authors.lastname: Plyusnin
authors.forename: Alexandr V
authors.initials: AV
authors.lastname: Kolomeets
authors.forename: Vyacheslav P
authors.initials: VP
authors.lastname: Grivin
authors.forename: Stanislav V
authors.initials: SV
authors.lastname: Larionov
authors.forename: Helge
authors.initials: H
authors.lastname: Lemmetyinen
mesh_terms: D002251:Carbon Tetrachloride / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D004220:Disulfides / Q000737:chemistry; D007700:Kinetics; D007834:Lasers; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D010782:Photolysis; D012996:Solutions
chemical_list: D004220:Disulfides; D009942:Organometallic Compounds; D012996:Solutions; D003300:Copper; D002251:Carbon Tetrachloride