Photochemistry of Dithiocarbamate Cu(II) Complex in CCl4

详细信息    查看全文

• 作者：Victor F. Plyusnin ; Alexandr V. Kolomeets ; Vyacheslav P. Grivin ; Stanislav V. Larionov ; Helge Lemmetyinen
• 刊名：Journal of Physical Chemistry A
• 出版年：2011
• 出版时间：March 17, 2011
• 年：2011
• 卷：115
• 期：10
• 页码：1763-1773
• 全文大小：1133K
• 年卷期：v.115,no.10(March 17, 2011)
• ISSN：1520-5215

文摘

Laser pulse photolysis was used to study the nature and reactions of intermediates in the photochemistry of the flat dithiocarbamate complex Cu(Et₂dtc)₂ in CCl₄. A nanosecond laser pulse (355 nm) is shown to induce intermediate absorption bands of bivalent copper complex whose coordination sphere contains a dithiocarbamate radical Et₂dtc^{鈥?/sup> and a chloride ion at the axial position ([(Et₂dtc)Cu(Et₂dtc鈥?/sup>)Cl_a]). At room temperature during some microseconds after the laser pulse, this intermediate interacts with the initial complex to form presumably a dimer [Cu₂(Et₂dtc)₃(Et₂dtc鈥?/sup>)Cl]. The latter vanishes in the second-order reaction. Analysis of kinetic and spectral features gives the arguments for the formation of a cluster [Cu₂(Et₂dtc)₃Cl-tds-Cu₂(Et₂dtc)₃Cl], which produces a new absorption band at 345 nm. The cluster decomposes in 5 ms into final products, a binuclear complex [Cu₂(Et₂dtc)₃Cl] and tetraethylthiuramdisulfide (Et₄tds).}