The coordination structure of cupric tartrate(Cu−TA)complex was investigated by ultraviolet−visible(UV-Vis)and liquid chromatography/mass spectrometer(LC-MS)firstly;furthermore,effective coordination configurations an...The coordination structure of cupric tartrate(Cu−TA)complex was investigated by ultraviolet−visible(UV-Vis)and liquid chromatography/mass spectrometer(LC-MS)firstly;furthermore,effective coordination configurations and electronic properties of Cu−TA in aqueous solution were systematically revealed by density functional theory(DFT)calculations.Consistently,Job plots show the possible existence of[Cu(TA)]and[Cu(TA)_(2)]^(2-)at 230 and 255 nm based on UV-Vis results.LC-MS results confirm the existence of the single and high coordination complexes[Cu_(2)(TA)_(2)]^(+),[Cu(TA)_(2)]^(+)and[Cu_(2)(TA)_(3)(H_(2)O)_(2)(OH)_(2)]^(2+).DFT calculation results show that carboxylic oxygen and hydroxyl oxygen of tartaric acid(TA)are preferred sites for Cu(Ⅱ)coordination.[Cu(TA)](1H,3H sites O of TA coordinated with Cu(Ⅱ)),[Cu(TA)_(2)]^(2-)(two 1^(C),2^(H) sites O of TA coordinated with Cu(Ⅱ)),and[Cu(TA)_(3)]^(4-)(three 2H,3H sites O of TA coordinated with Cu(Ⅱ))should be dominant coordination configurations of Cu−TA.The corresponding Gibbs reaction energies are-170.1,-136.2,and-90.2 kJ/mol,respectively.展开更多
基金the National Key Research and Development Program of China(No.2019YFC0408303)the Natural Science Foundation of Hunan Province,China(No.2021JJ20069)+2 种基金the Changsha Science and Technology Project,China(Nos.kq2106016,kq2009005)Higher Education Discipline Innovation Project(111 Project),China(No.B14034)the Fundamental Research Funds for the Central Universities of Central South University,China(No.2021zzts0887).
文摘The coordination structure of cupric tartrate(Cu−TA)complex was investigated by ultraviolet−visible(UV-Vis)and liquid chromatography/mass spectrometer(LC-MS)firstly;furthermore,effective coordination configurations and electronic properties of Cu−TA in aqueous solution were systematically revealed by density functional theory(DFT)calculations.Consistently,Job plots show the possible existence of[Cu(TA)]and[Cu(TA)_(2)]^(2-)at 230 and 255 nm based on UV-Vis results.LC-MS results confirm the existence of the single and high coordination complexes[Cu_(2)(TA)_(2)]^(+),[Cu(TA)_(2)]^(+)and[Cu_(2)(TA)_(3)(H_(2)O)_(2)(OH)_(2)]^(2+).DFT calculation results show that carboxylic oxygen and hydroxyl oxygen of tartaric acid(TA)are preferred sites for Cu(Ⅱ)coordination.[Cu(TA)](1H,3H sites O of TA coordinated with Cu(Ⅱ)),[Cu(TA)_(2)]^(2-)(two 1^(C),2^(H) sites O of TA coordinated with Cu(Ⅱ)),and[Cu(TA)_(3)]^(4-)(three 2H,3H sites O of TA coordinated with Cu(Ⅱ))should be dominant coordination configurations of Cu−TA.The corresponding Gibbs reaction energies are-170.1,-136.2,and-90.2 kJ/mol,respectively.
