New polyselenidoarsenate salts with transition metal complexes as counterions: solvothermal synthesis, crystal structures, and properties of [M(dien)(2)]As2Se6 (M = Co, Ni) and [Mn(dap)(3)]As2Se6

作者：Zhao, Jing; Liang, Jingjing; Pan, Yingli; Zhang, Yong; Jia, Dingxian^*

来源：Monatshefte fur Chemie, 2011, 142(12): 1203-1209.

DOI：10.1007/s00706-011-0561-z

• Chalcogenides
• Metal complexes
• Solvothermal synthesis
• X-ray structure determination

New polyselenidoarsenates [Co(dien)(2)]As2Se6, [Ni(dien)(2)]As2Se6 (dien = diethylenetriamine), and [Mn(dap)(3)]As2Se6 (dap = 1,2-diaminopropane) were synthesized by the reaction of As2O3, Se, and transition metal chloride in dien or dap solvent under solvothermal conditions. The compounds consist of a polyselenidoarsenate anion [As2Se6](2-) and an octahedral complex cation [M(dien)(2)](2+) (M = Co, Ni) or [Mn(dap)(3)](2+). Two trigonal-pyramidal AsSe3 units are joined through two Se-Se bonds forming the dimeric [As2Se6](2-) anion with a six-membered ring As2Se4 in chair conformation. In the crystal structures the anion and cations are connected into extended structures via weak N-H center dot center dot center dot Se hydrogen bonds. Thermogravimetric analyses show that the dien-containing compounds decompose in one step under nitrogen stream, whereas the Mn compound exhibits a two-step decomposition process.

• 出版日期2011-12
• 单位苏州大学