Thioarsenate anions acting as ligands: Solvothermal syntheses, crystal structures and characterizations of transition metal complexes of thioarsenate and polyethyleneamine ligands
Abstract New members of transition metal complexes with thioarsenate ligands, [Co(peha)[Co(As 3 S 3 2 (peha pentaethylenehexamine) 1 [Co(trien)(AsS 3 2 [Cr(trien)(AsS 3 (trien triethylenetetramine) 3 and [Cr(en) 2 (AsS 3 (en ethylenediamine) 4 were prepared by solvothermal reactions in polyamines. In 1 two As 3 S 3 units coordinate to a Co 2+ ion with both As and S donor atoms in the 1k 2 As 1 ,As 2 :1kS 1 As 3 S 3 coordination mode to form the novel [Co(As 3 S 3 2 2 anionic cluster, in which CoAs 2 CoAs 2 S 2 and CoAs 3 S 2 rings are formed. Another Co 2+ ion is coordinated by a hexadentate peha ligand to form a octahedral [Co(peha) 2+ complex cation. Both Co 3+ and Cr 3+ ions are coordinated by a tetradentate trien ligand and a bidentate chelating ligand [AsS 3 3 and neutral complexes [Co(trien)(AsS 3 2 and [Cr(trien)(AsS 3 3 are formed. The Cr 3+ is coordinated by two en ligands and a bidentate chelating ligand [AsS 3 3 to form neutral complex Cr(en) 2 (AsS 3 4 Complexes 2 4 represent the first examples of TM thioarsenate complexes with polyethyleneamine coligands. Compounds 1 4 are potential semiconductors with narrow well defined optical band gaps in the range of 1.45 1.74 eV. Thermal properties of 1 4 were investigated via thermogravimetric analyses.