Sousa-Pedrares Antonio, Durán María Luz, García-Vázquez José Arturo, Romero Jaime, Sousa Antonio, Real José A
Departamento de Química Inorgánica, Universidad de Santiago de Compostela, 15782 Santiago de Compostela, Spain.
Inorg Chem. 2009 May 4;48(9):4031-43. doi: 10.1021/ic8019099.
The reactions of [Cu(R-pySe)], R = H, 3-CF(3), with 2,2'-bipyridine or 1,10-phenanthroline in acetonitrile yielded the one-dimensional complexes {[Cu(SeO(3))(phen)] x 2 (H(2)O)}(n), 1, {[Cu(SeO(3))(bipy)] x 2 (H(2)O)}(n), 2. Recrystallization of 1 and 2 from a 1:1 methanol/water mixture led to the formation of the dinuclear complexes Cu(SeO(3))(phen)(H(2)O), 3, and Cu(SeO(3))(bipy)(H(2)O), 4. Single crystal X-ray diffraction analysis revealed that 1 and 2 have a polymeric structure in which each oxygen atom of the selenite group coordinates to a copper atom. The two other coordination positions are occupied by two nitrogen atoms of the organic ligand, and this defines an almost square pyramidal geometry around the metal. Both compounds show a very weak antiferromagnetic coupling (J = -0.9 for 1 and -0.6 cm(-1) for 2). Compounds 3 and 4 consist of dinuclear species with the copper atoms lying in a square pyramidal geometry in which the selenite group acts as a bridge between two copper atoms and one oxygen atom is uncoordinated. The two copper ions in 3 show antiferromagnetic coupling with J = -22.1 cm(-1).
[Cu(R - pySe)]（R = H，3 - CF(3)）与2,2'-联吡啶或1,10 - 菲咯啉在乙腈中的反应生成了一维配合物{[Cu(SeO(3))(phen)]·2(H(2)O)}n，1，{[Cu(SeO(3))(bipy)]·2(H(2)O)}n，2。1和2从甲醇/水1:1混合物中重结晶导致形成双核配合物[Cu(SeO(3))(phen)(H(2)O)]2，3，和[Cu(SeO(3))(bipy)(H(2)O)]2，4。单晶X射线衍射分析表明1和2具有聚合物结构，其中亚硒酸根基团的每个氧原子与一个铜原子配位。另外两个配位位置由有机配体的两个氮原子占据，这定义了金属周围几乎为四方锥的几何构型。两种化合物都表现出非常弱的反铁磁耦合（1的J = -0.9，2的J = -0.6 cm(-1)）。化合物3和4由双核物种组成，铜原子呈四方锥几何构型，其中亚硒酸根基团作为两个铜原子之间的桥，且有一个氧原子未配位。3中的两个铜离子表现出反铁磁耦合，J = -22.1 cm(-1)。
