Departamento de Química Inorgánica, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Ciudad Universitaria, E-28040 Madrid, Spain.
Dalton Trans. 2014 Feb 28;43(8):3227-37. doi: 10.1039/c3dt52727a.
The first bromo and iodo tetraamidatodiruthenium compounds of the type [Ru2X(μ-NHOCC6H4-R)4]n [X = Br, R = o-Me (1), m-Me (2), p-Me (3); X = I, R = o-Me (4), m-Me (5), p-Me (6)] have been prepared using solvothermal or microwave activation procedures. In these reactions ethanol or methanol as solvents have been used to make the synthesis procedures more environment-friendly. Solvothermal synthesis has allowed us to isolate single crystals of these extremely insoluble compounds and the crystal structures of all of them have been determined using single crystal X-ray diffraction. The change of the bridging halide ligand permits us to discuss the properties of these complexes on the basis of their structure. Complex 1 shows a Ru-Br-Ru angle of 180.0° whereas in complexes 2-6 the Ru-X-Ru angle varies from 110.16(2) to 115.39(4)°. In all compounds the ruthenium atom has a cis-RuN2O2 environment except in compound 1 that shows a positional disorder of N and O atoms. The bromide complex 1 shows a linear arrangement of the paddlewheel units in the resulting 1D coordination polymer. The fit of the magnetic data indicates that these compounds have non-negligible values of zero-field splitting with D values ranging from 41.10 to 60.10 cm(-1) and antiferromagnetic coupling constants from 0.00 to -4.13 cm(-1). Compound 1 is the first linear paddlewheel diruthenium compound that does not show a maximum in the representation of the magnetic susceptibility towards temperature. The electrical conductivity measurements in the temperature range 300-400 K of compounds 1, 4 and [Ru2Cl(μ-NHOCC6H4-o-Me)4]n (7) show that these compounds present semiconducting behaviours with conductivity values at 400 K in the range 0.3-3.0 × 10(-8) S cm(-1) for the Cl derivative (7), 7-18 × 10(-8) S cm(-1) for the Br derivative (1) and 27-68 × 10(-8) S cm(-1) for the I derivative (4) with average values of 1.4 × 10(-8), 13 × 10(-8) and 47 × 10(-8) S cm(-1), respectively.
第一组溴和碘四氨合二钌化合物[Ru2X(μ-NHOCC6H4-R)4]n（X=Br，R=邻-甲基（1），间-甲基（2），对-甲基（3）；X=I，R=邻-甲基（4），间-甲基（5），对-甲基（6））已通过溶剂热或微波激活程序制备。在这些反应中，乙醇或甲醇被用作溶剂，以使合成过程更加环保。溶剂热合成使我们能够分离出这些极难溶化合物的单晶，并使用单晶 X 射线衍射确定了它们的晶体结构。桥连卤化物配体的变化允许我们根据它们的结构讨论这些配合物的性质。配合物 1 显示 Ru-Br-Ru 角为 180.0°，而在配合物 2-6 中，Ru-X-Ru 角从 110.16(2)变化到 115.39(4)°。在所有化合物中，钌原子具有 cis-RuN2O2 环境，除了配合物 1 中存在 N 和 O 原子的位置无序。溴化物配合物 1 显示出桨轮单元在所得 1D 配位聚合物中的线性排列。磁性数据的拟合表明，这些化合物具有不可忽略的零场分裂值，D 值范围为 41.10 至 60.10 cm(-1)，反铁磁耦合常数范围为 0.00 至-4.13 cm(-1)。配合物 1 是第一个不显示温度下磁敏度最大值的线性桨轮二钌化合物。在 300-400 K 温度范围内对化合物 1、4 和[Ru2Cl(μ-NHOCC6H4-o-Me)4]n（7）进行的电导率测量表明，这些化合物具有半导体行为，在 400 K 时，Cl 衍生物（7）的电导率值在 0.3-3.0×10(-8) S cm(-1)范围内，Br 衍生物（1）的电导率值在 7-18×10(-8) S cm(-1)范围内，I 衍生物（4）的电导率值在 27-68×10(-8) S cm(-1)范围内，平均值分别为 1.4×10(-8)、13×10(-8)和 47×10(-8) S cm(-1)。
