Barral M Carmen, Gallo Teresa, Herrero Santiago, Jiménez-Aparicio Reyes, Torres M Rosario, Urbanos Francisco A
Departamento de Química Inorgánica, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Ciudad Universitaria, 28040 Madrid, Spain.
Chemistry. 2007;13(36):10088-95. doi: 10.1002/chem.200700494.
The reaction of [Ru(2)Cl(O(2)CMe)(DPhF)(3)] (DPhF=N,N'-diphenylformamidinate) with aqueous HCl leads to the substitution of the acetate ligand to give the complex [Ru(2)Cl(2)(DPhF)(3)] (1). Similar reaction of [Ru(2)(O(2)CMe)(DPhF)(3)(H(2)O)]BF(4) with aqueous HBr or HI produces [Ru(2)Br(2)(DPhF)(3)] (2), and [Ru(2)I(2)(DPhF)(3)] (3), respectively. The reaction of 1 with AgBF(4) to form the highly unsaturated unit Ru(2)(DPhF)(3), which is isolated as [Ru(2)(BF(4))(DPhF)(3)(H(2)O)]BF(4) (4), and Ru(2)(MeCN)(2)(DPhF)(3)(2) (5), is also reported. The use of AgNO(3) instead of AgBF(4) leads to [Ru(2)(NO(3))(2)(DPhF)(3)] (6). The magnetic behaviour of complexes 1-4 and 6 is intermediate between high- and low-spin configurations. A relationship between the magnetic behaviour and the visible-near-infrared (Vis-NIR) spectra is apparent. In addition, the crystal structure determinations of 2, 4.THF, and 6, have been carried out. Complexes 1-3, 5 and 6 are the first examples of open-paddlewheel structures in diruthenium chemistry. The BF(4) (-) bridging the metal centres in 4THF is activated and forms very short Ru-F bonds.
[Ru₂Cl(O₂CMe)(DPhF)₃]（DPhF = N,N'-二苯基甲脒）与盐酸水溶液反应会导致乙酸根配体被取代，生成配合物[Ru₂Cl₂(DPhF)₃]（1）。[Ru₂(O₂CMe)(DPhF)₃(H₂O)]BF₄与氢溴酸或氢碘酸水溶液发生类似反应，分别生成[Ru₂Br₂(DPhF)₃]（2）和[Ru₂I₂(DPhF)₃]（3）。还报道了1与AgBF₄反应形成高度不饱和单元[Ru₂(DPhF)₃]²⁺，该单元以[Ru₂(BF₄)(DPhF)₃(H₂O)]BF₄（4）和Ru₂(MeCN)₂(DPhF)₃₂（5）的形式被分离出来。使用AgNO₃代替AgBF₄会生成[Ru₂(NO₃)₂(DPhF)₃]（6）。配合物1 - 4和6的磁行为介于高自旋和低自旋构型之间。磁行为与可见 - 近红外（Vis - NIR）光谱之间存在明显的关系。此外，还对2、4·THF和6进行了晶体结构测定。配合物1 - 3、5和6是二钌化学中开桨轮结构的首个实例。在4·THF中桥接金属中心的BF₄⁻被活化并形成非常短的Ru - F键。
