Kadish Karl M, Nguyen Minh, Van Caemelbecke Eric, Bear John L
Department of Chemistry, University of Houston, Houston, TX 77204-5003, USA.
Inorg Chem. 2006 Jul 24;45(15):5996-6003. doi: 10.1021/ic060267k.
Reaction of the metal-metal bonded complex Ru(2)(O2CCH3)4Cl with 2-anilino-4-methylpyridine leads to the (3,1) isomer of the diruthenium(III,II) complex Ru2(ap-4-Me)4Cl, 1 while the same reaction with 2-anilino-6-methylpyridine gives the monoruthenium(III) derivative Ru(ap-6-Me)3, 2. Both compounds were examined as to their structural, electrochemical, and UV-visible properties, and the data were then compared to that previously reported for (4,0) Ru2(2-Meap)4Cl and other (3,1) isomers of Ru2(L)4Cl with similar anionic bridging ligands. ESR spectroscopy indicates that the monoruthenium derivative 2 contains low-spin Ru(III), and the presence of a single ruthenium atom is confirmed by an X-ray structure of the compound. The combined electrochemical and UV-vis spectroelectrochemical data indicate that the diruthenium complex 1 is easily converted to its Ru2(4+) and Ru2(6+) forms upon reduction or oxidation by one electron while the monoruthenium derivative 2 also undergoes metal-centered redox processes to give Ru(II) and Ru(IV) complexes under the same solution conditions. The reactivity of 1 with CO and CN- was also examined.
金属-金属键合配合物Ru₂(O₂CCH₃)₄Cl与2-苯胺基-4-甲基吡啶反应生成二钌(III,II)配合物Ru₂(ap-4-Me)₄Cl的(3,1)异构体1，而与2-苯胺基-6-甲基吡啶的相同反应得到单钌(III)衍生物Ru(ap-6-Me)₃，即2。对这两种化合物的结构、电化学和紫外-可见性质进行了研究，然后将数据与先前报道的(4,0) Ru₂(2-Meap)₄Cl以及具有类似阴离子桥连配体的Ru₂(L)₄Cl的其他(3,1)异构体的数据进行了比较。电子顺磁共振光谱表明单钌衍生物2含有低自旋Ru(III)，并且通过该化合物的X射线结构证实了单个钌原子的存在。电化学和紫外-可见光谱电化学数据相结合表明，二钌配合物1在通过一个电子还原或氧化时很容易转化为其Ru₂(4+)和Ru₂(6+)形式，而单钌衍生物2在相同的溶液条件下也经历以金属为中心的氧化还原过程，生成Ru(II)和Ru(IV)配合物。还研究了1与CO和CN⁻的反应活性。
