一种混合价态钌配合物的合成、晶体结构和电化学性质

Ru6(μ-O2CCH3)12(CH3OH)2(HCOO)2]Ru2(μ-O2CCH3)4(H2O)2](PF6)2.2H2O(Ru2(Ⅱ,Ⅲ)混合价)是通过二步反应合成的。首先Ru2(O2CCH3)4Cl在加热条件下与甲醇反应得到红棕色中间物,然后将该中间物在甲醇水(体积比7∶1)溶液中用Ag2SO4和NH4PF6进行脱氯配位反应得到此化合物。用元素分析、红外光谱、热重分析、循环伏安、X-衍射单晶结构分析等对其进行了表征。晶体结构表明,标题化合物的晶体属单斜晶系,空间群为P21/n,晶胞参数:a=0.85362(14)nm,b=1.19589(19)nm,c=3.6642(6)nm,β=92.316(3)°,Z=2,每个结构基元包含2个不同的配离子,其中Ru2(μ-O2CCH3)4(H2O)2]+是1个双核钌配离子,Ru6(μ-O2CCH3)12(CH3OH)2(HCOO)2]+是由另1个由甲醇配位、甲酸根桥连的六核钌配离子。2个独立的结构单元通过氢键形成三维超分子网络结构。采用循环伏安法对其电化学性质进行了表征,结果为一对准可逆的氧化还原峰,表明该配合物的中心金属二价钌原子Ru(Ⅱ)与三价钌原子Ru(Ⅲ)之间存在电子转移。

Synthesis, Crystal Structure and Electrochemical Properties of a Mixed Valence Ruthenium Complex

Ru6(μ-02CCH3)12(CH30H)2(HCOO)2]Ru2(μ-02CCH3)4(H20)2](PFs)2·2H20(with mixed valence Ru2(Ⅱ,Ⅲ))was synthesized by two-step reactions.Firstly,heat Ru2(02CCH3)4Cl in methanol under argon to get a brown red intermediate,then treat the intermediate with methanol aqueous solution in the presence of Ag2SO4 and NH4PF6 to get the title compound.The compound was characterized by elemental analysis,IR spectra,thermogravimetric analysis,cyclic voltammetry,and X-ray single crystal structure analysis.Its crystal belongs to monoclinic system with P21/n space group,in which a=0.853 62(14)am,b=1.195 89(19)nm,c=3.664 2(6)am,β=92.316(3)°and Z=2.Each structure element of the crystal contains two different match ions,Ru2(μ-O2CCH3)2(H20)2]+andRu6(μ=02CCH3)12(CH30H)2(HCOO)2]+.The former is a dinuclear ruthenium match ion.The latter is a six nuclear ruthenium match ion in coordination with methanol and bridge with formic acid.As independent components,the two elements were connected by hydrogen bond to form a three-dimensional supramolecular network.The electrochemical property of ruthenium complex has been studied by means of cyclic vohametry,the results show that electron transfer between Ru(II)and Ru(Ⅲ)in electrolysis is quasi-reversible process.CCDC:793726.