CAJ | 학술논문

[Rus(μ-O2CCH3)12(CH3OH)2(HCOO)2][Ru:(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)4CI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NH,PF6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=O.853 62(14)nm,b=1.195 89(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(H20)2]+是1个双核钉配离子,[Rus(μ-O2CCH3)12(CH3OH)2(HC00)2]+是由另1个由甲醇配位、甲酸根桥连的六核钉配离子.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,结果为一对准町逆的氧化还原峰,表明该配合物的中心金属二价钉原子Ru(Ⅱ)与三价钉原子Ru(Ⅲ)之间存在电子转移.
[Rus(μ-O2CCH3)12(CH3OH)2(HCOO)2][Ru:(μ-O2CCH3)4(H2O)2](PF6)2·2H2O(Ru2(II,Ⅲ)혼합개)시통과이보반응합성적.수선Ru2(O2CCH3)4CI재가열조건하여갑순반응득도홍종색중간물,연후장해중간물재갑순수(체적비7:1)용액중용Ag2sO4화NH,PF6진행탈록배위반응득도차화합물.용원소분석、홍외광보、열중분석、순배복안、X-연사단정결구분석등대기진행료표정.정체결구표명,표제화합물적정체속단사정계,공간군위P21/n,정포삼수:a=O.853 62(14)nm,b=1.195 89(19)nm,c=3.6642(6)nm,β=92.316(3)°,Z=2,매개결구기원포함2개불동적배리자,기중[Ru2(μ-O2CCH3)4(H20)2]+시1개쌍핵정배리자,[Rus(μ-O2CCH3)12(CH3OH)2(HC00)2]+시유령1개유갑순배위、갑산근교련적륙핵정배리자.2개독립적결구단원통과경건형성삼유초분자망락결구.채용순배복안법대기전화학성질진행료표정,결과위일대준정역적양화환원봉,표명해배합물적중심금속이개정원자Ru(Ⅱ)여삼개정원자Ru(Ⅲ)지간존재전자전이.
[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]+and[Ru6(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.