两个新的双二茂铁硫脲衍生物FcL_1和FcL_2的合成、结构及电化学性质

Synthesis, Crystal Structure and Electrochemical Properties of Two Novel Diferrocenyl Thiourea Derivatives FcL_1 And FcL_2

以二茂铁苯甲酰氯和二茂铁间(对)苯胺为原料,合成了两个新的双二茂铁硫脲衍生物FcL1和FcL2.通过IR,1HNMR和元素分析等手段确定了标题化合物的结构.X射线单晶结构分析表明,FcL1属于三斜晶系,P1空间群,R1=0.0786,wR=0.1762.电化学分析结果表明,FcL1和FcL2的电化学性质相似,说明化合物中的两个二茂铁基所处的化学环境基本相同.间苯胺取代和对苯胺取代对化合物在电极表面的扩散系数影响不大,但对其反应速率常数则有较大的影响.

Two novel diferrocenyl thiourea derivatives FcL_1 and FcL_2 were synthesized. The structures of the compounds were determined by elemental analysis, IR and ()~1H NMR spectra. The X-ray single crystal structure analysis of FcL_1 indicates that the crystal belongs to triclinic system, P1 space group, there was a hydrogen bond in the compound. It was found that the electrochemical property of FcL_1 was very similar with that of FcL_2, the redox couple(FcL_1: E_(1/2)=600 mV; FcL_2: E_(1/2)=605 mV) was corresponding to the progress of 2Fc^(3+)+2e^-2Fc^(2+), which can be rationalized by the equivalent environment of the ferrocene subunit in each case. The difference between m-ferrocenylaniline and p-ferrocenylaniline didn′t cause the distinct change for their diffusion coefficient(D), but caused the distinct change for their electrochemical reaction rate constant(k_s).