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电化学  1999 

乙腈溶液中锇氮化合物电化学诱导桥氮偶联过程的原位FTIR反射光谱研究(英)

, PP. 254-260

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Abstract:

采用原位红外反射光谱(in_situFTIRS)结合紫外可见光谱(UV/Vis)和电化学循环伏安技术(CV),研究了[OsVI(N)(NH3)4](CF3SO3)3的电化学诱导桥氮偶联过程.首次在Pt电极上检测到桥氮混合价锇物种[Os_N≡N_Os]及其随电位的变化过程.在约2mmol/L〔OsVI(N)(NH3)4〕(CF3SO3)3+0.1mol/LTBAH的乙腈溶液中,选取0.4~-1.0V电位区间100mV/s扫描速度,对Pt或GC电极进行电化学循环伏安处理,处理后的电极表面均可积累一层深绿色的沉积物,表明电化学诱导N_N偶联效应已在电极上发生,并形成了混合价桥氮络合物.同时,在上述过程中所生成的混合价锇氮物种,有可能较强地吸附在电极表面,且形成一定厚度的表面层,从而减缓了体系中OsVI≡N物种在电极上的继续还原.同时可以看到,随着CV的不断进行,溶液颜色将逐渐地由黄变绿.经过长时间(约

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