摘 要

本研究以銠(III)金屬與二亞胺基雙螯配位子2,2'-bipyridine（bipy），1,10-phenanthroline（phen）、N,N'-dipyridylamine（HDPA）及去質子形式的HDPA（DPA－）所形成的混配基型d6金屬錯合物cis-[Rh(L-L)(HDPA)Cl2]+、cis-Rh(L-L)(DPA)Cl2（L-L=bipy或phen）與cis-[Rh(HDPA)2Cl2]+在Acetonitrile中，利用白金工作電極，於0～+1.80 V及0～-1.80 V vs SCE（saturated calomel electrode）的範圍內進行實驗。
cis-[Rh(L-L)(HDPA)Cl2]Cl在0～+1.80 V vs. SCE有一個可逆的氯離子氧化峰為+1.07～+1.08 V，其相對還原峰為+0.85～+0.87 V；在0～-1.80 V vs. SCE有兩個不可逆還原峰，皆為一個電子的轉移過程，且還原後均伴隨氯離子的脫落，故推測出其氧化還原軌域是定域於金屬的d*軌域。
cis-Rh(L-L)(DPA)Cl2在放光中初步認定為πd*的過渡。在電化學研究中，於0～+1.80 V vs. SCE並無氧化峰出現；在0～-1.80 V vs. SCE只見到一個不可逆還原峰，在此電位定電位電解，得知此處是一個電子的轉移，且電解後有氯離子的脫去，經由電化學所得結果，更加支持這兩種錯合物是屬於πd*的過渡。
cis-[Rh(HDPA)2Cl2]Cl在0～+1.80 V vs. SCE有一可逆氯離子氧化峰出現為+1.08 V，其相對還原峰為+0.89 V；在0～-1.80 V vs. SCE有一個不可逆還原峰，包含了兩個電子的還原過程，且還原之後並伴隨兩個氯離子快速脫去的化學反應，其氧化還原軌域亦是定域於金屬的d*軌域上。

Abstract

Cyclic voltametric data have been obtained for mixed-ligand complexes of rhodium(III) containing N,N'–dipyridylamine，cis-[Rh(L-L)(HDPA)Cl2]Cl、cis-Rh(L-L)(DPA)Cl2（L-L=bipy or phen）and cis-[Rh(HDPA)2Cl2]Cl in acetonitrile. For cis-[Rh(L-L)(HDPA)Cl2]
Cl，between 0～+1.80 V vs. SCE there is a reversible oxidation peak which is +1.07～+1.08 V and reduction peak is +0.85～+0.87 V. This is attributed to oxidation of chloride ion. There are two irreversible reduction peaks between 0～-1.80 V vs. SCE. Each of the reductions is one-electron reduction step followed by fast elimination of a chloride which is consistant with an ECEC（E：electron transfer，C：chemical reaction）mechanism. One can therefore suggest that their redox orbitals are assigned to be metal-localized.
The luminescence had been suggested as πd* for cis-Rh(L-L)(DPA)Cl2. In electrochemical studies of these complexes，there is no peak observed between 0～+1.80 V vs. SCE and only one irreversible reduction peak observed between 0～-1.80 V vs. SCE. This reduction is one-electron reduction step followed by elimination of a chloride，which assigns that complexes belong to πd* transition.
For cis-[Rh(HDPA)2Cl2]Cl，between 0～+1.80 V vs. SCE there is a reversible oxidation peak which is +1.08 V and reduction peak is +0.89 V. This is attributed to oxidation of chloride ion. There is one irreversible reduction peak between 0～-1.80 V vs. SCE. This reduction peak including two reduction steps followed by fast elimination of a chloride is consistent with an ECEC reaction. Therefore，the redox orbitals are also assigned to be metal-localized.

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