O-donor forming a five-membered chelate ring and the OsN5O coordination sphere is distorted octahedral. Cyclic voltammetry shows a reversible osmium (II)–osmium (III) oxidation in the range of 0.37–0.51 V vs SCE followed by an irreversible osmium (III)-osmium (IV) oxidation in the range of 1.36–1.50 V vs SCE. These oxidation potentials are sensitive to the electronic nature of the substituent R in the 2-
摘要五个2-(芳基偶氮)
苯酚配体(通常缩写为Hap-R,其中H代表
酚质子)与[Os(bpy)2Br2]的反应提供了[OsII(bpy)2(ap- R)] +,已分离为
高氯酸盐。络合物是抗磁性的(低旋转d 6,S = 0),在
乙腈溶液中在可见光区显示出数个MLCT跃迁。[Os(bpy)2(ap-Me))
ClO4络合物的结构已通过X射线晶体学测定。2-(芳基偶氮)
苯酚酸根阴离子作为二齿N,O-给体与coordinate配位,形成一个五元螯合环,OsN5O配位域呈八面体形。循环伏安法显示,相对于SCE,(II)-os(III)的可逆氧化范围为0.37-0.51 V,然后不可逆的(III)-os(IV)的氧化范围为1.36-1。50 V vs SCE。这些氧化电势对2-(芳基偶氮)
酚盐
配体中的取代基R的电子性质敏感。低于-1.0 V的SCE负极上还显示了三联的bpy
配体的单电子还原。[OsII(bpy)2(ap-R)]