MIXED-VALENCE SEMI-QUINONE CATECHOLATE IRON COMPLEXES
MIXED-VALENCE SEMI-QUINONE CATECHOLATE IRON COMPLEXES
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DOI：
10.1021/ja00389a016
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发表时间：
1982-01-01
影响因子：
15
通讯作者：
HENDRICKSON, DN
中科院分区：
文献类型：
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作者：
LYNCH, MW;VALENTINE, M;HENDRICKSON, DN
9，10-菲醌[用于模拟细菌光合作用中的电子转移]形成的配合物[Fe(HenSQ)3].cntdot.henQ与2，2‘-联吡啶(Bpy)、1，10-邻菲咯啉(Phen)或5，5’-二甲基-2，2‘-联吡啶(Dmbpy)反应，得到式为Fe(HenSQ)(HenCAT)(双齿氮碱)的配合物。~(57)Fe穆斯堡尔谱和磁化率数据表明，这3个配合物均为高自旋Fe(III)配合物。在固态和低介电常数溶剂中，通过观察到1100 nm处的价间转移[IT]带，证实了1-半醌-1-儿茶酚(PhenCAT2-)配体的混合价性质。在高介电性溶剂中没有IT带，其他特征发生变化，表明分子内电子转移到FeII(PhSQ)2(双齿氮碱)物种。Fe(DBSQ)3是3，5-二叔丁基-1，2-苯二酚的半喹酮形式，与bpy、phen、dmbpy、py和en[乙二胺]反应可得到5个类似化合物。这5个配合物的组成为FeIII(DBSQ)(DBCAT)(氮碱)，在固态下最有可能是低聚物。没有观察到这5个络合物的IT谱带；然而，从红外光谱中得到了对混合价组成的支持。
The complex [Fe(phenSQ)3].cntdot.phenQ, where phenQ and phenSQ are quinone and semiquinone forms, respectively, of 9,10-phenanthrenequinone [used to model electron transfer in bacterial photosynthesis], reacts with either 2,2''-bipyridine (bpy), 1,10-phenanthroline (phen), or 5,5''-dimethyl-2,2''-bipyridine (dmbpy) to give complexes of the formulation Fe(phenSQ)(phenCAT)(bidentate nitrogen base). 57Fe Mossbauer and magnetic susceptibility data indicate that these 3 complexes are high-spin Fe(III) complexes. The mixed-valence character with 1 semiquinone and 1 catecholate (phenCAT2-) ligand is substantiated by the observation of an intervalence transfer [IT] band at 1100 nm in the solid state and in low dielectric constant solvents. In high dielectric solvents there is no IT band and other features are changed, suggesting an intramolecular electron transfer to a FeII(phenSQ)2(bidentate nitrogen base) species. Five analogous compounds can be prepared by the reaction of Fe(DBSQ)3, where DBSQ is the semiquinone form of 3,5-di-tert-butyl-1,2-benzoquinone, with bpy, phen, dmbpy, py and en [ethylene diamine]. These 5 complexes have the composition FeIII(DBSQ)(DBCAT)(nitrogen base) and are most likely oligomeric in the solid state. No IT bands are seen for these 5 complexes; however, support for the mixed-valance composition is drawn from IR spectra.