COMPLETE ELECTRON-TRANSFER SERIES OF [M-N4] TYPE
COMPLETE ELECTRON-TRANSFER SERIES OF [M-N4] TYPE
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DOI：
10.1021/ja00974a031
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发表时间：
1966-01-01
影响因子：
15
通讯作者：
HOLM, RH
中科院分区：
文献类型：
--
作者：
BALCH, AL;HOLM, RH
以邻苯二胺的二价阴离子为基本配体体系，对Co、Ni、Pd、Pt等通型[M-N4]z电子传递系列的存在性进行了深入研究。提出了五元系列双螯合物，其中成员的净电荷为 z=—2,—1, 0,+ 1,+ 2。镍系列的中心（z= 0）成员已确定为深蓝色配合物 Ni [C6H4-(NH) 2] 2 ，最初由 Feigl 和 Fiirth 在镍离子和空气存在下在氨水溶液中氧化邻苯二胺而制备。通过类似的途径，合成了配合物M [C6H4 (NH) 2] 2,= Co, Pd, Pt，并确定了它们的结构。非水溶剂中的极谱法已证实 Ni、Pd、Pt 存在完整的五元系列，Co 则存在 z=—2,—1, 0,+ 1 元。 z=-2,-1 的配合物由于其氧化不稳定性而无法通过化学方法制备。通过受控电位电解产生的 [M-N4] _ 物种的 EPR 研究揭示了玻璃中高度各向异性的 g 张量（如在 [M-S4]“配合物中观察到的），这有助于识别这些物种。除了 [M-N4] 配合物之外，还通过化学方法制备了 [M-N4] I 盐
Theexistence of the electron-transfer series of the generaltype [M-N4] z has been thoroughly investigated using the dianion of ophenylenediamine as the basic ligand system and= Co, Ni, Pd, and Pt. A five-membered series of bis chelate complexes is proposed in which the members have the net charges z=—2,—1, 0,+ 1,+ 2. The central (z= 0) member of the nickel series has been definitely established as the deep blue complex Ni [C6H4-(NH) 2] 2, which was originally prepared by Feigl and Fiirth from the oxidation of ophenylenediamine in aqueous ammoniacal solution in the presence of nickel ion and air. By a similar route thecomplexes M [C6H4 (NH) 2] 2,= Co, Pd, Pt, have been synthesized and their structuresestablished. Polarographyin nonaqueoussolvents has estab-lished the existence of the complete five-membered series for Ni, Pd, Pt, and the existence of the z=—2,—1, 0,+ 1 members for Co. Complexes with z=-2,-1 were not chemically prepared due to their oxidative instability. Epr studies of the [M-N4] _ species produced by controlled potential electrolysis reveal in glasses highly anisotropic g tensors (as observed in [M-S4]“complexes), which serve to identify these species. In addition to the [M-N4] com-plexes,[M-N4] I salts were chemically prepared for