Dinuclear cobalt(II) and cobalt(III) complexes of bis-bidentate napthoquinone ligands
Dinuclear cobalt(II) and cobalt(III) complexes of bis-bidentate napthoquinone ligands
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双二齿萘醌配体的双核钴(II)和钴(III)配合物
DOI：
10.1039/c3dt52811a
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发表时间：
2014
期刊：
影响因子：
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通讯作者：
C.
中科院分区：
文献类型：
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作者：
Mulyana;Y. ; Alley;K. G ; Davies;K. M. ; Abrahams;B. F. ; Moubaraki;B. : Murray;K. S. : Boskovic;C.
衍生自 3,3-双-2-羟基-1,4-萘醌 (bhnqH2) 的桥联双齿氧化还原活性配体、基于三(2-吡啶基甲基)胺 (tpa) 的辅助配体和钴盐的组合提供了新的双核钴配合物家族。 [Co2(bhnq)(tpa)2]2+ (1)、[Co2(bhnq)(Metpa)2]2+ (2)、[Co2(bhnq)(Me2tpa)2]2+ (3) [Co2(bhnq)(Me3tpa)2]2+ (4)、[Co2(bhnq)(tpa)2]4+ (5) 的化合物， [Co2(bhMenaph)(tpa)2]2+ (6) 和 [Co2(bhPronaph)(tpa)2]2+ (7) （Mentpa 在 tpa 吡啶环的 6 位上包含 n = 0、1、2 和 3 个甲基；bhMenaphH4 = 双-3,4-二羟基-4-甲氧基萘-1-一；bhPronaphH4 =双-3,4-二羟基-4-(2-氧代丙基)萘-1(4H)-酮)已通过单晶X射线衍射进行了表征。虽然配合物 1-4 具有二价钴中心，但配合物 5-7 中明显存在三价钴。双齿氧化还原活性桥配体在配合物 1-5 中保持抗磁性醌 bhnq2− 氧化还原态。与甲醇盐或丙酮烯醇化物离子的金属催化反应产生了 6 和 7 中的衍生桥配体。 1-7 化合物的电子性质已通过红外光谱和变温磁测量在固态中通过电子吸收光谱和循环伏安法进行了探索。
The combination of bridging bis-bidentate redox-active ligands derived from 3,3-bis-2-hydroxy-1,4-naphthoquinone (bhnqH2), ancillary ligands based on tris(2-pyridylmethyl)amine (tpa) and cobalt salts has afforded a new family of dinuclear cobalt complexes. Compounds of the complexes [Co2(bhnq)(tpa)2]2+ (1), [Co2(bhnq)(Metpa)2]2+ (2), [Co2(bhnq)(Me2tpa)2]2+ (3) [Co2(bhnq)(Me3tpa)2]2+ (4), [Co2(bhnq)(tpa)2]4+ (5), [Co2(bhMenaph)(tpa)2]2+ (6) and [Co2(bhPronaph)(tpa)2]2+ (7) (Mentpa involves n = 0, 1, 2 and 3 methyl groups at the 6-position of the tpa pyridine rings; bhMenaphH4 = bis-3,4-dihydroxy-4-methoxynaphthalene-1-one; bhPronaphH4 = bis-3,4-dihydroxy-4-(2-oxopropyl)naphthalen-1(4H)-one) have been characterised by single crystal X-ray diffraction. While complexes 1–4 possess divalent cobalt centres, trivalent cobalt is evident in complexes 5–7. The bis-bidentate redox-active bridging ligand remains in the diamagnetic quinone bhnq2− redox state in complexes 1–5. Metal-catalysed reaction with methoxide or acetone enolate ions gives rise to the derivatised bridging ligands present in 6 and 7. The electronic properties of compounds of 1–7 have been explored in the solid state by infrared spectroscopy and variable temperature magnetic measurements and in solution by electronic absorption spectroscopy and cyclic voltammetry.