Research Institute for Physical Chemical Problems, Belarusian State University, Leningradskaya 14, 220030 Minsk, Belarus.
Dalton Trans. 2013 Feb 28;42(8):2985-97. doi: 10.1039/c2dt32512h.
For the first time, a representative of the 2,5-disubstituted tetrazoles, namely, 2-tert-butyl-5-(2-pyridyl)-2H-tetrazole (L), has been found to participate in oxidative dissolution of copper powder in homometalic systems Cu0–L–NH4X–DMSO (X = Cl, SCN, ClO4) and heterobimetallic ones Cu0–Mn(OAc)2–L–NH4OAc–Solv (Solv = DMSO, DMF), providing the formation of molecular homometallic complexes [CuL2Cl2] (1), [CuL2(SCN)2] (2), and CuL2(H2O)2 (3), heterobimetallic complex [Cu2MnL2(OAc)6] (4) from DMF solution and its mixture with complex [Cu2MnL2(OAc)6]·2DMSO (5) from DMSO solution. Free ligand L and complexes 1–4 were characterized by elemental analysis, IR spectroscopy, thermal and X-ray single crystal analyses, whereas complex 5 was characterized by X-ray analysis only. Compounds 1–3 are mononuclear complexes, with chelating coordination mode of L via the tetrazole ring N4 and pyridine ring N7 atoms. Heterobimetallic complexes 4 and 5 possess trinuclear structures, with a linear Cu–Mn–Cu arrangement of the metal atoms, linked by the acetate anions; each copper(II) atom is decorated by a chelating unit of L via the tetrazole ring N1 and pyridine ring N7 atoms in complex 4, and via the N4, N7 atoms in complex 5. Temperature-dependent magnetic susceptibility measurements of complex 4 revealed a weak antiferromagnetic coupling between the paramagnetic copper(II) and manganese(II) ions (J = −2.5 cm(−1), g(Cu) = 2.25 and g(Mn) = 2.01), with magnetic exchange through the acetato bridges.
首次发现，2,5-二取代四唑的代表物 2-叔丁基-5-(2-吡啶基)-2H-四唑（L）参与了铜粉在均相体系 Cu0-L-NH4X-DMSO（X=Cl、SCN、ClO4）和异双金属体系 Cu0-Mn(OAc)2-L-NH4OAc-Solv（Solv=DMSO、DMF）中的氧化溶解，生成了分子均相配合物[CuL2Cl2]（1）、[CuL2(SCN)2]（2）和CuL2(H2O)2（3），以及来自 DMF 溶液的异双金属配合物[Cu2MnL2(OAc)6]（4）及其与配合物[Cu2MnL2(OAc)6]·2DMSO（5）的混合物来自 DMSO 溶液。游离配体 L 和配合物 1-4 通过元素分析、红外光谱、热分析和 X 射线单晶分析进行了表征，而配合物 5 仅通过 X 射线分析进行了表征。化合物 1-3 为单核配合物，L 通过四唑环 N4 和吡啶环 N7 原子呈现螯合配位模式。异双金属配合物 4 和 5 具有三核结构，金属原子呈线性 Cu-Mn-Cu 排列，通过醋酸根阴离子连接；每个铜（II）原子都通过配合物 4 中四唑环 N1 和吡啶环 N7 原子以及配合物 5 中 N4、N7 原子被 L 的螯合单元修饰。配合物 4 的温度依赖磁化率测量显示，顺磁铜（II）和锰（II）离子之间存在弱反铁磁耦合（J=-2.5 cm(-1)，g(Cu)=2.25 和 g(Mn)=2.01），通过醋酸酯桥进行磁交换。
