Titanium and manganese complexes supported by a xanthene-bridged bis(tripodal N_2O_2) ligand: Isomerization, intramolecular hydrogen bonding and metal-binding ability

Hirotsu M.; Kawamoto K.; Tanaka R.; Nagai Y.; Ueno K.; Teki Y.; Kinoshita I.

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Titanium and manganese complexes supported by a xanthene-bridged bis(tripodal N_2O_2) ligand: Isomerization, intramolecular hydrogen bonding and metal-binding ability

机译：x吨桥联双（三脚架N_2O_2）配体支持的钛和锰配合物：异构化，分子内氢键和金属结合能力

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A new bis(N_2O_2) ligand, L~(4-), in which two tripodal diamine-bis(phenolate) moieties are bridged by a xanthene backbone, was prepared. The reaction of H_4L with 2 equiv. of [Ti(O ~iPr)_4] produced C_2 and C_s symmetrical isomers of the dititanium(iv,iv) complex [Ti_2(L)(O ~iPr)_4]. The isolated C_2 isomer was slowly converted to the C_s isomer via Ti-N bond cleavage to form a 3:2 mixture in equilibrium. A similar dimanganese(iii,iii) complex [Mn _2(L)(OMe)_2(MeOH)_2] was synthesized from a 1:2 mixture of H_4L and manganese(ii) perchlorate in the presence of triethylamine. An X-ray analysis of [Mn_2(L)(OMe)_2(MeOH) _2] revealed that two Mn-N_2O_4 octahedrons are connected by intramolecular hydrogen bonds as well as a xanthene bridge to form a C_2 symmetrical structure. The dimanganese(iii,iii) complex further reacted with manganese(ii) acetate to form the mixed-valence trimanganese(iii,ii,iii) complex [Mn_3(L)(μ-OMe) _2(μ-OAc)_2]. Electrochemical data of the trimanganese(iii,ii,iii) complex indicated that the xanthene-bridged dimanganese(iii,iii) unit effectively binds a Mn~II ion in solution.

机译：制备了一个新的双（N_2O_2）配体L〜（4-），其中两个三脚架二胺-双（酚酸酯）部分被an吨骨架桥接。 H_4L与2当量的反应。 [Ti（O〜iPr）_4]的生成二钛（iv，iv）络合物[Ti_2（L）（O〜iPr）_4]的C_2和C_s对称异构体。通过Ti-N键裂解将分离的C_2异构体缓慢转化为C_s异构体，以形成平衡的3：2混合物。在三乙胺存在下，由H_4L和高氯酸锰（ii）的1：2混合物合成了类似的二锰（iii，iii）络合物[Mn _2（L）（OMe）_2（MeOH）_2]。 X射线分析[Mn_2（L）（OMe）_2（MeOH）_2]显示，两个Mn-N_2O_4八面体通过分子内氢键和a吨桥连接以形成C_2对称结构。二锰（iii，iii）配合物进一步与乙酸锰（ii）反应形成混合价三茂锰（iii，ii，iii）配合物[Mn_3（L）（μ-OMe）_2（μ-OAc）_2]。三苯甲基（iii，ii，iii）配合物的电化学数据表明，x吨桥联的二锰（iii，iii）单元可有效结合溶液中的Mn〜II离子。

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《Dalton transactions: An international journal of inorganic chemistry》 |2013年第34期|共8页
作者
Hirotsu M.; Kawamoto K.; Tanaka R.; Nagai Y.; Ueno K.; Teki Y.; Kinoshita I.;
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Titanium; equilibrium; Electrochemical;

机译：钛;平衡;电化学;

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1. Titanium and manganese complexes supported by a xanthene-bridged bis(tripodal N_2O_2) ligand: Isomerization, intramolecular hydrogen bonding and metal-binding ability [J] . Hirotsu M., Kawamoto K., Tanaka R., Dalton transactions: An international journal of inorganic chemistry . 2013,第34期

机译：x吨桥联双（三脚架N_2O_2）配体支持的钛和锰配合物：异构化，分子内氢键和金属结合能力
2. Synthesis and coordination chemistry of the tetradentate ligands 6,6'-bis(3-pyrazolyl)-2,2'-bipyridine and 6,6'-bis(2-hydroxyphenyl)2,2'-bipyridine: intramolecular hydrogen-bonding in complexes of Cu(II), and a dinuclear double helicate with Ag(I) [J] . Samantha M. Couchman, John C. Jeffery, Michael D. Ward Polyhedron: The International Journal for Inorganic and Organometallic Chemistry . 1999,第20期

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3. Bioinorganic Chemistry of Group 12 Complexes Supported by Tetradentate Tripodal Ligands Having Internal Hydrogen-Bond Donors [J] . Lisa M.Berreau European journal of inorganic chemistry . 2006,第2期

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5. The structures and reactivities of Group 12 metal complexes coordinated by tripodal nitrogen/sulfur ligands possessing internal hydrogen bond donors. [D] . Allred, Russell A. 2003

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Titanium and manganese complexes supported by a xanthene-bridged bis(tripodal N_2O_2) ligand: Isomerization, intramolecular hydrogen bonding and metal-binding ability

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