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Synthesis and characterization of iron(II) and iron(III) complexes with a tridentate O,N,O '-ligand

机译:具有三齿O,N,O'-配体的铁(II)和铁(III)配合物的合成与表征

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The coordination chemistry of the ligand precursor 1-benzoyl-4,5-dihydro-3,5-bis(trifluoromethyl)-1H-pyrazol-5-ol (1a) to iron(II) acetate was studied. In dependence of the added co-ligand different complex geometries were observed. In case of 4-dimethylaminopyridine (DMAP) as co-ligand an octahedral iron(II) complex was found with an O,N,O'-coordination of the tridentate ligand (1a-2H), in which the ligand is planar, the oxygen donors are trans to each other, and the nitrogen donor is in a cis position. The other coordination sites on the iron center are occupied by DMAP ligands. In contrast to that, with triphenylphosphane as the co-ligand an oxidation process took place, which revealed an octahedral iron(III) complex with a comparable geometry for the tridentate ligand-(O,N,O'-coordination, 1a-2H) demonstrating the usefulness of 1a-2H to stabilize different oxidation states. The additional coordination sites are occupied by one triphenylphosphane oxide and ethoxide ligands. Interestingly, the ethoxide ligands act as bridging ligands to form a bimetallic complex. (C) 2014 Elsevier B.V. All rights reserved.
机译:研究了配体前体1-苯甲酰基-4,5-二氢-3,5-双(三氟甲基)-1H-吡唑-5-醇(1a)与乙酸铁(II)的配位化学。根据添加的共配体,观察到不同的复杂几何形状。如果以4-二甲基氨基吡啶(DMAP)作为配体,则发现八面体铁(II)配合物的三齿配体(1a-2H)的O,N,O'配位,其中配体是平面的,氧供体彼此反式,氮供体处于顺式位置。铁中心上的其他配位位点被DMAP配体占据。与此相反,使用三苯基膦作为共配体,发生了氧化过程,揭示了八面体铁(III)配合物,其三齿配体-(O,N,O'-配位,1a-2H)具有可比的几何形状证明了1a-2H可以稳定不同的氧化态。另外的配位点被一个三苯基膦氧化物和乙醇氧化物配体占据。有趣的是,乙醇氧化物配体充当桥接配体以形成双金属配合物。 (C)2014 Elsevier B.V.保留所有权利。

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