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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >The modular synthesis of rare earth-transition metal heterobimetallic complexes utilizing a redox-active ligand
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The modular synthesis of rare earth-transition metal heterobimetallic complexes utilizing a redox-active ligand

机译：利用氧化还原活性配体的稀土化过渡金属偏振络合物的模块化合成

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摘要

We report a robust and modular synthetic route to heterometallic rare earth-transition metal complexes. We have used the redox-active bridging ligand 1,10-phenathroline-5,6-dione (pd), which has selective N,N or O,O binding sites as the template for this synthetic route. The coordination complexes [Ln(hfac)(3)(N,N'-pd)] (Ln = Y [1], Gd [2]; hfac = hexafluoroacetylacetonate) were synthesised in high yield. These complexes have been fully characterised using a range of spectroscopic techniques. Solid state molecular structures of 1 and 2 have been determined by X-ray crystallography and display different pd binding modes in coordinating and non-coordinating solvents. Complexes 1 and 2 are unusually highly coloured in coordinating solvents, for example the vis-NIR spectrum of 1 in acetonitrile displays an electronic transition centred at 587 nm with an extinction coefficient consistent with significant charge transfer. The reaction between 1 and 2 and VCp2 or VCp2t (Cp-t = tetramethylcyclopentadienyl) resulted in the isolation of the heterobimetallic complexes, [Ln(hfac)(3)(N,N-O,O-pd)VCp2] (Ln = Y [3], Gd [4]) or [Ln(hfac)(3)(N,N-O,O-pd)VCp2t] (Ln = Y [5], Gd [6]). The solid state molecular structures of 3, 5 and 6 have been determined by X-ray crystallography. The spectroscopic data on 3-6 are consistent with oxidation of V(ii) to V(iv) and reduction of pd to pd(2-) in the heterobimetallic complexes. The spin-Hamiltonian parameters from low temperature X-band EPR spectroscopy of 3 and 5 describe a (2)A(1) ground state, with a V(iv) centre. DFT calculations on 3 are in good agreement with experimental data and confirm the SOMO as the d(x)(2)-y(2) orbital localised on vanadium.
机译：我们报告了一种稳健和模块化的合成途径，可加入差异稀土化土过渡金属配合物。我们使用了氧化还原活性桥接配体1,10-母酚碱-5,6-二酮（Pd），其具有选择性N，N或O，o结合位点作为该合成途径的模板。合成高产合成协调络合物[LN（HFAC）（3）（3）（N，N，N，N，N，Gd [1]，Gd [2]; HFAC =六氟乙酰丙酮）。这些配合物已经使用一系列光谱技术完全表征。通过X射线晶体学确定固态分子结构1和2，并在配位和非配位溶剂中显示不同的PD结合模式。配合物1和2在配位溶剂中非常高度着色，例如乙腈中的1的Vis-Nir光谱显示在587nm处以587nm为中心的电子转换，其消光系数与显着的电荷转移一致。 1和2和VCP2或VCP2T（CP-T =四甲基环戊二烯基）之间的反应导致杂化物复合物的分离，[LN（HFAC）（3）（N，NO，O-Pd）Vcp2]（Ln = Y [ 3]，Gd [4]）或[LN（HFAC）（3）（3）（N，NO，O-Pd）Vcp2t]（Ln = Y [5]，Gd [6]）。通过X射线晶体学确定了3,5和6的固态分子结构。 3-6上的光谱数据与V（II）至V（IV）的氧化一致，并在异组合物中还原Pd（2-）。来自低温X波段EPR光谱的旋转Hamiltonian参数为3和5描述了（2）（1）个接地状态，具有V（IV）中心。 3对3的DFT计算与实验数据吻合良好，并确认SOMO为D（x）（2）-Y（2）型钒的轨道。

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