Rare earth benzene tetraanion-bridged amidinate complexes†

IF 7.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Peng-Bo Jin, Qian-Cheng Luo, Gemma K. Gransbury, Richard E. P. Winpenny, David P. Mills and Yan-Zhen Zheng
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引用次数: 0

Abstract

The benzene tetraanion-bridged rare earth inverse arene amidinate complexes [{Ln(κ16-Piso)}2(μ-η66-C6H6)] (2-Ln, Ln = Gd, Tb, Dy, Y; Piso = {(NDipp)2CtBu}, Dipp = C6H3iPr2-2,6) were prepared by the reduction of parent Ln(III) bis-amidinate halide precursors [Ln(Piso)2X] (Ln = Tb, Dy; X = Cl, I) or [Ln(Piso)2I] (Ln = Gd, Y) with 3 eq. KC8 in benzene, or by the reaction of the homoleptic Ln(II) complexes [Ln(Piso)2] (Ln = Tb, Dy) with 2 eq. KC8 in benzene. The arene exchange reaction of 2-Tb with toluene gave crystals of [{Tb(κ16-Piso)}2(μ-η66-C7H8)] (3-Tb), while no reactions were observed when C6D6 solutions of 2-Y were separately treated with biphenyl, naphthalene or anthracene. The reactivity study shows that 2-Y can behave as a four-electron reductant to reduce 1,3,5,7-cyclooctatetraene (COT). Complexes 2-Ln were characterized by single crystal X-ray diffraction, elemental analysis, SQUID magnetometry, UV-vis-NIR, ATR-IR, NMR, density functional theory (DFT) and ab initio calculations. These data consistently show that 2-Ln formally contain Ln(III) centres with arene-capped inverse-sandwich Dipp–Ln(III)–(C6H6)4−–Ln(III)–Dipp configurations, and DFT calculations on a model of 2-Y revealed strong Y–(C6H6)4− δ-bonding interactions between the filled π-orbitals of the benzene tetraanion and vacant 4d orbitals of the Y(III) ions. A strong intermolecular coupling interaction between the two Tb(III) centres in 2-Tb (Jtot = −6.84 cm−1) was evidenced by a step in a magnetization vs. field plot of 2-Tb at ca. 3.4 T at 2 K, which we attribute to an anti-ferromagnetic transition of the magnetic moment; we also determined an exchange coupling constant Jex = −0.25(1) cm−1 for 2-Gd.

Abstract Image

稀土苯四阴离子桥接氨基酸盐配合物
苯四阴离子桥接稀土反相芳烃酰胺酸配合物[{Ln(κ1:η6-Piso)}2(μ-η6:η6-C6H6)] (2-Ln, Ln = Gd, Tb, Dy, Y;Piso = {(NDipp)2CtBu}, Dipp = c6h3ipr2 -2,6)是由母体Ln(III)双氨基卤化物前体[Ln(Piso)2X] (Ln = Tb, Dy;X = Cl, I)或[Ln(Piso)2I] (Ln = Gd, Y)与苯中的3等KC8反应,或通过同感Ln(II)配合物[Ln(Piso)2] (Ln = Tb, Dy)与苯中的2等KC8反应。2-Tb与甲苯的芳烃交换反应生成[{Tb(κ1:η - 6- piso)}2(μ-η6:η - c7h8)] (3-Tb)晶体,而将2- y的C6D6溶液分别与联苯、萘或蒽处理时未见反应。反应性研究表明,2-Y可以作为四电子还原剂还原1,3,5,7-环四烯(COT)。通过单晶x射线衍射、元素分析、SQUID磁强计、UV-vis-NIR、ATR-IR、NMR、密度泛函理论(DFT)和从头计算对配合物2-Ln进行了表征。这些数据一致地表明,2-Ln在形式上包含具有芳烃覆盖的反夹心Dipp-Ln (III) - (C6H6)4—Ln(III) - dipp构型的Ln(III)中心,在2-Y模型上的DFT计算表明,苯四阴离子的填充π轨道和Y(III)离子的空4d轨道之间存在强的Y - (C6H6)4 - δ键相互作用。2-Tb中两个Tb(III)中心之间强烈的分子间耦合相互作用(Jtot =−6.84 cm-1)被证明是由2-Tb在约3.4 T时的磁化与磁场图中的一个步骤证明的,我们将其归因于磁矩的反铁磁跃迁;我们还确定了2-Gd的交换耦合常数Jex = -0.25 (1) cm-1。
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来源期刊
Chemical Science
Chemical Science CHEMISTRY, MULTIDISCIPLINARY-
CiteScore
14.40
自引率
4.80%
发文量
1352
审稿时长
2.1 months
期刊介绍: Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.
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