非纯 2,2'-联吡啶在锌配合物中的氧化还原活性：实验和理论研究,ACS Omega

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非纯 2,2'-联吡啶在锌配合物中的氧化还原活性：实验和理论研究
ACS Omega ( IF 3.7 ) Pub Date : 2021-07-06 , DOI: 10.1021/acsomega.1c02201
Bin Li ₁ , Blaise L Geoghegan _{1,

2} , Christoph Wölper ₁ , George E Cutsail _{1,

2} , Stephan Schulz _{1,

1}

Affiliation

我们报告了 β-二酮亚胺锌配合物与氧化还原活性 2,2'-联吡啶 (bpy) 的系统反应性研究。LZnI (L = HC[C(Me)N( _2,6 - i Pr ₂ C ₆ H ₃ )] ₂ ) 与 NaB(C ₆ F ₅ ) ₄在 bpy 存在下反应生成 [LZn(bpy) ][B(C ₆ F ₅ ) ₄ ] ( 1 )，bpy 作为中性配体，而 LZnI 与 1 或 2 当量的 KC ₈在 bpy 存在下的还原反应得到自由基复合物 LZn(bpy) ( 2 ) 和 [2.2.2-Cryptand-K][LZn(bpy)] ( 3)，其中 bpy 分别充当 π 自由基阴离子或抗磁性二价阴离子。通过溶液磁化率测量证实了2的顺磁性，紫外-可见光谱表明2表现出 bpy 自由基物种的典型吸收带。2及其氘代类似物2- d ₈的 EPR 谱表明自旋密度位于 bpy 配体上。密度泛函理论计算和自然键轨道分析被雇用来阐明复合物的电子结构1 - 3并准确再现了结构实验数据。结果表明，bpy 部分的减少导致 β-diketiminate 共配体咬合角的减小和 Zn-N(β-diketiminate) 键的伸长，它们通过减少 Zn 与 bpy 配体协同和协同作用–N(bpy) 键长以稳定 LUMO 的能量。

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Redox Activity of Noninnocent 2,2′-Bipyridine in Zinc Complexes: An Experimental and Theoretical Study

We report on a systematical reactivity study of β-diketiminate zinc complexes with redox-active 2,2′-bipyridine (bpy). The reaction of LZnI (L = HC[C(Me)N(2,6-iPr₂C₆H₃)]₂) with NaB(C₆F₅)₄ in the presence of bpy yielded [LZn(bpy)][B(C₆F₅)₄] (1), with bpy serving as a neutral ligand, whereas reduction reactions of LZnI with 1 or 2 equiv of KC₈ in the presence of bpy gave the radical complex LZn(bpy) (2) and [2.2.2-Cryptand-K][LZn(bpy)] (3), in which bpy either acts as a π-radical anion or a diamagnetic dianion, respectively. The paramagnetic nature of 2 was confirmed via solution magnetic susceptibility measurements, and UV–vis spectroscopy shows that 2 exhibits absorption bands typical for bpy radical species. The EPR spectra of 2 and its deuterated analog 2-d₈ demonstrate that the spin density is localized to the bpy ligand. Density functional theoretical calculations and natural bond orbital analysis were employed to elucidate the electronic structure of complexes 1–3 and accurately reproduced the structural experimental data. It is shown that reduction of the bpy moiety results in a decrease in the β-diketiminate co-ligand bite angle and elongation of the Zn–N(β-diketiminate) bonds, which act cooperatively and in synergy with the bpy ligand by decreasing Zn–N(bpy) bond lengths to stabilize the energy of the LUMO.

更新日期：2021-07-20

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