Accessing Lanthanide Metallocene Two-Electron Reduction Chemistry Using 2,2′-Bipyridine
Accessing Lanthanide Metallocene Two-Electron Reduction Chemistry Using 2,2′-Bipyridine
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使用 2,2-联吡啶获取镧系金属茂双电子还原化学
DOI：
10.1021/acs.organomet.3c00074
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发表时间：
2023
期刊：
影响因子：
2.8
通讯作者：
Evans, William J.
中科院分区：
文献类型：
--
作者：
Stennett, Cary R.;Nguyen, Joseph Q.;Ziller, Joseph W.;Evans, William J.
研究了氧化还原活性的2，2‘-联吡啶(Bipy)作为一种合成方便的电子载体，使稀土金属茂化合物实现两电子还原化学的可行性。以LnCl3、KCP*和BiPy为原料，在一锅中以75-81%的产率合成了Ln(III)前驱体配合物Cp*2LnCl(Bipy)，1-Ln(Ln=Nd，Gd；Cp*=C5Me5)，并经X-射线单晶学鉴定。1-Ln与K/KI(4.3wt%)反应，得到Cp*2Ln(Bipy)，2-Ln，根据它们的光谱特征和X-射线晶体结构，它们含有(Bipy)1-配体。还测定了以前报道的2-Eu的分子结构，其结构特征与中性的bipy配体一致。进一步还原2-Ndor2-Gd或以前报道的2-Sm，2-Eu和2-Yb与K/KI(4.3wt%)在2.2.2-加密(Cret)的存在下，在58-88%得到盐[K(Crypt)][Cp*2Ln(Bipy)]，3-Ln，其X-射线晶体学鉴定的测量参数与3-Eu和3-Yband a(Bipy)2-配体的3-Nd，3-Sm和3-Gd的(Bipy)1-配体一致。用3-Ln络合物考察了偶氮苯(phn=nPh)的两电子还原为(phn−nPh)2-的概念。3-Nd、3-Sm和3-Yb与偶氮苯以1：1的摩尔比以36-79%的产率合成了[K(Cryt)][Cp*2Ln(N2Ph2)]，4-Ln(Ln=Nd，Sm，Yb)配合物，并对其晶体结构进行了表征。在另一个两电子还原3-Ln的例子中，3-Ndor3-Sm与元素硫的处理以70%-75%的产率[K(Crypt)][Cp*2Ln(S5)]，5-Ln(Ln=Nd，Sm)，由结晶学证明是罕见的含有(S5)2-配体的非元素有机金属配合物。
The feasibility of using redox-active 2,2′-bipyridine (bipy) as a synthetically convenient electron carrier to enable lanthanide metallocenes to effect two-electron reduction chemistry has been examined. The Ln(III) precursor complexes, Cp*2LnCl(bipy),1-Ln(Ln = Nd, Gd; Cp* = C5Me5), were readily synthesized in 75–81% yield in one pot from LnCl3, KCp*, and bipy and were identified by X-ray crystallography. Treatment of the1-Lncompounds with K/KI (4.3 wt %) afforded in 74–77% yield the products, Cp*2Ln(bipy),2-Ln, which contain (bipy)1–ligands based on their spectroscopic characteristics and X-ray crystal structures. The molecular structure of the previously reported2-Euwas also determined, which showed structural features consistent with a neutral bipy ligand. Further reduction of2-Ndor2-Gd, or the previously reported2-Sm,2-Eu, and2-Ybwith K/KI (4.3 wt %) in the presence of 2.2.2-cryptand (crypt) afforded in 58–88% yield the salts, [K(crypt)][Cp*2Ln(bipy)],3-Ln, which show metrical parameters identified by X-ray crystallography that are consistent with a (bipy)1–ligand for3-Euand3-Yband a (bipy)2–ligand for3-Nd,3-Sm, and3-Gd. The two-electron reduction of azobenzene (PhN=NPh) to (PhN−NPh)2–using the3-Lncomplexes was examined as a proof of concept. The 1:1 reactions of3-Nd,3-Sm, and3-Ybwith azobenzene afforded in 36–79% yield the [K(crypt)][Cp*2Ln(N2Ph2)],4-Ln(Ln = Nd, Sm, Yb) complexes, each of which were crystallographically characterized. In another example of two-electron reduction by3-Ln, treatment of3-Ndor3-Smwith elemental sulfur afforded in 70–75% yield [K(crypt)][Cp*2Ln(S5)],5-Ln(Ln = Nd, Sm), which were shown by crystallography to be rare examples off-element organometallic complexes that contain the (S5)2–ligand.
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影响因子：
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