Reductive C–O Cleavage of Ethereal Solvents and 18-Crown-6 in Ln(NR 2 ) 3 /KC 8 Reactions (R = SiMe 3 )
Reductive C–O Cleavage of Ethereal Solvents and 18-Crown-6 in Ln(NR 2 ) 3 /KC 8 Reactions (R = SiMe 3 )
复制标题
Ln(NR 2 ) 3 /KC 8 反应中醚类溶剂和 18-Crown-6 的还原 C−O 裂解 (R = SiMe 3 )
DOI：
10.1021/acs.inorgchem.3c00689
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发表时间：
2023
影响因子：
4.6
通讯作者：
Evans, William J.
中科院分区：
文献类型：
--
作者：
Chung, Amanda B.;Stennett, Cary R.;Moore, William N.;Fang, Ming;Ziller, Joseph W.;Evans, William J.
三（酰胺）配合物Ln(NR2)3（R = SiMe3）与石墨钾在多种醚存在下还原的高反应活性通过与Ln = Y, Ho， Er和Lu的六种不同类型的C-O键裂解反应产物的晶体结构得到证明。具体来说，1,2-二甲氧基乙烷（DME）可以在Ln(NR2)3/ kc8反应中被三种不同类型的晶体所切割：[K (crypt)][(R2N)3Y(OCH2CH2OCH3)],1- y, [(R2N)2Y(μ-OCH2CH2OCH3-κO,κO ')]2,2- y和[K2(18-c-6)3]{[(R2N)3Lu]2[(μ-OCH2CH2O)]},3- lu （18-c-6 = 18-冠-6；crypt = 2.2.2-cryptand）。通过Y(NR2)3/ kc8反应体系，THF可以开环，如图所示，丁醇的晶体[K(crypt)][(R2N)3Y(OCH2CH2CH2CH3)],4-Y。环乙烷OC3H6在Ln(NR2)3/ kc8反应中开环，形成丙醇[K(18-c-6)(OC3H6)][(R2N)3Ln(OCH2CH2CH3)]，5-Ln晶体，Ln = Ho和Er。在Et2O中，Y(NR2)3/ kc8反应不攻击溶剂，但18-c-6的C-O裂解形成{[(R2N)2]Y[μ-η1:η1-O2(C10H20O4)K]}2,6-Y。这些Ln(NR2)3/ KC8C-O裂解反应通常伴随着C-H键活化反应，形成[K(crypt)]{(R2N)2Ln[N(SiMe3)(SiMe2CH2)-κC,κN]}、7-Ln（Ln = Y, Ho, Er）和[K(18-c-6)]{(R2N)2Y[N(SiMe3)(SiMe2CH2)-κC，κN]}、8-Y等环金属酸盐，是Ln(NR2)3反应的常见分解产物。此外，本研究还分离出了氢化物配合物[K(18-c-6)][(R2N)3YH],9-Y。核磁共振分析表明，钇反应形成的混合物始终包含环金属酸钇7- y8 - y8为主要成分。这些结果显示了Ln(NR2)3/ kc8体系反应途径的多样性，并突出了分离含有[Ln(NR2)3]1阴离子的Ln（II）配合物的固有困难。
The high reactivity accessible from the reduction of the tris(amide) complexes Ln(NR2)3(R = SiMe3) with potassium graphite in the presence of a variety of ethers is demonstrated by crystal structures of six different types of products of C–O bond cleavage reactions with Ln = Y, Ho, Er, and Lu. Specifically, 1,2-dimethoxyethane (DME) can be cleaved in Ln(NR2)3/KC8reactions as shown by three different types of crystals: [K (crypt)][(R2N)3Y(OCH2CH2OCH3)],1-Y, [(R2N)2Y(μ-OCH2CH2OCH3-κO,κO′)]2,2-Y, and [K2(18-c-6)3]{[(R2N)3Lu]2[(μ-OCH2CH2O)]},3-Lu(18-c-6 = 18-crown-6; crypt = 2.2.2-cryptand). THF can be ring opened by the Y(NR2)3/KC8reaction system, as shown by crystals of the butoxide, [K(crypt)][(R2N)3Y(OCH2CH2CH2CH3)],4-Y. The cyclic ether, oxetane, OC3H6, ring opens in Ln(NR2)3/KC8reactions to form crystals of the propoxide, [K(18-c-6)(OC3H6)][(R2N)3Ln(OCH2CH2CH3)],5-Ln, for Ln = Ho and Er. In Et2O, the Y(NR2)3/KC8reactions do not attack the solvent, but C–O cleavage of 18-c-6 is observed to form {[(R2N)2]Y[μ-η1:η1-O2(C10H20O4)K]}2,6-Y. These Ln(NR2)3/KC8C–O cleavage reactions are typically accompanied by C–H bond activation reactions, which form cyclometalates such as [K(crypt)]{(R2N)2Ln[N(SiMe3)(SiMe2CH2)-κC,κN]},7-Ln(Ln = Y, Ho, Er), and [K(18-c-6)]{(R2N)2Y[N(SiMe3)(SiMe2CH2)-κC,κN]},8-Y, which are common decomposition products of Ln(NR2)3reactions. In addition, in this study, the hydride complex, [K(18-c-6)][(R2N)3YH],9-Y, was isolated. NMR analysis indicates that the yttrium reactions form mixtures that consistently contain the yttrium cyclometalates7-Yand8-Yas major components. These results show the diversity of available reaction pathways for the Ln(NR2)3/KC8system and highlight the inherent difficulties in isolating Ln(II) complexes containing the [Ln(NR2)3]1–anion.