Reactivity of Aluminum Complexes of Redox-Active Ligand toward N-Heterocyclic Carbene and Its Thione,Organometallics

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Reactivity of Aluminum Complexes of Redox-Active Ligand toward N-Heterocyclic Carbene and Its Thione
Organometallics ( IF 2.5 ) Pub Date : 2019-12-16 , DOI: 10.1021/acs.organomet.9b00611
Vladimir G. Sokolov ₁ , Tatyana S. Koptseva ₁ , Roman V. Rumyantcev ₁ , Xiao-Juan Yang ₂ , Yanxia Zhao ₂ , Igor L. Fedushkin _{1,

2}

Affiliation

The reaction of dialane (dpp-Bian)Al–Al(dpp-Bian) (1) (dpp-Bian is dianion of 1,2-bis[(2,6-diisopropylphenyl)imino]-acenaphthene) with 1 mol equiv of 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene (iPr₂Im^Me) results in the Al-carbene adduct (dpp-Bian)(iPr₂Im^Me)Al–Al(dpp-Bian) (3). In the course of the reaction of dialane 1 with 2 mol equiv of 1,3-diisopropyl-4,5-dimethylimidazol-2-thione (iPr₂Imt^Me) a half of the thione amount undergoes a cleavage of sulfur–carbon double bond. In the product (dpp-Bian)(iPr₂Im^Me)Al(μ-S)Al(iPr₂Imt^Me)(dpp-Bian) (4) aluminum atoms coordinate carbene as well as thione ligands. Compound 4 is thermally robust: no reduction of C═S bond in thione moiety by the dpp-Bian ligands could be observed in toluene for 24 h at 100 °C. Complex {(dpp-Bian)(iPr₂Im^Me)Al}₂(μ-S) (5) was isolated from the reaction of dialane 1, iPr₂Im^Me, and iPr₂Imt^Me (1:1:1). The reaction of mononuclear (dpp-Bian)AlH(THF) (2) (THF = tetrahydrofuran) affords compound (dpp-Bian)AlH(iPr₂Im^Me) (6). Compounds 3–6 were characterized by ¹H NMR and IR spectroscopy; their molecular structures were established by single-crystal X-ray analysis.

中文翻译：

氧化还原活性配体的铝配合物对N-杂环卡宾及其亚硫醚的反应性

二烷（dpp-Bian）Al-Al（dpp-Bian）（1）（dpp-Bian是1,2-双[（2,6-二异丙基苯基）亚氨基] -ena啶的二价阴离子）与1摩尔当量的1,3-二异丙基-4,5-二甲基咪唑-2-亚烷基（i Pr ₂ Im ^Me）导致铝卡宾加成物（dpp-Bian）（i Pr ₂ Im ^Me）Al-Al（dpp-Bian）（3）。在二烷1与2摩尔当量的1,3-二异丙基-4,5-二甲基咪唑-2-硫酮（i Pr ₂ Imt ^Me）反应的过程中，一半的硫酮经历了硫-碳双裂解键。在乘积（dpp-Bian）（iPr ₂ Im ^Me）Al（μ-S）Al（i Pr ₂ Imt ^Me）（dpp-Bian）（4）铝原子配位卡宾以及硫酮配体。化合物4具有良好的耐热性：在100°C的甲苯中放置24 h，未发现dpp-Bian配体使硫酮部分的C═S键还原。从dial烷1，i Pr ₂ Im ^Me和i Pr ₂ Imt ^Me的反应中分离出复合物{（dpp-Bian）（i Pr ₂ Im ^Me）Al} ₂（μS）（5）（1：1：1）。单核（dpp-Bian）AlH（THF）（2）（THF ＝四氢呋喃）的反应得到化合物（dpp-Bian）AlH（i Pr ₂ Im ^Me）（6）。化合物3 - 6进行了表征¹ H NMR和IR光谱; 通过单晶X射线分析确定了它们的分子结构。

更新日期：2019-12-17

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