FLP-型铝氢化合物的合成及其放H2反应研究

doi:10.6023/cjoc202510011

研究论文

FLP-型铝氢化合物的合成及其放H₂反应研究

陈艺林^*,a,b, 朱成建^*,a

^a南京大学化学化工学院, 南京 210023
^b江苏南大光电材料股份有限公司, 苏州 215000

收稿日期:2025-10-16 修回日期:2025-11-24
基金资助:
国家自然科学基金面上项目 22271144

Study on Synthesis and H₂-Liberation Reaction of the FLP-type Aluminum Hydrides

Yilin Chen^*,a,b, Chengjian Zhu^*,a

¹School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023
²Jiangsu Nata Opto-electronic Material Co., Ltd., Soochow, 215000

Received:2025-10-16 Revised:2025-11-24
Contact: *E-mail: chenyl@natachem.com
Supported by:
National Natural Science Foundation of China (22271144)

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摘要/Abstract

研究了N/Al 受阻Lewis酸碱对(FLP)型的铝氢化合物的合成和放氢反应性能. 以2,2,6,6-四甲基哌啶、碘苯、正丁基锂、三氯化铝和四氢锂铝为原料, 采用五步的金属有机法路线, 合成了含分子内N→Al键作用的FLP-型铝二氢化合物(o-TMP-C₆H₄)AlH₂ (1, TMP = N(CMe₂CH₂)₂CH₂). 化合物1在甲苯溶剂中80 °C下发生自岐化放氢反应, 得到铝单氢化合物(o-TMP-C₆H₄)₂AlH (2); 2在 50 °C下引发N-甲基吲哚3-sp²-CH脱氢的放氢反应, 生成化合物[(o-TMP-C₆H₄)]₂Al(3-C₈H₅NMe) (3). 化合物1在‒30 °C下发生吲哚NH氢的放氢反应, 生成铝单氢化合物[(o-TMP-C₆H₄)Al(μ-H)(NC₈H₆)]₂ (4); 4在室温下也与吲哚NH基产生放氢反应, 生成化合物(o-TMP-C₆H₄)Al(NC₈H₆)₂ (5). 化合物1与B(C₆F₅)₃发生Al‒H/B‒C₆F₅的基团交换反应, 生成Al(μ-H)₂B 3c-2e键化合物(o-TMP-C₆H₄)(C₆F₅)Al(μ-H)₂B(C₆F₅)₂(6); 与Al(C₆F₅)₃则进行Al‒H/Al‒C₆F₅的基团交换, 给出Al(μ-H)₂Al 3c-2e键产物[(o-TMP-C₆H₄)(C₆F₅)Al(μ-H)]₂ (7). 化合物1‒7都是具有N/Al FLP-特性的化合物, 1‒2和4在放氢反应中受助于N/Al FLP的协同作用.

关键词: N/Al FLP-型铝氢化合物, 放氢反应, sp²-C-H和N‒H键的FLP-型活化, Al(μ-H)₂B和Al(μ-H)₂Al 3c-2e键化合物

Synthesis and the H₂-liberation reaction of the N/Al frustrated Lewis pair (FLP)-type aluminum hydrides have herein been studied in detail. By the use of 2,2,6,6-tetramethylpiperidine, iodobenzene, nBuLi, AlCl₃, and LiAlH₄ as precursor materials for the five-step organometallic synthesis route, FLP aluminum dihydride (o-TMP-C₆H₄)AlH₂ (1, TMP = N(CMe₂CH₂)₂CH₂) was prepared that features an intremolecular N→Al bonding. Compound 1 occurred by a disproportionational H₂-liberation in toluene at 80 °C to give aluminum monohydride (o-TMP-C₆H₄)₂AlH (2), while 2 was able to react by further H₂-liberation at 50 °C via dehydrogenation of the 3-sp²-CH of N-methylindole, affording compound [(o-TMP-C₆H₄)]₂Al(3-C₈H₅NMe) (3). When compound 1 reacted at ‒30 °C with indole readily to form an H₂-releasing compound [(o-TMP-C₆H₄)Al(μ-H)(NC₈H₆)]₂ (4), 4 did further well react with indole at room temperature generating (o-TMP-C₆H₄)Al(NC₈H₆)₂ (5). Finally, compound 1 reacted with B(C₆F₅)₃ by a group exchange between Al‒H and B‒C₆F₅ bonds to produce (o-TMP-C₆H₄)(C₆F₅)Al(μ-H)₂B(C₆F₅)₂(6) of the Al(μ-H)₂B 3c-2e bond character, and with Al(C₆F₅)₃ the metathesis of the Al‒H and Al‒C₆F₅ bonds happened to give the Al(μ-H)₂Al 3c-2e bond product [(o-TMP-C₆H₄)(C₆F₅)Al(μ-H)]₂ (7). Compounds 1‒7 are all of the N/Al FLP-character. The H₂-liberation reactions of 1‒2 and 4 were all asisted under the N/Al FLP concerted activation of either the sp²-C‒H or N‒H bonds.

Key words: N/Al FLP-Type aluminum hydride, H₂-Liberation reaction, FLP-Type activation of sp²-C-H and N‒H bonds, Al(μ-H)₂B and Al(μ-H)₂Al 3c-2e bond compounds

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陈艺林, 朱成建. FLP-型铝氢化合物的合成及其放H₂反应研究[J]. 有机化学, doi: 10.6023/cjoc202510011.

Yilin Chen, Chengjian Zhu. Study on Synthesis and H₂-Liberation Reaction of the FLP-type Aluminum Hydrides[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202510011.

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FLP-型铝氢化合物的合成及其放H₂反应研究

Study on Synthesis and H₂-Liberation Reaction of the FLP-type Aluminum Hydrides

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