受阻Lewis酸碱对(FLP)型铝氢化合物的合成及其放H2反应研究

doi:10.6023/cjoc202510011

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, 通过五步金属有机合成路线, 制备了含分子内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 ℃下发生自岐化放氢反应, 得到铝单氢化合物(o-TMP-C₆H₄)₂AlH (2); 化合物2在50 ℃下引发N-甲基吲哚3-C(sp²)—H脱氢放氢反应, 生成[(o-TMP- C₆H₄)]₂Al(3-C₈H₅NMe) (3). 化合物1在－30 ℃下发生吲哚NH的放氢反应, 生成铝单氢化合物[(o-TMP-C₆H₄)Al- (μ-H)(NC₈H₆)]₂ (4); 化合物4在室温下也与吲哚NH基产生放氢反应, 生成(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, 得到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, 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, FLP-型活化, 3c-2e键化合物

Synthesis and H₂-liberation properties of N/Al frustrated Lewis pair (FLP)-type aluminum hydrides have been studied. By use of 2,2,6,6-tetramethylpiperidine, iodobenzene, n-BuLi, 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] that featured an intremolecular N→Al bonding was prepared. Compound 1 was occurred by a disproportionational H₂-liberation in toluene at 80 ℃ to give aluminum monohydride (o-TMP-C₆H₄)₂AlH (2), while compound 2 was able to react by further H₂- liberation at 50 ℃ via dehydrogenation of 3-C(sp²)—H of N-methylindole, affording [(o-TMP-C₆H₄)]₂Al(3-C₈H₅NMe) (3). Compound 1 reacted readily with indole at －30 ℃ to afford H₂-releasing compound [(o-TMP-C₆H₄)Al(μ-H)(NC₈H₆)]₂ (4). Compound 4 further reacted with indole at room temperature to generate (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 afford (o-TMP-C₆H₄)(C₆F₅)Al(μ-H)₂- B(C₆F₅)₂ (6), which features an Al(μ-H)₂B 3c-2e bond. Upon treatment with Al(C₆F₅)₃, metathesis between Al—H and Al—C₆F₅ bonds occurred to give [(o-TMP-C₆H₄)(C₆F₅)Al(μ-H)]₂ (7) containing an Al(μ-H)₂Al 3c-2e bond. Compounds 1~7 all exhibit N/Al FLP-character. The H₂-liberation reactions of 1, 2 and 4 were assisted by the concerted activation of either the C(sp²)—H or N—H bonds via the N/Al FLP moieties.

Key words: N/Al FLP-type aluminum hydride, H₂-liberation reaction, FLP-type activation, 3c-2e bond compound

引用此文

陈艺林, 朱成建. 受阻Lewis酸碱对(FLP)型铝氢化合物的合成及其放H₂反应研究[J]. 有机化学, 2026, 46(3): 881-887.

Yilin Chen, Chengjian Zhu. Study on Synthesis and H₂-Liberation Reaction of the Frustrated Lewis Pair (FLP)-Type Aluminum Hydrides[J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 881-887.

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图/表 11

图式1. (o-TMP-C6H4)I的合成路线

Scheme 1. Synthetic route to (o-TMP-C6H4)I

图式2. N/Al FLP-铝二氢化合物1的合成路线

Scheme 2. Synthetic route to N/Al FLP compound 1

图式3. 化合物1的溶剂热法放氢反应合成化合物2

Scheme 3. H2-Liberation reaction by solvent thermal treatment of compound 1 for synthesis of compound 2

图1. 化合物2(左)和3(右)的50%热椭圆球体晶体结构图

Figure 1. X-ray crystal structures of compounds 2 (left) and 3 (right) with thermal ellipsoids at 50% probability

图2. 1H NMR谱跟踪反应的测试结果

Figure 2. Result for the 1H NMR spectrium-traced reaction (a) 1H NMR spectrium of 1 in CDCl3; (b) 1H NMR spectrium-traced heat treatment of 1 in CDCl3; (c) 1H NMR spectrium of 2 in CDCl3

图式4. 化合物2脱N-甲基吲哚C(sp2)—H氢的放氢反应及其FLP型协同作用的机理

Scheme 4. H2-Liberation reaction by dehydrogenation of the C(sp2)—H of N-methylindole of compound 2 and the related FLP-type activation mechanism

Compd.	Al—C	Al—N	C—Al—N	Al—H
1^a	0.1944(1)	0.2311(1)	66.90(1)	0.1478(18) 0.1585(16)
2	0.1990(7) 0.1990(7)	0.2416(6) 0.2461(6)	64.30(2) 64.70(2)	0.1520(4)
3	0.1959(4) 0.1987(3)	0.2678(3) 0.3129	51.70 60.0(6)
4	0.1937(2)	0.2233(2)	68.70(9)	0.1520(2) 0.1967(2)
6	0.1918(3)	0.2133(2)	71.25(8)	0.1740(2) 0.1868(18)
7	0.1940(2)	0.2288(2)	67.59(7)	0.1596(2) 0.1940(18)

表1. FLP-型化合物1~4和6, 7中(o-TMP-C6H4)Al和AlH基的键长(nm)和健角(°)

Table 1. Bond lengths (nm) and angles (°) for (o-TMP-C6H4)Al and AlH moieties of the FLP compounds 1~4 and 6, 7

图式5. 化合物1脱吲哚NH氢的放氢反应及其FLP型协同作用的机理

Scheme 5. H2-Liberation reaction by dehydrogenation of the NH of indole using compound 1 and the related FLP-type concerted activation mechanism

图3. 化合物4的50%热椭圆球体晶体结构

Figure 3. X-ray crystal structure of compounds 4 with thermal ellipsoids at 50% probability

图式6. 化合物1和B(C6F5)3及Al(C6F5)3的反应合成化合物6和7

Scheme 6. Reactions of compound 1 with the respective B(C6F5)3 and Al(C6F5)3 for synthesis of compounds 6 and 7

图4. 化合物6(左)和7(右)的50%热椭圆球体晶体结构

Figure 4. X-ray crystal structures of 6 (left) and 7 (right) with both thermal ellipsoids at 50% probability level

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受阻Lewis酸碱对(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 Frustrated Lewis Pair (FLP)-Type Aluminum Hydrides

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