稀土金属配合物催化的甲胺基硼烷脱氢聚合反应

doi:10.6023/cjoc202301026

摘要/Abstract

报道了稀土金属配合物催化的胺基硼烷脱氢聚合反应. 双茂稀土烷基配合物[(C₅Me₄R)₂LnR', R=Me, H; Ln=Sc, Y; R'=CH₂SiMe₃, CH(SiMe₃)₂]可以有效地实现甲基胺基硼烷(MeNH₂•BH₃, MAB)脱氢反应, 生成相应的硼氮聚合物[(MeNH-BH₂)_n, PMAB]. 研究表明随着稀土金属离子半径的增大或者茂基配体空间位阻的减小, 聚合活性会随之降低. 在机理研究中, 通过催化剂与底物的化学计量反应, 成功分离得到一例具有β-B-agostic结构的钪胺基硼烷配合物; 同时通过控制实验证实了活性的钪氢中间体可能为催化活性物种.

关键词: 稀土, 胺基硼烷, 脱氢, 聚合, β-氢消除

Rare-earth metal complexes-catalyzed dehydropolymerization of amine-borane was achieved. Rare-earth metallo- cene alkyl complexes [(C₅Me₄R)₂LnR', R=Me, H; Ln=Sc, Y; R'=CH₂SiMe₃, CH(SiMe₃)₂] were found to be active catalysts for the dehydropolymerization of methylamine-borane (MAB), generating corresponding boron-nitrogen polymer [(MeNHBH₂)_n, PMAB]. The results showed that the polymerization activity would decrease with the increase of ion radius of the metal center or the decrease of the steric hindrance of the supporting ligands. In the mechanistic study, a β-B-agostic-type scandium amidoborane complex was successfully isolated through the stoichiometric reaction of Sc complex with MAB. Moreover, the control experiment confirmed the existence of scandium hydride species, which may be the catalytic active intermediate.

Key words: rare-earth, amine-borane, dehydrogenation, polymerization, β-hydride elimination

引用此文

蒋胜杰, 王杨, 徐信. 稀土金属配合物催化的甲胺基硼烷脱氢聚合反应[J]. 有机化学, 2023, 43(5): 1786-1791.

Shengjie Jiang, Yang Wang, Xin Xu. Rare-Earth Metal Complexes-Catalyzed Dehydropolymerization of Methylamine-Boranes[J]. Chinese Journal of Organic Chemistry, 2023, 43(5): 1786-1791.

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图/表 7

图式1. 胺基硼烷的脱氢聚合反应与代表性催化剂

Scheme 1. Dehydropolymerization of amine-boranes and the representative examples of pre-catalysts

Entry	Cat.	Catalyst/ mol%	T/℃	Time/h	Conv./%	M_n/	Ð (M_w/M_n)
1	1	5	25	5	>99	3010	1.4
2	2	5	25	6	>99	5070	1.5
3	3	5	25	24	>99	3050	1.3
4	4	5	25	12	>99	2550	1.3
5	1	3	25	7.5	>99	2440	1.3
6	1	5	0	24	44	2670	1.3
7	1	5	60	24	>99^b	—	—

表1. 茂稀土金属烷基配合物催化的MAB脱氢聚合反应a

Table 1. MAB dehydropolymerization catalyzed by rare-earth metallocene alkyls

图式2. 茂基钪烷基配合物1与MAB的反应

Scheme 2. Stoichiometric reaction of scandocene alkyl complex 1 with MAB

图1. 配合物5的分子结构

Figure 1. Molecular structure of complex 5 Hydrogen atoms (except for N—H and B—H) are omitted for clarity, and displacement ellipsoids are drawn at the 30% probability level. Selected bond lengths (nm) and angles (°): Sc(1)—N(1), 0.2206(3); Sc(1)—H(1A), 0.205(3); N(1)—B(1), 0.1568(5); N(1)—H(2), 0.100(4); B(1)—H(1A), 0.112(3); B(1)—H(1B), 0.109(4); B(1)—H(1C), 0.114(4); N(1)—Sc(1)—H(1A), 60.6(8); Sc(1)—N(1)—B(1), 86.0(2); H(1A)—B(1)—N(1), 105.1 (17)

图式3. 配合物5与DMAP的反应

Scheme 3. Stoichiometric reaction of complex 5 with DMAP

图2. 配合物6的分子结构

Figure 2. Molecular structure of complex 6 Hydrogen atoms (except for N—H and B—H) are omitted for clarity, and displacement ellipsoids are drawn at the 30% probability level. Selected bond lengths (nm) and angles (°): Sc(1)—N(1), 0.2245(4); Sc(1)—N(2), 0.2205(17); N(2)—B(1), 0.1574(11); B(1)—C(21), 0.1611(9); N(1)—C(21), 0.1364(7); B(1)—H(1A), 0.111(8); B(1)—H(1B), 0.120(8); N(1)—Sc(1)—N(2), 78.5(4); Sc(1)—N(2)—B(1), 114.8(10); N(2)—B(1)—C(21), 109.6(8); N(1)—C(21)—B(1), 118.3(4); Sc(1)—N(1)—C(21), 116.9(3)

图式4. 稀土烷基配合物催化MAB脱氢聚合可能的反应机理

Scheme 4. A plausible mechanism for MAB dehydropolymerization catalyzed by rare-earth metal alkyl complexes

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