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2026 26070231

DOI: https://doi.org/10.6023/A26070231

研究论文

钽联吡啶化合物与腈、异(硫)氰酸酯和碳二亚胺的反应性研究

  • 张磊 ,
  • 张萍 ,
  • 张艳峰
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  • 河北师范大学 化学与材料科学学院 石家庄 050024

收稿日期: 2026-07-01

  网络出版日期: 2026-08-19

基金资助

国家自然科学基金 (21801059)和河北师范大学科研基金 (L2025ZD08)资助.

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Diversified Reactivity of (2,6-iPr2C6H3O)3Ta(bipy) toward Nitriles, Iso(thio)cyanates and Carbodiimides

  • Zhang Lei ,
  • Zhang Ping ,
  • Zhang Yanfeng
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  • College of Chemistry and Materials Science, Hebei Normal University, Shijiazhuang 050024

Received date: 2026-07-01

  Online published: 2026-08-19

Supported by

National Natural Science Foundation of China (21801059) and the Science Foundation of Hebei Normal University (L2025ZD08).

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摘要

钽联吡啶化合物(2,6-iPr2C6H3O)3Ta(bipy) (1)对有机不饱和小分子表现出了丰富的反应性。例如,PhCN中的C≡N三键可以被化合物1还原,进而选择性地与联吡啶基团的C6/C6′发生C-C偶联并进一步发生1,5-氢迁移,生成钽亚胺化合物(2,6-iPr2C6H3O)3Ta(=NCHPh)(C10H7N2) (2);2可继续通过1,5-氢迁移生成二氮杂钽杂环戊烯化合物(2,6-iPr2C6H3O)3Ta(N2C10H7C(Ph)NH) (3)。同样,p-MeC6H4CH2CN、MeCN、CyCN和tBuCN均可与1发生类似的反应,生成化合物(2,6-iPr2C6H3O)3Ta(=NCH(R))(C10H7N2) (R = p-MeC6H4CH2 (4), Me (5), Cy (6), tBu (7));除7之外,化合物4~6可进一步转化为1,5-氢迁移产物(2,6-iPr2C6H3O)3Ta(N2C10H7C(R)NH) (R = p-MeC6H4CH2 (8), Me (9), Cy (10))。另外,异(硫)氰酸酯可以选择性地与化合物1中联吡啶基团的C2/C2′发生C-C偶联,生成插入产物(2,6-iPr2C6H3O)3Ta(bipy)(PhNCS) (11), (2,6-iPr2C6H3O)3Ta(bipy)(CyNCO) (12)和(2,6-iPr2C6H3O)3Ta(bipy)(tBuNCO) (13);化合物1还可作为Ta(III)合成子与碳二亚胺发生双电子转移反应,生成中性联吡啶配位的钽亚胺化合物(2,6-iPr2C6H3O)3Ta(=NPh)(bipy0) (R = Ph (14), iPr (15), Cy (16))。

关键词： 反应性; 有机钽化合物; 联吡啶配合物; 小分子活化; 合成

本文引用格式

张磊 , 张萍 , 张艳峰 . 钽联吡啶化合物与腈、异(硫)氰酸酯和碳二亚胺的反应性研究[J]. 化学学报, 2026 : 26070231 . DOI: 10.6023/A26070231

Abstract

Complexes of main group metals, lanthanides and actinides bearing reduced bipy ligand have garnered considerable attention and demonstrated notable potential in small-molecule activation. Nevertheless, the detailed reactivity studies on 2,2′-bipyridine-derived tantalum complexes remain largely unexplored. In this work, the divergent reactivity of a direduced bipyridyl tantalum complex (2,6-iPr2C6H3O)3Ta(bipy) (1) toward small molecules bearing highly unsaturated functional groups is explored. For instance, when treatment of complex 1 with 1.0 equivalent of benzonitrile (PhCN) at room temperature, the C≡N bond in PhCN can insert into the bipy moiety of complex 1 through the reduction of C≡N bond followed by C-C coupling occurring at C6 or C6′ of bipy in 1 and 1,5-H migration, forming the imido complex (2,6-iPr2C6H3O)3Ta(=NCHPh)(C10H7N2) (2), which can further undergo 1,5-H migration at 100 oC to yield the bis-amido complex (2,6-iPr2C6H3O)3Ta(N2C10H7C(Ph)NH) (3). The aliphatic nitriles, including p-tolylacetonitrile (p-MeC6H4CH2CN), acetonitrile (MeCN), cyclohexanecarbonitrile (CyCN) and pivalonitrile (tBuCN) with primary, secondary, tertiary and quaternary carbons at the α-position of cyano group, respectively, react with 1 to form the analogous imido products (2,6-iPr2C6H3O)3Ta(=NCH(R))(C10H7N2) (R = p-MeC6H4CH2 (4), Me (5), Cy (6) and tBu (7)). Among which, complexes 4-6 can also transform via 1,5-H migration into bis-amido complexes (2,6-iPr2C6H3O)3Ta(N2C10H7C(p-MeC6H4CH2)NH) (8), (2,6-iPr2C6H3O)3Ta(N2C10H7C(Me)NH) (9) and (2,6-iPr2C6H3O)3Ta(N2C10H7C(Cy)NH) (10), respectively, whereas, complex 7 remains inert even when its toluene solution was heated at 120 oC for one week. Furthermore, phenyl isothiocyanate (PhNCS) and alkyl isocyanates (CyNCO and tBuNCO) can regioselectively couple with C2 or C2′ of bipy moiety in 1 to form the insertion products (2,6-iPr2C6H3O)3Ta(bipy)(PhNCS) (11), (2,6-iPr2C6H3O)3Ta(bipy)(CyNCO) (12), and (2,6-iPr2C6H3O)3Ta(bipy)(tBuNCO) (13), respectively. During this process, the C=S and C=O bonds in iso(thio)cyanates are reduced, whereas the N=C double bonds remain intact, as confirmed by X - ray diffraction analysis. Conversely, 1 acts as a low valent Ta(III) synthon for (2,6-iPr2C6H3O)3Ta(III)(bipy) when reacted with organic carbodiimides (RN=C=NR) (R = Ph, iPr and Cy), yielding the neutral bipy coordinated tantalum imido complexes (2,6-iPr2C6H3O)3Ta(=NR)(bipy0) (R = Ph (14), iPr (15) and Cy (16)) via two-electron redox process.

Key words： reactivity; organotantalum; bipyridyl complex; small molecule activation; synthesis

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