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2026 26070231

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

Article

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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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

Cite this article

Zhang Lei , Zhang Ping , Zhang Yanfeng . Diversified Reactivity of (2,6-iPr2C6H3O)3Ta(bipy) toward Nitriles, Iso(thio)cyanates and Carbodiimides[J]. Acta Chimica Sinica, 2026 : 26070231 . DOI: 10.6023/A26070231

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