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

doi:10.6023/A26070231

摘要/Abstract

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

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

引用此文

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, doi: 10.6023/A26070231.

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, doi: 10.6023/A26070231.

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