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Reactivity of [Sm(DippForm)2(thf)2] with Substrates Containing Azo Linkages

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WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejic.202300583

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lanthanoid complexes; one- and two-electron reduction; reductive trapping; samarium; trans-azobenzene

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This paper investigates the interaction between divalent [Sm(DippForm)(2)(thf)(2)] and substrates containing azo linkages. It is found that treatment with trans-azobenzene results in the formation of mononuclear or dinuclear complexes, as well as [Sm(DippForm)(3)]. Moreover, the reaction of [Sm(DippForm)(2)(thf)(2)] with 1H-1,2,3-benzotriazole yields a trivalent samarium complex containing benzotriazolate.
This paper explores the interaction of divalent [Sm(DippForm)(2)(thf)(2)] with substrates containing azo linkages. Treatment of [Sm(DippForm)(2)(thf)(2)] with trans-azobenzene results in formation of mononuclear [Sm-lll(DippForm)(2)(Ph2N2)(thf)] & sdot; 3THF (1) or dinuclear [Sm-lll(DippForm)(Ph2N2)(thf)](2) & sdot; 4THF (2) and [Sm(DippForm)(3)] depending on the reaction stoichiometry, where azobenzene has undergone either a one or two electron reduction. These reactions parallel the corresponding reactions of [Sm(C5Me5)(2)(thf)(2)], but the coordination of [N2Ph2](-) in 1 differs significantly from that of {Sm(C5Me5)(2)(Ph2N2)(thf)}. On the other hand, the structure of 2 is similar to that of the pentamethylcyclopentadienyl analogue. The reaction of [Sm(DippForm)(2)(thf)(2)] with 1H-1,2,3-benzotriazole also yielded a trivalent samarium complex containing benzotriazolate (btz), [Sm-lll(DippForm)(2)(btz)(thf)] & sdot; THF (3), and suggests more utilization of 1H-1,2,3-benzotriazole in divalent lanthanoid reduction chemistry is possible.

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