Multiple and Highly Selective Alkyne-Isonitrile C−C and C−N Couplings at Group 4 Metallocenesстатья
Статья опубликована в высокорейтинговом журнале
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Дата последнего поиска статьи во внешних источниках: 18 марта 2017 г.
Аннотация:Reactions of the group 4 metallocene alkyne complexes [Cp′2M(η2‐Me3SiC2SiMe3)] [Cp′2=rac‐(ebthi)=rac‐1,2‐ethylene‐1,1′‐bis(η5‐tetrahydroindenyl): M=Ti, Zr, Hf; Cp′2=Cp*2 (Cp*=η5‐pentamethylcyclopentadienyl): M=Zr] with 2,6‐dimethylphenyl isocyanide (2‐xylyl isonitrile, XyNC) were investigated. Depending on the metal, the Cp′ ligand, and/or the stoichiometry, as well as the reaction temperature and time, different products were obtained. The products included simple end‐on coordination compounds of XyNC in addition to those of the coupling of Me3SiC2SiMe3 with two, three, or four isonitriles to form enimine complexes, aza‐metallacycloallenes, and fused heterocyclic systems, respectively. One example of the latter tricyclic compounds was subject to demetalation by using HCl. Molecular structures of the heterometallacycles were determined by X‐ray crystallography. The interconversion of the products was investigated by 1H NMR spectroscopy.