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Multiple and Highly Selective Alkyne–Isonitrile C−C and C−N Couplings at Group 4 Metallocenes
Author(s) -
Altenburger Kai,
Arndt Perdita,
Becker Lisanne,
Reiß Fabian,
Burlakov Vladimir V.,
Spannenberg Anke,
Baumann Wolfgang,
Rosenthal Uwe
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201601465
Subject(s) - alkyne , chemistry , isocyanide , ligand (biochemistry) , stoichiometry , ethylene , metallocene , stereochemistry , nuclear magnetic resonance spectroscopy , metal , crystallography , medicinal chemistry , organic chemistry , catalysis , polymerization , biochemistry , polymer , receptor
Abstract Reactions of the group 4 metallocene alkyne complexes [Cp′ 2 M(η 2 ‐Me 3 SiC 2 SiMe 3 )] [Cp′ 2 = rac ‐(ebthi)= rac ‐1,2‐ethylene‐1,1′‐bis(η 5 ‐tetrahydroindenyl): M=Ti, Zr, Hf; Cp′ 2 =Cp* 2 (Cp*=η 5 ‐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 Me 3 SiC 2 SiMe 3 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 1 H NMR spectroscopy.