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Chem Commun (Camb). 2014 Jan 14;50(4):418-20. doi: 10.1039/c3cc48166b.

Synthesis and structure of the azidogermyliumylidene azide complex [L(N3)Ge:](+)N3- with covalently and ionically bonded azide ligands at germanium(II) [L = bis(N-heterocyclic carbene)].

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Technische Universit├Ąt Berlin, Department of Chemistry, Metalorganics and Inorganic Materials, Sekr. C2, Strasse des 17. Juni 135 D-10623, Berlin, Germany.


Starting from the chlorogermyliumylidene chloride salt [L(Cl)Ge:]Cl (1) (L = 1,1'-methylene-3,3'-di-2,6-diisopropyl-phenylimidazole-2,2'-diylidene), the chloride ion can be easily substituted by BPh4 to yield [L(Cl)Ge:]BPh4 (3). Reaction of the latter with NaN3 furnishes [L(N3)Ge:]BPh4 (4). In contrast, the direct reaction of 1 with NaN3 affords exclusively the first azidogermyliumylidene azide salt [L(N3)Ge:]N3 (2). The latter represents the first isolable diazido Ge(II) complex with a covalently bonded azido ligand and a weakly coordinating azide anion as the counterion. All new compounds 2, 3, and 4 were fully characterized, including using X-ray diffraction analysis.


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