First Insertions of Carbene Ligands into Ge−N and Si−N Bonds. Issue 18 (15th March 2017)

• Record Type: Journal Article
• Authors: Álvarez‐Rodríguez, Lucía; Cabeza, Javier A.; García‐Álvarez, Pablo; Gómez‐Gallego, Mar; Merinero, Alba D.; Sierra, Miguel A.
• Is Part Of: Chemistry. Volume 23:Issue 18(2017)
• Page Start: 4287
• Page End: 4291
• Publication Date: 2017-03-15
• Subjects: carbene insertion -- Fischer carbenes -- germanium -- silicon -- tetrylenes; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201700828
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: The insertion of carbene ligands into Ge−N (three examples) and Si−N (one example) bonds has been achieved for the first time by treating Fischer carbene complexes (M=W, Cr) with bulky amidinatotetrylenes (E=Ge, Si). These reactions, which start with a nucleophilic attack of the amidinatotetrylene heavier group 14 atom to the carbene C atom, proceed through a stereoselective insertion of the carbene fragment into an E−N bond of the amidinatotetrylene ENCN four‐membered ring, leading to [M(CO)5 L] derivatives in which L belongs to a novel family of tetrylene ligands comprising an ECNCN five‐membered ring. Abstract : Caught with a ring : The 4‐membered ring of amidinatotetrylenes has been expanded with Fischer carbene complexes. These reactions, which afford complexes containing a novel type of 5‐membered ring tetrylene ligand, proceed through unprecedented insertions of carbene ligands into Ge−N and Si−N bonds.