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Stabilizing Doubly Deprotonated Diazomethane: Isolable Complexes with CN22- and CN2- Radical Ligands.
Lv, Ze-Jie; Engel, Philipp D; Alig, Lukas; Maji, Sandipan; Holthausen, Max C; Schneider, Sven.
Afiliación
  • Lv ZJ; Institut für Anorganische Chemie, University of Göttingen, Tammannstraße 4, 37077 Göttingen, Germany.
  • Engel PD; Institut für Anorganische und Analytische Chemie, Goethe-Universität, Max-von-Laue-Strasse 7, 60438 Frankfurt am Main, Germany.
  • Alig L; Institut für Anorganische Chemie, University of Göttingen, Tammannstraße 4, 37077 Göttingen, Germany.
  • Maji S; Institut für Anorganische Chemie, University of Göttingen, Tammannstraße 4, 37077 Göttingen, Germany.
  • Holthausen MC; Institut für Anorganische und Analytische Chemie, Goethe-Universität, Max-von-Laue-Strasse 7, 60438 Frankfurt am Main, Germany.
  • Schneider S; Institut für Anorganische Chemie, University of Göttingen, Tammannstraße 4, 37077 Göttingen, Germany.
J Am Chem Soc ; 144(48): 21872-21877, 2022 Dec 07.
Article en En | MEDLINE | ID: mdl-36410000
Transition metal complexes with a doubly deprotonated diazomethane (CNN2-) ligand have been proposed as fleeting intermediates in nitrogen transfer reactions. However, in contrast to isoelectronic azide (N3-), well-defined examples are unknown. We here report the synthesis and characterization of isolable complexes with terminal and bridging CNN2- ligands, stabilized by platinum(II) pincer fragments. Bonding within the allenic dimetallanitrilimine core (Pt-N═N═C-Pt) was probed by oxidation of the bridging ligand. Enhanced reactivity toward [3 + 2]-cycloaddition with CO2 was obtained. Photofragmentation favors N-NC over NN-C bond cleavage as a route to cyanide and a transient metallonitrene complex.
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: J Am Chem Soc Año: 2022 Tipo del documento: Article País de afiliación: Alemania Pais de publicación: Estados Unidos
Texto completo
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: J Am Chem Soc Año: 2022 Tipo del documento: Article País de afiliación: Alemania Pais de publicación: Estados Unidos