Molybdenum-mediated N2-splitting and functionalization in the presence of a coordinated alkyne

• Verfasst von: Wagner, Hannah [VerfasserIn]
• Verfasst von: Wadepohl, Hubert [VerfasserIn]
• Verfasst von: Ballmann, Joachim [VerfasserIn]
• Titel: Molybdenum-mediated N2-splitting and functionalization in the presence of a coordinated alkyne
• Verf.angabe: Hannah K. Wagner, Hubert Wadepohl, and Joachim Ballmann
• E-Jahr: 2021
• Jahr: 07 October 2021
• Umfang: 5 S.
• Fussnoten: Im Titel ist die Ziffer "2" beim Ausdruck "N2-splitting" tiefgestellt ; Gesehen am 02.09.2022
• Titel Quelle: Enthalten in: Angewandte Chemie. International edition
• Ort Quelle: Weinheim : Wiley-VCH, 1998
• Jahr Quelle: 2021
• Band/Heft Quelle: 60(2021), 49, Seite 25804-25808
• ISSN Quelle: 1521-3773
• DOI: doi:10.1002/anie.202111325
• Datenträger: Online-Ressource
• Sprache: eng
• Bibliogr. Hinweis: Parallele Sprachausgabe : deutschWagner, Hannah: Molybdän-vermittelte N2-Spaltung und Funktionalisierung in Gegenwart eines koordinierten Alkins
• Sach-SW: molybdenum
• Sach-SW: N-functionalization
• Sach-SW: nitrides
• Sach-SW: nitrogen fixation
• Sach-SW: phosphino alkyne ligands
• K10plus-PPN: 1815731036
• K10plus-PPN:
  Universitätsbibliothek
• Lokale URL UB: Zum Volltext

Abstract

A new [PCCP]-coordinated molybdenum platform comprising a coordinated alkyne was employed for the cleavage of molecular dinitrogen. The coordinated η2-alkyne was left unaffected during this reduction. DFT calculations suggest that the reaction proceeds via an initially generated terminal N2-complex, which is converted to a dinuclear μ-(η1:η1)-N2-bridged intermediate prior to N−N bond cleavage. Protonation, alkylation and acylation of the resulting molybdenum nitrido complex led to the corresponding N-functionalized imido complexes. Upon oxidation of the N-acylated imido derivative in MeCN, a fumaronitrile fragment was built up via C−C coupling of MeCN to afford a dinuclear molybdenum complex. The key finding that the strong N≡N bond may be cleaved in the presence of a weaker, but spatially constrained C≡C bond contradicts the widespread paradigm that coordinated alkynes are in general more reactive than gaseous N2.