Molybdenum-Mediated N 2 -Splitting and Functionalization in the Presence of a Coordinated Alkyne

A new [PCCP]-coordinated molybdenum platform comprising a coordinated alkyne was employed for the cleavage of molecular dinitrogen. The coordinated η -alkyne was left unaffected during this reduction. DFT calculations suggest that the reaction proceeds via an initially generated terminal N -complex,...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2021-12, Vol.60 (49), p.25804-25808
Main Authors: Wagner, Hannah K, Wadepohl, Hubert, Ballmann, Joachim
Format: Article
Language:English
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Summary:A new [PCCP]-coordinated molybdenum platform comprising a coordinated alkyne was employed for the cleavage of molecular dinitrogen. The coordinated η -alkyne was left unaffected during this reduction. DFT calculations suggest that the reaction proceeds via an initially generated terminal N -complex, which is converted to a dinuclear μ-(η :η )-N -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 N .
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202111325