Molybdenum-mediated N2-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 η2-alkyne was left unaffected during this reduction. DFT calculations suggest that the reaction proceeds via an initially generated terminal N2-complex,...
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| Main Authors: | , , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
07 October 2021
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| In: |
Angewandte Chemie. International edition
Year: 2021, Volume: 60, Issue: 49, Pages: 25804-25808 |
| ISSN: | 1521-3773 |
| DOI: | 10.1002/anie.202111325 |
| Online Access: | Verlag, kostenfrei, Volltext: https://doi.org/10.1002/anie.202111325 Verlag, kostenfrei, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/anie.202111325 
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| Author Notes: | Hannah K. Wagner, Hubert Wadepohl, and Joachim Ballmann |
| Summary: | 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. |
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| Item Description: | Im Titel ist die Ziffer "2" beim Ausdruck "N2-splitting" tiefgestellt Gesehen am 02.09.2022 |
| Physical Description: | Online Resource |
| ISSN: | 1521-3773 |
| DOI: | 10.1002/anie.202111325 |