N2 Functionalization via Molybdenum‐Nitride Complex: Stepwise BH Bond Additions

Reactivity of (triphosphine)MoIV‐nitrido complex generated by N2 splitting, toward boranes is reported. The simple adduct Mo≡N→BH3 is observed with BH3.SMe2 while 1,2 addition is evidenced with 9‐BBN leading to H−Mo=NBR2. A second addition of BH3.SMe2 is facile and forms an unprecedented complex fea...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2024-07, Vol.63 (29), p.e202402586-n/a
Main Authors: Benaissa, Idir, Rialland, Barbara, Bennaamane, Soukaina, Espada, Maria F., Saffon‐Merceron, Nathalie, Fustier‐Boutignon, Marie, Clot, Eric, Mézailles, Nicolas
Format: Article
Language:English
Subjects:
boranes
Chemical Sciences
DFT calculations
Hydrogen bonds
Molybdenum
N2 reduction
nitride functionalization
Splitting
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Summary:Reactivity of (triphosphine)MoIV‐nitrido complex generated by N2 splitting, toward boranes is reported. The simple adduct Mo≡N→BH3 is observed with BH3.SMe2 while 1,2 addition is evidenced with 9‐BBN leading to H−Mo=NBR2. A second addition of BH3.SMe2 is facile and forms an unprecedented complex featuring two bridging H between two B and the Mo centers. Addition of PMe3 or BH3.SMe2 promotes reductive elimination and N−H bond formation. The full sequence of functionalization at Mo≡N obtained after N2 splitting is therefore evidenced in this work. The functionalization of the Mo≡N bond of a [(PPP)Mo(N)I] complex, which is obtained by N2 splitting, reveals guiding principles to N2 splitting and functionalization to give amine derivatives. The reaction of the N at a Mo center with BH bonds depends on the R2BH reagent.
ISSN:1433-7851
1521-3773
1521-3773
DOI:10.1002/anie.202402586