Direct formation of an organonitrogen compound from a molybdenum nitrido species

Henderickx, Huub; Kwakkenbos, Gerard; Peters, Alexander; Spoel, J. van der; Vries, Koen de

doi:10.1039/b305774g

Cited by 44 publications

(38 citation statements)

References 14 publications

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“…The N−C bond forming reaction took place in between a Nb V nitride and an acyl chloride species. The first well defined transfer of the nitride ligand from [Mo VI (N t BuAr)( 15 N)] ( 2 – 15 N ) to an organic molecule was achieved using trifluoroacetic anhydride as an acceptor [80] . Quantitative formation of CF 3 CO 15 NH 2 was observed with concomitant decomposition of the molybdenum complex.…”

Section: Dissociative Mechanismmentioning

confidence: 99%

Dinitrogen Fixation: Rationalizing Strategies Utilizing Molecular Complexes

Masero

Perrin

Dey

et al. 2020

Chemistry A European J

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Dinitrogen (N2) is the most abundant gas in Earth's atmosphere, but its inertness hinders its use as a nitrogen source in the biosphere and in industry. Efficient catalysts are hence required to ov. ercome the high kinetic barriers associated to N2 transformation. In that respect, molecular complexes have demonstrated strong potential to mediate N2 functionalization reactions under mild conditions while providing a straightforward understanding of the reaction mechanisms. This Review emphasizes the strategies for N2 reduction and functionalization using molecular transition metal and actinide complexes according to their proposed reaction mechanisms, distinguishing complexes inducing cleavage of the N≡N bond before (dissociative mechanism) or concomitantly with functionalization (associative mechanism). We present here the main examples of stoichiometric and catalytic N2 functionalization reactions following these strategies.

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Section: Dissociative Mechanismmentioning

confidence: 99%

Dinitrogen Fixation: Rationalizing Strategies Utilizing Molecular Complexes

Masero

Perrin

Dey

et al. 2020

Chemistry A European J

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“…The starting species 117 could be recovered with a view to catalytic N 2 functionalization (Scheme ) 71. Species 117 was also able to react with trifluoromethylacetic acid anhydride to yield CF 3 CONH 2 72…”

Section: N≡n Bond Scission Reactionsmentioning

confidence: 99%

Reactivity of Dinitrogen Bound to Mid‐ and Late‐Transition‐Metal Centers

et al. 2015

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This review presents a comprehensive overview of the reactions of N 2 within the coordination sphere of transition metals of groups 6 to 9. Many of these metals mediate the reaction of N 2 with protons under reductive conditions, which can lead to the (catalytic) formation of ammonia or hydrazine, and the mechanisms of these reactions somewhat resemble the mode of action of nitrogenase enzymes. Alternatively, coordinated N 2 can react with carbon and silicon electrophiles and radicals to allow, for example, the catalytic formation of[a] Van '567 silylamines. Another approach in N 2 activation involves the homolytic splitting of dinitrogen to form intermediate nitrides in analogy to the Haber-Bosch process. Thus formed nitrides can undergo follow-up reactions with protons or carbon electrophiles. Molybdenum, tungsten, and iron reveal the richest chemistry of coordinated N 2 ; however, chromium, manganese, rhenium, osmium, and cobalt systems provide alternative pathways in the making and breaking of bonds on the dinitrogen molecule.Nitesh Khoenkhoen (1989) received his Bachelor of Science degree in chemistry at Utrecht University, The Netherlands, where he participated in undergraduate research under the supervision of Prof. Petra E. de Jongh in the area of inorganic chemistry and catalysis. After a short internship at the University of Amsterdam, he moved to the VU University Amsterdam, where he is currently a master's student in the laboratory of Professor Koop Lammertsma and is studying the generation of free phosphinidenes. Bas de Bruin (1971) did his PhD research at the RUN in Nijmegen (Prof. A. W. Gal, 1999). He did his postdoctoral research at the MPI für Bio-Anorganische Chemie in Mülheim a/d Ruhr (Prof. K. Wieghardt), after which he returned to the RUN as an assistant professor. In 2005, he moved to the University of Amsterdam (UvA, The Netherlands), where he was promoted to associate professor in 2008 and to full professor in 2013. He is involved in various research activities, including radical organometallic chemistry, EPR spectroscopy, olefin oxygenation, polymer synthesis, mechanistic studies, and computational catalysis with a focus on the development of new (bio-inspired) catalytic transformations. Joost N. H. Reek (1967) completed his PhD in Nijmegen with a thesis on supramolecular chemistry (Prof. Nolte). After a postdoctoral fellowship in Sydney Australia with Prof. Crossley, he joined the group of Prof. van Leeuwen at the University of Amsterdam (UvA, The Netherlands) as an assistant professor (1998), where he started research activities that focused on transition-metal catalysis. He was promoted to associate professor in 2003, and in 2006 he became full professor and elected member of the Young Royal Academy of Science. In 2009, he started a spin-off company (InCatT) to explore the commercial potential of new supramolecular strategies for combinatorial approaches in (asymmetric) catalysis. In 2013, he became the director of the Van 't Hoff Institute for Molecular Science. His current research ...

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“…There are a number of recent studies that have detailed cleavage of N 2 using group 5 (3)(4)(5) and group 6 (6-8) derivatives to generate metal nitride species. While the product nitrides are generally extremely stable, further functionalization of the molybdenum nitride NϵMo(N[Ar]-t-Bu) 3 , formed from Mo(N[Ar]-t-Bu) 3 and N 2 , has recently been reported (9). With regard to alkyne metathesis, the prototypical reactions involve group 6 alkoxide systems, typically RCϵW(O-t-Bu) 3 (1), and related Mo derivatives (10), along with a variety of in-situ-generated active catalysts (11).…”

Section: Introductionmentioning

confidence: 99%

Activation and cleavage of alkynes by the dinuclear tantalum complexes ([NPN]Ta)₂(µ-H)₄ and ([NPN]Ta)₂(µ-η¹:η²-N₂)(µ-H)₂ (where NPN = PhP(CH₂SiMe₂NPh)₂)

Shaver¹,

Johnson²,

Fryzuk³

2005

Can. J. Chem.

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Reaction of phenylacetylene with the dinuclear tetrahydride complex ([NPN]Ta) 2 (µ-H) 4 gives the product ([NPN]Ta) 2 (µ-PhCCH)(µ-H) 2 (where NPN is PhP(CH 2 SiMe 2 NPh) 2 ). Activation of other terminal alkynes by ([NPN]Ta) 2 (µ-H) 4 accesses ([NPN]Ta) 2 (µ-RCCH)(µ-H) 2 (R = n-Pr, t-Bu). Crystallographic analysis of the R = Ph derivative showed it to be a bis(µ-alkylidene) bound asymmetrically to the two tantalum centres. Storage of solutions of ([NPN]Ta) 2 (µ-PhCCH)(µ-H) 2 under vacuum promotes the loss of H 2 and cleavage of the C-C bond to give a bis(µ-alkylidyne) complex, ([NPN]Ta) 2 (µ-CPh)(µ-CH). Addition of diphenylacetylene did not give the desired ([NPN]Ta) 2 (µ-CPh) 2 , but rather promotes a complex decomposition of the supporting [NPN] ligands. Reaction of phenylacetylene with the dinitrogen complex ([NPN]Ta) 2 (µ-η 1 :η 2 -N 2 )(µ-H) 2 results in the dissociation of the bound dinitrogen and the formation of ([NPN]Ta) 2 (µ-PhCCH)(µ-H) 2 , which is identical to that derived from the reaction with the dinuclear tetrahydride. Résumé : La réaction du phénylacétylène avec le complexe tétrahydrure dinucléaire ([NPN]Ta) 2 (µ-H) 4 conduit au produit ([NPN]Ta) 2 (µ-PhCCH)(µ-H) 2 dans lesquels NPN = PhP(CH 2 SiMe 2 NPh) 2 . L'activation d'autres alcynes terminaux par du ([NPN]Ta) 2 (µ-H) 4 permet d'accéder aux composés ([NPN]Ta) 2 (µ-RCCH)(µ-H) 2 dans lesquels R = n-propyle et tbutyle. Une analyse cristallographique du dérivé avec R = Ph montre qu'il s'agit d'un bis(µ-alkylidène) lié d'une façon asymétrique aux deux centres de tantale. L'entreposage de solutions de ([NPN]Ta) 2 (µ-PhCCH)(µ-H) 2 sous vide facilite la perte de H 2 et le clivage de la liaison C-C pour conduire à la formation d'un complexe bis(µ-alkylidyne), ([NPN]Ta) 2 (µ-CPh)(µ-CH). L'addition de diphénylacétylène n'a pas conduit au ([NPN]Ta) 2 (µ-CPh) 2 attendu, mais a plutôt favorisé une décomposition complexe des ligands supports [NPN]. La réaction du phéhylacétylène avec le complexe de diazote ([NPN]Ta) 2 (µ-η 1 :η 2 -N 2 )(µ-H) 2 conduit à une dissociation du diazote lié et à la formation de ([NPN]Ta) 2 (µ-PhCCH)(µ-H) 2 identique à celui obtenu par réaction avec le tétrahydrure dinucléaire.

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Direct formation of an organonitrogen compound from a molybdenum nitrido species

Cited by 44 publications

References 14 publications

Dinitrogen Fixation: Rationalizing Strategies Utilizing Molecular Complexes

Dinitrogen Fixation: Rationalizing Strategies Utilizing Molecular Complexes

Reactivity of Dinitrogen Bound to Mid‐ and Late‐Transition‐Metal Centers

Activation and cleavage of alkynes by the dinuclear tantalum complexes ([NPN]Ta)₂(µ-H)₄ and ([NPN]Ta)₂(µ-η¹:η²-N₂)(µ-H)₂ (where NPN = PhP(CH₂SiMe₂NPh)₂)

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Direct formation of an organonitrogen compound from a molybdenum nitrido species

Cited by 44 publications

References 14 publications

Dinitrogen Fixation: Rationalizing Strategies Utilizing Molecular Complexes

Dinitrogen Fixation: Rationalizing Strategies Utilizing Molecular Complexes

Reactivity of Dinitrogen Bound to Mid‐ and Late‐Transition‐Metal Centers

Activation and cleavage of alkynes by the dinuclear tantalum complexes ([NPN]Ta)2(µ-H)4 and ([NPN]Ta)2(µ-η1:η2-N2)(µ-H)2 (where NPN = PhP(CH2SiMe2NPh)2)

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Activation and cleavage of alkynes by the dinuclear tantalum complexes ([NPN]Ta)₂(µ-H)₄ and ([NPN]Ta)₂(µ-η¹:η²-N₂)(µ-H)₂ (where NPN = PhP(CH₂SiMe₂NPh)₂)