Synthesis of Benzonitrile from Dinitrogen

Klopsch, Isabel; Schendzielorz, Florian; Volkmann, Christian; Würtele, Christian; Schneider, Sven

doi:10.1002/zaac.201800181

Cited by 24 publications

(21 citation statements)

References 30 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Reduction of this trichloride complex with sodium mercury amalgam under dinitrogen regenerated the putative rhenium nitride 33 and closed the chemical cycle which produced acetonitrile from ethyl triflate and N 2 . The very same protocol was applied for the synthesis of benzonitrile with in situ generated benzyl triflate as the carbon source [85] . Use of a sterically less demanding pincer ligand (isopropyl instead of tertiary butyl substituents on the phosphorous) enabled the formation of benzonitrile and benzamide from dinitrogen and benzoyl chloride (Scheme 18 b).…”

Section: Dissociative Mechanismmentioning

confidence: 99%

Dinitrogen Fixation: Rationalizing Strategies Utilizing Molecular Complexes

Masero

Perrin

Dey

et al. 2020

Chemistry A European J

View full text Add to dashboard Cite

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.

show abstract

Section: Dissociative Mechanismmentioning

confidence: 99%

Dinitrogen Fixation: Rationalizing Strategies Utilizing Molecular Complexes

Masero

Perrin

Dey

et al. 2020

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…This model reveals some basic principles in comparison to our previously reported system. [7,13] Use of as terically less encumbered pincer ligand stabilizes higher coordination numbers.I n consequence,t hermal N 2 splitting becomes less favorable which can be overcome by photolysis with visible light. Based on the experimental and theoretical data, the photochemical reactivity is associated with the population of ad issociative state with Re!N 2 MLCT character.The higher coordination number weakens nitride bonding,t hus enabling the use of aw eaker electrophile than alkyl triflates.I mportantly,t he cooperating pincer ligand serves as ar eservoir for nitrogen hydrogenolysis upon 2e À /2H + -PCET and electrochemical rehydrogenation.…”

Section: Angewandte Chemiementioning

confidence: 99%

“…[4] Thed irect synthesis of compounds other than NH 3 from N 2 remains af ormidable challenge.C atalytic protocols are only known for trisilylamine. [5] Nitriles, [6][7][8] isocyanates, [9] silylamines, [10,11] and borylamines [12] have been synthesized within stoichiometric,c yclic reaction sequences,w hich allow for evaluating strategies to offset the extremely strong NNbond (225 kcal mol À1 ), enable EÀN(E= C, Si, B) bond formation and deliver six reduction equivalents.A ll reported "synthetic cycles" proceed through initial N 2 cleavage into nitride complexes. Subsequent nitrogen transfer typically requires strong electrophiles like alkyl triflates.T he thermochemistry of N 2 splitting must therefore be tuned to avoid nitride overstabilization and enable functionalization with reagents that are more compatible with reductive conditions.…”

mentioning

confidence: 99%

“…Heating of 6 with PhC(O)Cl (2 equiv) at 80 8 8Ci n1 ,4dioxane over 15 hg ives an ew rhenium species (7)i n7 1% yield (Scheme 2). Paramagnetically shifted and sharp NMR signals support reduction to Re III .T wo chemically inequivalent phosphorus atoms (d P = À1592.6, À1615.5 ppm; 2 J PP = 248 Hz) and the 1 Hand 13 CNMR signatures are in agreement with pincer oxidation to an imine ligand.…”

mentioning

confidence: 99%

See 1 more Smart Citation

Metal‐Ligand Cooperative Synthesis of Benzonitrile by Electrochemical Reduction and Photolytic Splitting of Dinitrogen

et al. 2018

Self Cite

View full text Add to dashboard Cite

Thermal nitrogen fixation relies on strong reductants to overcome the extraordinarily large N À Nb ond energy. Photochemical strategies that drive N 2 fixation are scarcely developed. Here,t he synthesis of ad inuclear N 2 -bridged complex is presented upon reduction of arhenium(III) pincer platform. Photochemical splitting into terminal nitride complexes is triggered by visible light. Clean nitrogen transfer with benzoyl chloride to free benzamide and benzonitrile is enabled by cooperative 2H + /2 e À transfer of the pincer ligand. Athreestep cycle is demonstrated for N 2 to nitrile fixation that relies on electrochemical reduction, photochemical N 2 -splitting and thermal nitrogen transfer. Figure 3. Left:CVof7 in presence of 0-15 equiv.b enzoic acid.Right: CV of 7 with 10 equiv 2,6-dichlorophenol under N 2 before CPE (orange), after 8hCPE at À1.65 V( pink) and after subsequent 5h CPE at À1.85 V(blue).Scheme 3. Optimized, three-steps ynthetic cycle. Angewandte ChemieCommunications 833

show abstract

“… 3 , 4 , 9 Several groups demonstrated the suitability of dissociative mechanistic scenarios, e.g., to synthesize organic nitriles from N 2 , within stepwise, cyclic reaction schemes (“synthetic cycles”). 10 − 13 However, truly catalytic protocols that allow for the direct transformation of N 2 to organic products remain unknown to date.…”

Section: Introductionmentioning

confidence: 99%

Cyanate Formation via Photolytic Splitting of Dinitrogen

Schluschaß

Borter

Rupp

et al. 2021

JACS Au

Self Cite

View full text Add to dashboard Cite

Light-driven N 2 cleavage into molecular nitrides is an attractive strategy for synthetic nitrogen fixation. However, suitable platforms are rare. Furthermore, the development of catalytic protocols via this elementary step suffers from poor understanding of N–N photosplitting within dinitrogen complexes, as well as of the thermochemical and kinetic framework for coupled follow-up chemistry. We here present a tungsten pincer platform, which undergoes fully reversible, thermal N 2 splitting and reverse nitride coupling, allowing for experimental derivation of thermodynamic and kinetic parameters of the N–N cleavage step. Selective N–N splitting was also obtained photolytically. DFT computations allocate the productive excitations within the {WNNW} core. Transient absorption spectroscopy shows ultrafast repopulation of the electronic ground state. Comparison with ground-state kinetics and resonance Raman data support a pathway for N–N photosplitting via a nonstatistically vibrationally excited ground state that benefits from vibronically coupled structural distortion of the core. Nitride carbonylation and release are demonstrated within a full synthetic cycle for trimethylsilylcyanate formation directly from N 2 and CO.

show abstract

Synthesis of Benzonitrile from Dinitrogen

Cited by 24 publications

References 30 publications

Dinitrogen Fixation: Rationalizing Strategies Utilizing Molecular Complexes

Dinitrogen Fixation: Rationalizing Strategies Utilizing Molecular Complexes

Metal‐Ligand Cooperative Synthesis of Benzonitrile by Electrochemical Reduction and Photolytic Splitting of Dinitrogen

Cyanate Formation via Photolytic Splitting of Dinitrogen

Contact Info

Product

Resources

About