Selectivity of tungsten mediated dinitrogen splitting <i>vs.</i> proton reduction

Schluschaß, Bastian; Abbenseth, Josh; Demeshko, Serhiy; Finger, Markus; Franke, Alicja; Herwig, Christian; Würtele, Christian; Limberg, Christian; Telser, Joshua; Schneider, Sven

doi:10.1039/c9sc03779a

Cited by 39 publications

(55 citation statements)

References 52 publications

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“…The reaction of [(N 2 ){WCl(PNP)} 2 ] ( 1 ) 31 with CO (1 atm) results in quantitative formation of [(N 2 ){WCl(CO)(PNP)} 2 ] ( 2 ) ( Scheme 1 ) within 20 min. Longer reaction times lead to loss of N 2 and formation of [WCl(CO) 2 (PNP)] ( vide infra ).…”

Section: Resultsmentioning

confidence: 99%

“… 3 , 4 As a general feature, the precursors to N 2 splitting exhibit electronic ground state configurations with 10 electrons in the {MNNM} π-MO manifold, such as [(N 2 ){ReCl(PNP)} 2 ] ( D , π 1 4 π 2 4 δ 1 2 δ 2 2 π 3 2 ) or [(N 2 ){MCl(HPNP)} 2 ] 2+ (π 1 4 π 2 4 δ 1 1 δ 2 1 π 3 2 ), respectively (M = Mo, W; PNP = N(CH 2 CH 2 P t Bu 2 ) 2 ). 28 − 31 Full N–N cleavage is associated with an electronic rearrangement from the π*−π–π* to the N–N σ* MO via a zigzag transition state of the {MNNM} core. So far, this simple picture has proven fully consistent with computational electronic structure treatment of related systems.…”

Section: Introductionmentioning

confidence: 99%

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Cyanate Formation via Photolytic Splitting of Dinitrogen

Schluschaß

Borter

Rupp

et al. 2021

JACS Au

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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.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Cyanate Formation via Photolytic Splitting of Dinitrogen

Schluschaß

Borter

Rupp

et al. 2021

JACS Au

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“…Population of this N–N antibonding orbital subsequently promotes full dinitrogen cleavage. Dinitrogen scission was also demonstrated by the analogous tungsten complex [46] …”

Section: Dissociative Mechanismmentioning

confidence: 94%

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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“…The Schrock and Mézailles research groups have reported the formation of molybdenum‐nitride complexes via direct cleavage of dinitrogen from the reduction of molybdenum(III) halide complexes bearing similar pincer ligands under atmospheric pressure of dinitrogen gas although no dinitrogen‐bridged dimolybdenum complexes were observed as key reactive intermediates . More recently, Schneider and co‐workers found that dinitrogen‐bridged dimolybdenum and ditungsten complexes bearing an anionic PNP‐type pincer ligand worked as key reactive intermediates in the process of direct cleavage of dinitrogen under mild reaction conditions . However, no transformations of the nitride complexes into the starting dinitrogen complexes via the corresponding ammonia complexes that would complete the catalytic cycle were seen for the formation of ammonia from dinitrogen.…”

Section: Introductionmentioning

confidence: 99%

Cycling between Molybdenum‐Dinitrogen and ‐Nitride Complexes to Support the Reaction Pathway for Catalytic Formation of Ammonia from Dinitrogen

Arashiba

Tanaka

Yoshizawa

et al. 2020

Chemistry A European J

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Cycling between molybdenum(I)-dinitrogen and molybdenum(IV)-nitridec omplexes was investigated under ambient reactionc onditions. Ak inetics tudyo ft he secondorder reactionr ate for the conversion of the molybdenumdinitrogen complex into the molybdenum-nitride complex indicates that the formation of the dinitrogen-bridged dimolybdenum complex is involved in the rate-determining step. DFT calculations indicate that the molybdenum-dinitrogen complex transformsi nto the molybdenum-nitride complex via direct cleavageo ft he nitrogen-nitrogen triple bond of the bridging dinitrogen ligand of the dinitrogen-bridged dimolybdenum complex. The corresponding reactiono ft he molybdenum-nitride complext ransforming into the molybdenum-dinitrogen complex proceeds via the ligand exchange of ammonia for dinitrogen at the dinitrogen-bridged dimolybdenumc omplexes. An ew modified reactionp athway has been proposedb ased on the findings of our experimental andt heoretical results.

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Selectivity of tungsten mediated dinitrogen splitting vs. proton reduction

Abstract: An N2-bridged ditungsten complex is presented that undergoes N2-splitting or hydrogen evolution upon protonation depending on the acid and reaction conditions. Spectroscopic, kinetic and computational results emphasize the impact of hydrogen bonding on the reaction selectivity.

Cited by 39 publications

References 52 publications

Cyanate Formation via Photolytic Splitting of Dinitrogen

Cyanate Formation via Photolytic Splitting of Dinitrogen

Dinitrogen Fixation: Rationalizing Strategies Utilizing Molecular Complexes

Cycling between Molybdenum‐Dinitrogen and ‐Nitride Complexes to Support the Reaction Pathway for Catalytic Formation of Ammonia from Dinitrogen

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