Direct synthesis of cyanate anion from dinitrogen catalysed by molybdenum complexes bearing pincer-type ligand

Itabashi, Takayuki; Arashiba, Kazuya; Egi, Akihito; Tanaka, Hiromasa; Sugiyama, Keita; Suginome, Shun; Kuriyama, Shogo; Yoshizawa, Kazunari; Nishibayashi, Yoshiaki

doi:10.1038/s41467-022-33809-5

Cited by 35 publications

(30 citation statements)

References 39 publications

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“…As described in here, we consider that the use of the BDFE(N-H) values of key reactive intermediates, such as molybdenum-imide, molybdenum-amide and molybdenum-ammine complexes estimated by DFT calculations provides a suitable and reliable predicting method to develop more effective catalysts under ambient reaction conditions. The catalysts successfully developed will be applied not only to the catalytic nitrogen fixation driven by visible light 62 and electrochemical energy, but also to the catalytic formation of nitrogen-containing organic compounds directly from nitrogen gas under mild reaction conditions 63 . We believe that these findings can contribute to the development of an environmentally friendly next-generation nitrogen-fixation system in the near future.…”

Section: Discussionmentioning

confidence: 99%

Catalytic production of ammonia from dinitrogen employing molybdenum complexes bearing N-heterocyclic carbene-based PCP-type pincer ligands

et al. 2023

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Mechanistic insight into the catalytic production of ammonia from dinitrogen is needed to improve the synthesis of this vital molecule. Here we study the use of samarium diiodide (SmI2) and water in the presence of molybdenum complexes that bear PCP-type pincer ligands to synthesize ammonia. The proton-coupled electron transfer during the formation of a N–H bond on the molybdenum imide complex was found to be the rate-determining step at high catalyst concentrations. Additionally, the dimerization step of the catalyst became the rate-determining step at low catalyst concentrations. We designed PCP-type pincer ligands with various substituents at the 5- and 6-positions and observed that electron-withdrawing groups promoted the reaction rate, as predicted by density functional theory calculations. A molybdenum trichloride complex that bears a trifluoromethyl group functioned as the most effective catalyst and produced up to 60,000 equiv. ammonia based on the molybdenum atom of the catalyst, with a molybdenum turnover frequency of up to 800 equiv. min−1. The findings reported here can contribute to the development of an environmentally friendly next-generation nitrogen-fixation system.

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Section: Discussionmentioning

confidence: 99%

Catalytic production of ammonia from dinitrogen employing molybdenum complexes bearing N-heterocyclic carbene-based PCP-type pincer ligands

et al. 2023

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“…This goal first began in the 1960s, when Vol’pin synthesized aniline from dinitrogen by reacting titanium salts with PhLi under a dinitrogen atmosphere . Most recently, Nishibayashi et al provided the first successful example of the catalytic transformation of N 2 to NCO – under ambient reaction conditions . Holland et al reported a remarkable milestone to carry out N 2 coupling with arene to generate aniline by the key step of aryl group migration to the partial silylated iron-dinitrogen complex (Figure B) …”

Section: Introductionmentioning

confidence: 99%

“…9 Most recently, Nishibayashi et al provided the first successful example of the catalytic transformation of N 2 to NCO − under ambient reaction conditions. 10 Holland et al reported a remarkable milestone to carry out N 2 coupling with arene to generate aniline by the key step of aryl group migration to the partial silylated irondinitrogen complex (Figure 1B). 11 N 2 activation and direct insertion into a non-activated aliphatic Csp 3 −H bond to form an aliphatic C−N bond seems a very challenging goal.…”

Section: ■ Introductionmentioning

confidence: 99%

Direct Incorporation of Dinitrogen into an Aliphatic C–H Bond

Xie

Huang

et al. 2023

J. Am. Chem. Soc.

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The activation of dinitrogen (N 2 ) and direct incorporation of its N atom into C−H bonds to create aliphatic C−N compounds remains unresolved. Incompatible conditions between dinitrogen reduction and C−H functionalization make this process extremely challenging. Herein, we report the first example of dinitrogen insertion into an aliphatic Csp 3 −H bond on the ligand scaffold of a 1,3-propane-bridged [N 2 N] 2− -type dititanium complex. Mechanistic investigations on the behaviors of dinuclear and mononuclear Ti complexes indicated the intramolecular synergistic effect of two Ti centers at a C−N bond-forming step. Computational studies revealed the critical isomerization between the inactive side-on N 2 complex and the active nitridyl complex, which is responsible for the Csp 3 −H amination. This strategy maps an efficient route toward the future synthesis of aliphatic amines directly from N 2 .

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“…In principle, the addition of an activated N 2 unit to unsaturated organic substrates could offer an atom-efficient route for the synthesis of organonitrogen compounds. However, studies toward this goal remained limited despite great interest and recent advances. − The nucleophilic addition of N 2 or N 2 -derived nitrido and imido species to unsaturated carbon-heteroatom bonds such as CO, − CO 2 , ,,− aldehydes/ketones, − acid halides, − nitriles, , and heteroallenes ,,,,− has been reported. However, the addition reaction of N 2 with unsaturated C–C bonds has remained almost unexplored to date. , In particular, the addition of an N 2 unit to an α,β-unsaturated carbonyl compound through the C–N bond formation to produce an NN-functionalized organic compound has not been reported previously.…”

Section: Introductionmentioning

confidence: 99%

Aza-Michael Addition of Dinitrogen to α,β-Unsaturated Carbonyl Compounds in a Dititanium Framework

Zhuo,

Yang,

Zhou

et al. 2023

J. Am. Chem. Soc.

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The direct use of dinitrogen (N 2 ) as a building block for the synthesis of NN-containing organic compounds is of fundamental interest and practical importance but has remained a formidable challenge to date. Here, we report an unprecedented 1,4-conjugate (aza-Michael) addition of N 2 to α,β-unsaturated carbonyl compounds in a dititanium framework. The resulting hydrazinopropenolate products could be easily converted to diverse NN-containing organic compounds such as β-hydrazinefunctionalized esters and amides, pyrazolidinones, and pyrazolines depending on the types of Michael acceptors through protonation with MeOH. Further transformations of a hydrazinopropenolate titanium complex through C−C and N−C bond formations with electrophiles such as CO 2 and benzaldehyde have also been achieved. The mechanistic details of the N 2 addition reaction have been elucidated by computational studies, revealing the importance of redox-active metal centers in this event. This work showcases the potential of using N 2 as a building block for the synthesis of NN-containing organic compounds through activation and functionalization in a molecular metal framework.

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Direct synthesis of cyanate anion from dinitrogen catalysed by molybdenum complexes bearing pincer-type ligand

Cited by 35 publications

References 39 publications

Catalytic production of ammonia from dinitrogen employing molybdenum complexes bearing N-heterocyclic carbene-based PCP-type pincer ligands

Catalytic production of ammonia from dinitrogen employing molybdenum complexes bearing N-heterocyclic carbene-based PCP-type pincer ligands

Direct Incorporation of Dinitrogen into an Aliphatic C–H Bond

Aza-Michael Addition of Dinitrogen to α,β-Unsaturated Carbonyl Compounds in a Dititanium Framework

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