Reactivity of molybdenum–nitride complex bearing pyridine-based PNP-type pincer ligand toward carbon-centered electrophiles

Itabashi, Takayuki; Arashiba, Kazuya; Kuriyama, Shogo; Nishibayashi, Yoshiaki

doi:10.1039/d1dt03952k

Cited by 8 publications

(11 citation statements)

References 66 publications

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“…In addition, the formation of the isocyanate complexes from the reaction of the corresponding nitride complexes with CO was a key step for previously reported isocyanate derivatives synthesis from dinitrogen 22 , 25 . In contrast to these reports, the reaction of nitride complex 1 with CO did not afford an isocyanate complex but a cationic nitride carbonyl complex 33 . Therefore, this stoichiometric reaction is noteworthy as an alternative synthetic method for isocyanate derivatives from dinitrogen.…”

Section: Resultscontrasting

confidence: 83%

“…An iodo ligand and a chloro ligand are presented in cis and trans positions to the carbamate ligand, respectively. The bond distances and angles of 2 are similar to that of an acylimide complex [Mo(NCOCH 2 Ph)ICl(PNP)] 33 .…”

Section: Resultsmentioning

confidence: 67%

“…2a) [30][31][32] . In addition, we have investigated the reactions of 1 with various carbon-centred electrophiles towards preparing organonitrogen compounds 33 . The stoichiometric amount of organic amide is successfully synthesised from the reaction of 1 with acyl chloride and water.…”

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confidence: 99%

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

et al. 2022

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Dinitrogen is an abundant and promising material for valuable organonitrogen compounds containing carbon–nitrogen bonds. Direct synthetic methods for preparing organonitrogen compounds from dinitrogen as a starting reagent under mild reaction conditions give insight into the sustainable production of valuable organonitrogen compounds with reduced fossil fuel consumption. Here we report the catalytic reaction for the formation of cyanate anion (NCO−) from dinitrogen under ambient reaction conditions. A molybdenum–carbamate complex bearing a pyridine-based 2,6-bis(di-tert-butylphosphinomethyl)pyridine (PNP)-pincer ligand is synthesized from the reaction of a molybdenum–nitride complex with phenyl chloroformate. The conversion between the molybdenum–carbamate complex and the molybdenum–nitride complex under ambient reaction conditions is achieved. The use of samarium diiodide (SmI2) as a reductant promotes the formation of NCO− from the molybdenum–carbamate complex as a key step. As a result, we demonstrate a synthetic cycle for NCO− from dinitrogen mediated by the molybdenum–PNP complexes in two steps. Based on this synthetic cycle, we achieve the catalytic synthesis of NCO− from dinitrogen under ambient reaction conditions.

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Section: Resultscontrasting

confidence: 83%

Section: Resultsmentioning

confidence: 67%

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

et al. 2022

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“…[40] The reactions of 103 with phenylisocyanate and diphenylketene yielded the ureato complex 104 a and acylimido complex 104 b, respectively (Scheme 20). [41] In both reactions, two molecules of substrate were incorporated. The reaction may proceed via intermediate S, formed by the addition of the nitrido ligand and a benzylic proton to the heteroallene.…”

Section: Dinitrogen Functionalization With Heteroallenesmentioning

confidence: 99%

Dinitrogen Activation and Addition to Unsaturated C−E (E=C, N, O, S) Bonds Mediated by Transition Metal Complexes

et al. 2023

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Dinitrogen (N2) activation and functionalization is of fundamental interest and practical importance. This review focuses on N2 activation and addition to unsaturated substrates, including carbon monoxide, carbon dioxide, heteroallenes, aldehydes, ketones, acid halides, nitriles, alkynes, and allenes, mediated by transition metal complexes, which afforded a variety of N−C bond formation products. Emphases are placed on the reaction modes and mechanisms. We hope that this work would stimulate further explorations in this challenging field.

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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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Reactivity of molybdenum–nitride complex bearing pyridine-based PNP-type pincer ligand toward carbon-centered electrophiles

Abstract: A molybdenum-nitride complex bearing a pyridine-based PNP-type pincer ligand derived from dinitrogen is reacted with various kinds of carbon-centered electrophiles to functionalize the nitride ligand in the molybdenum complex. Methylation...

Cited by 8 publications

References 66 publications

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

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

Dinitrogen Activation and Addition to Unsaturated C−E (E=C, N, O, S) Bonds Mediated by Transition Metal Complexes

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

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