A Model for Protonation of Dinitrogen by Nitrogenase:  Protonation of Coordinated Dinitrogen on Tungsten with Hydrosulfido-Bridged Dinuclear Complexes<sup>1</sup>

Nishibayashi, Yoshiaki; Iwai, Shotaro; Hidai, Masanobu

doi:10.1021/ja981223g

Cited by 41 publications

(19 citation statements)

References 24 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Hydrazido tungsten species were observed when the reaction was performed with only 2 equiv. of 151 or 153 , which points to the operation of a typical mechanism of N 2 protonation on the tungsten center of 16 83…”

Section: N≡n Bond Scission Reactionsmentioning

confidence: 99%

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

et al. 2015

View full text Add to dashboard Cite

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 ...

show abstract

Section: N≡n Bond Scission Reactionsmentioning

confidence: 99%

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

et al. 2015

View full text Add to dashboard Cite

show abstract

“…[88] Coordinated N 2 is transformed into ammonia by the action of hydrosulfido-bridged dinuclear iridium and iron complexes, which may mimic the protonation reactions in the metal-sulfido core of the nitrogenase enzyme. [89] In a rare case, N À H bonds can form by addition of H 2 . The dinuclear zirconium…”

Section: Formation Of N à H Bonds From Coordinated Dinitrogenmentioning

confidence: 99%

Activation of Molecular Nitrogen: Coordination, Cleavage and Functionalization of N₂ Mediated By Metal Complexes

2003

View full text Add to dashboard Cite

show abstract

“…of ammonia on treatment with a sulfido-bridged dinuclear molybdenum complex [{Cp 2 Mo} 2 (l-S)(l-SH) (l-S 2 CH 2 )]OTf under atmospheric pressure of dihydrogen at 258C for an hour. [73] Fryzuk and coworkers have found that a dinuclear zirconium complex with a side-on bridging dinitrogen ligand reacts with molecular dihydrogen to produce a diazenido-bridged dizirconium complex, presumably via the isolable (dinitrogen)(dihydrogen)-bridged dizirconium complex where the N-H bond formation occurs (Scheme 6a), [74] but further ammonia formation was not successful. Formation of similar diazenido-bridged dizirconium or dihafnium complexes has been also reported by Sita and coworkers on treatment of a series of isolable dinitrogen-bridged dizirconium or dihafnium complexes with two atmospheres of dihydrogen.…”

Section: Cleavage Of Dinitrogen Coordinated To Transitionmetal Speciementioning

confidence: 99%

Catalytic Dinitrogen Fixation to Form Ammonia at Ambient Reaction Conditions Using Transition Metal-Dinitrogen Complexes

Tanabe

Nishibayashi

2016

The Chemical Record

Self Cite

View full text Add to dashboard Cite

This paper presents recent progress in catalytic transformation of molecular dinitrogen into ammonia or its equivalents, such as silylamine, especially using transition metal-dinitrogen complexes under ambient reaction conditions. Several catalytic systems have been recently established using molybdenum-, iron-, and cobalt-dinitrogen complexes or their precursors as catalysts, providing new approaches to the development of novel nitrogen fixation under ambient reaction conditions.

show abstract

A Model for Protonation of Dinitrogen by Nitrogenase: Protonation of Coordinated Dinitrogen on Tungsten with Hydrosulfido-Bridged Dinuclear Complexes¹

Cited by 41 publications

References 24 publications

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

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

Activation of Molecular Nitrogen: Coordination, Cleavage and Functionalization of N₂ Mediated By Metal Complexes

Catalytic Dinitrogen Fixation to Form Ammonia at Ambient Reaction Conditions Using Transition Metal-Dinitrogen Complexes

Contact Info

Product

Resources

About

A Model for Protonation of Dinitrogen by Nitrogenase: Protonation of Coordinated Dinitrogen on Tungsten with Hydrosulfido-Bridged Dinuclear Complexes1

Cited by 41 publications

References 24 publications

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

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

Activation of Molecular Nitrogen: Coordination, Cleavage and Functionalization of N2 Mediated By Metal Complexes

Catalytic Dinitrogen Fixation to Form Ammonia at Ambient Reaction Conditions Using Transition Metal-Dinitrogen Complexes

Contact Info

Product

Resources

About

A Model for Protonation of Dinitrogen by Nitrogenase: Protonation of Coordinated Dinitrogen on Tungsten with Hydrosulfido-Bridged Dinuclear Complexes¹

Activation of Molecular Nitrogen: Coordination, Cleavage and Functionalization of N₂ Mediated By Metal Complexes