Photolysis of aqueous [Os(NH3)5(N2)]2+: Dismutation of coordinated dinitrogen

Kunkely, Horst; Vogler, Arnd

doi:10.1016/j.ica.2012.04.021

Cited by 6 publications

(4 citation statements)

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“…For example, the interference of small residual amounts of oxygen may decrease this yield. Such an oxygen effect has been observed for the photolysis of [Os II (NH 3 ) 5 (N 2 )] 2+ [14]. In the context of our present observations it must be kept in mind that in the past the photoreduction of coordinated CO was not considered to be a reasonable possibility for the photolysis of metal carbonyls.…”

Section: Resultssupporting

confidence: 64%

Photoreduction of CO to Methanol. The Photolysis of Aqueous Solutions of [Os(NH₃)₅(CO)]²⁺

Kunkely¹,

Vogler²

2013

Zeitschrift Für Naturforschung B

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Section: Resultssupporting

confidence: 64%

Photoreduction of CO to Methanol. The Photolysis of Aqueous Solutions of [Os(NH₃)₅(CO)]²⁺

Kunkely¹,

Vogler²

2013

Zeitschrift Für Naturforschung B

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“…of NO 2 – (Scheme ). Small amounts of hydroxylamine were detected, which was proposed to be a result of the reaction with water 125. In the absence of O 2 , another pathway is operational.…”

Section: Groupmentioning

confidence: 97%

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

et al. 2015

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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 ...

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“…The highest turn-over-number of ammonia production using complexes of this type reached 84% per iron atom [23]. An osmium-containing complex [(NH 3 )5Os II (N 2 )Os III (NH 3 ) 5 ] 5+ is known to split and reduce N 2 molecules when irradiated with UV light under a mercury lamp [24]. A chalcogel system comprising biomimetic [Mo 2 Fe 6 S 8 ] 3+ clusters can produce ammonia under visible light irradiation [25].…”

Section: Introductionmentioning

confidence: 99%

Enhanced Activity of Titanocene Complex for Electrocatalytic Nitrogen Reduction Reaction

Fijałkowski

2021

Catalysts

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Enhanced titanocene (Cp2TiCl2) based electrocatalytic system for nitrogen reduction was shown, comprising glassy carbon electrode, high level of the catechol redox mediator, optimized binary THF/MeOH solvent and unique design of the reactor having ammonia permeable membrane at the outlet, which allowed constant nitrogen flow through the working solution during entire electrolysis without risk of evaporation of the solvent. Catalytic activity was observed in the potential range of (−1.5)–(−2.3) V, reaching TON of 2.83%, corresponding to the production of 0.566 μmol NH3 (9.64 μg) in 24 h hydrolysis at −2.3 V using 0.02 mmol TiCp2Cl2 (5 mg).

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Photolysis of aqueous [Os(NH3)5(N2)]2+: Dismutation of coordinated dinitrogen

Cited by 6 publications

References 8 publications

Photoreduction of CO to Methanol. The Photolysis of Aqueous Solutions of [Os(NH₃)₅(CO)]²⁺

Photoreduction of CO to Methanol. The Photolysis of Aqueous Solutions of [Os(NH₃)₅(CO)]²⁺

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

Enhanced Activity of Titanocene Complex for Electrocatalytic Nitrogen Reduction Reaction

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Photolysis of aqueous [Os(NH3)5(N2)]2+: Dismutation of coordinated dinitrogen

Cited by 6 publications

References 8 publications

Photoreduction of CO to Methanol. The Photolysis of Aqueous Solutions of [Os(NH3)5(CO)]2+

Photoreduction of CO to Methanol. The Photolysis of Aqueous Solutions of [Os(NH3)5(CO)]2+

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

Enhanced Activity of Titanocene Complex for Electrocatalytic Nitrogen Reduction Reaction

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Product

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Photoreduction of CO to Methanol. The Photolysis of Aqueous Solutions of [Os(NH₃)₅(CO)]²⁺

Photoreduction of CO to Methanol. The Photolysis of Aqueous Solutions of [Os(NH₃)₅(CO)]²⁺