Ammonia synthesis in the presence of rhodium-ruthenium-iridium carbonyl clusters

Fedoseev, I. V.; Соловьев, Н В

doi:10.1134/s0036023607070030

Cited by 5 publications

(1 citation statement)

References 4 publications

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“…The only example of a homogeneous system that contains ruthenium has been reported for a Ru–Ir–Rh carbonyl cluster dissolved in water at pH = 12. In the presence of N 2 and CO at 70 °C, up to 0.59 % ammonia was formed; however, no insight on the actual mechanism (or even the structure of pre‐catalyst) was provided 122…”

Section: Groupmentioning

confidence: 99%

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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Section: Groupmentioning

confidence: 99%

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

et al. 2015

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The dominant steric effect in the synthesis of ammine hydrido- and chlorido-Ru(II)- N , N -dimethylhydrazine and mixed alkyl–aryl phosphine complexes: Novel methyldiazene reduction intermediates

Ali

Singleton

Meijboom

2015

Inorganica Chimica Acta

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Computational Study of Metal–Dinitrogen Keggin-Type Polyoxometalate Complexes [PW₁₁O₃₉M^IIN₂)]^5– (M = Ru, Os, Re, Ir): Bonding Nature and Dinitrogen Splitting

Liu

Zheng

2015

Inorg. Chem.

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Molecular geometry, electronic structure, and metal-dinitrogen bonding nature of a series of metal-dinitrogen derivatives of Keggin-type polyoxometalates (POMs) [PW11O39M(II)N2)](5-) (M = Ru, Os, Re, Ir) have been studied by using a density functional theory (DFT) method with the M06L functional. Among these Keggin-type POM complexes, Os- and Re-substituted POM complexes are the most active for N2 adsorption with considerable adsorption energy. The electronic structure analysis shows that Os(II) and Re(II) centers in their metal-dinitrogen POM complexes possess π(2)xzπ(2)yzπ(2)xy and π(2)xzπ(2)yzπ(1)xy configurations, respectively. DFT-M06L calculations show that the possible synthesis routes proposed in this work for the Ru-, Os-, and Re-dinitrogen POM complexes are thermodynamically feasible under various solvent environments. Meanwhile, the Re-dinitrogen POM complex was assessed for the direct cleavage of dinitrogen molecule. In the reaction mechanism, a dimeric Keggin-type POM derivative of rhenium could represent the intermediate which undergoes N-N bond scission. The calculated free energy barrier (ΔG(⧧)) for a transition state with a zigzag conformation is 16.05 kcal mol(-1) in tetrahydrofuran, which is a moderate barrier for the cleavage of the N-N bond when compared with the literature values. In conclusion, regarding the direct cleavage of the dinitrogen molecule, the findings would be very useful to guide the search for a potential N2 cleavage compound into totally inorganic POM fields.

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Ammonia synthesis in the presence of rhodium-ruthenium-iridium carbonyl clusters

Cited by 5 publications

References 4 publications

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

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

The dominant steric effect in the synthesis of ammine hydrido- and chlorido-Ru(II)- N , N -dimethylhydrazine and mixed alkyl–aryl phosphine complexes: Novel methyldiazene reduction intermediates

Computational Study of Metal–Dinitrogen Keggin-Type Polyoxometalate Complexes [PW₁₁O₃₉M^IIN₂)]^5– (M = Ru, Os, Re, Ir): Bonding Nature and Dinitrogen Splitting

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Ammonia synthesis in the presence of rhodium-ruthenium-iridium carbonyl clusters

Cited by 5 publications

References 4 publications

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

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

The dominant steric effect in the synthesis of ammine hydrido- and chlorido-Ru(II)- N , N -dimethylhydrazine and mixed alkyl–aryl phosphine complexes: Novel methyldiazene reduction intermediates

Computational Study of Metal–Dinitrogen Keggin-Type Polyoxometalate Complexes [PW11O39MIIN2)]5– (M = Ru, Os, Re, Ir): Bonding Nature and Dinitrogen Splitting

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Computational Study of Metal–Dinitrogen Keggin-Type Polyoxometalate Complexes [PW₁₁O₃₉M^IIN₂)]^5– (M = Ru, Os, Re, Ir): Bonding Nature and Dinitrogen Splitting