Kinetics and Pathway Analysis Reveals the Mechanism of a Homogeneous PNP-Iron-Catalyzed Nitrile Hydrogenation DOI
Simon Velasquez Morales, Alan M. Allgeier

Inorganic Chemistry, Journal Year: 2022, Volume and Issue: 62(1), P. 114 - 122

Published: Dec. 21, 2022

Nitrile hydrogenation via the in situ-generated PNP-FeII(H)2CO (1) catalyst leads to a previously inexplicable loss of mass balance. Reaction kinetics, reaction progress analysis, situ pressure nuclear magnetic resonance, and X-ray diffraction analyses reveal mechanism comprising reversible imine self-condensation amine-imine condensation cascades that yield >95% primary amine. Imine has never been reported nitrile mechanism. The is first order hydrogen zero benzonitrile when using 2-propanol as solvent. Variable-temperature analysis revealed values for ΔG298 K⧧ (79.6 ± 26.8 kJ mol-1), ΔH⧧ (90.7 9.7 ΔS⧧ (37 28 J mol-1 K-1), consistent with solvent-mediated proton-shuttled dissociative transition state. This work provides basis future optimization essential data design continuous reactors earth-abundant catalysts.

Language: Английский

Study on the Hydrogenation of Ethyl Stearate to the Fatty Alcohol 1-Octadecanol over Ru on Tungstated Zirconia DOI Open Access

Diego Quintero-Ramos,

Manuel Checa, J.L. Jordá

et al.

Catalysts, Journal Year: 2023, Volume and Issue: 13(10), P. 1362 - 1362

Published: Oct. 11, 2023

Fatty alcohols are important products in the chemical industry, given that they frequently used formulation of surfactants and lubricants. In this context, work describes a catalytic heterogeneous approach for production 1-octadecanol (C18OH) from ethyl stearate (ES) using nanosized Ru-supported on tungstated zirconia (W/Zr). The activity selectivity series catalysts have been studied during hydrogenation ES batch reactor at 175 °C PH2 = 40 bar. so-prepared were characterized by sort characterization techniques (i.e., X-ray diffraction, H2-TPR, etc.), confirming high dispersion higher reducibility Ru nanoparticles W/Zr surface (primarily tetragonal zirconia) with respect to pure zirconia. Overall, significantly active. addition, strong synergistic effect was revealed between W species, according data. Finally, reaction sequence towards fatty alcohol has also elucidated, pointing ester hydrogenolysis aldehyde ulterior latter as main route formation.

Language: Английский

Citations

1
Mechanistic insights on C(acyl)−N functionalisation mediated by late transition metals DOI
V. Pillai, Kaycie R. Malyk, C. Rose Kennedy

et al.

Dalton Transactions, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Analysis of C(acyl)–N functionalisation mechanisms with a focus on recent developments involving unique to the late transition metals.

Language: Английский

Citations

0
Kinetics and Pathway Analysis Reveals the Mechanism of a Homogeneous PNP-Iron-Catalyzed Nitrile Hydrogenation DOI
Simon Velasquez Morales, Alan M. Allgeier

Inorganic Chemistry, Journal Year: 2022, Volume and Issue: 62(1), P. 114 - 122

Published: Dec. 21, 2022

Nitrile hydrogenation via the in situ-generated PNP-FeII(H)2CO (1) catalyst leads to a previously inexplicable loss of mass balance. Reaction kinetics, reaction progress analysis, situ pressure nuclear magnetic resonance, and X-ray diffraction analyses reveal mechanism comprising reversible imine self-condensation amine-imine condensation cascades that yield >95% primary amine. Imine has never been reported nitrile mechanism. The is first order hydrogen zero benzonitrile when using 2-propanol as solvent. Variable-temperature analysis revealed values for ΔG298 K⧧ (79.6 ± 26.8 kJ mol-1), ΔH⧧ (90.7 9.7 ΔS⧧ (37 28 J mol-1 K-1), consistent with solvent-mediated proton-shuttled dissociative transition state. This work provides basis future optimization essential data design continuous reactors earth-abundant catalysts.

Language: Английский

Citations

1