7 research outputs found
Iron(II) Complexes of the Linear <i>rac-</i>Tetraphos‑1 Ligand as Efficient Homogeneous Catalysts for Sodium Bicarbonate Hydrogenation and Formic Acid Dehydrogenation
No full textThe
linear tetraphosphine 1,1,4,7,10,10-hexaphenyl-1,4,7,10-tetraphosphadecane
(tetraphos-1, P4) was used as its <i>rac</i> and <i>meso</i> isomers for the synthesis of both molecularly defined
and in situ formed Fe(II) complexes. These were used as precatalysts
for sodium bicarbonate hydrogenation to formate and formic acid dehydrogenation
to hydrogen and carbon dioxide with moderate to good activities in
comparison to those for literature systems based on Fe. Mechanistic
details of the reaction pathways were obtained by NMR and HPNMR experiments,
highlighting the role of the Fe(II) monohydrido complex [FeH(<i>rac</i>-P4)]<sup>+</sup> as a key intermediate. X-ray crystal
structures of different complexes bearing <i>rac</i>-P4
were also obtained and are described herein
Selective Formic Acid Dehydrogenation Catalyzed by Fe-PNP Pincer Complexes Based on the 2,6-Diaminopyridine Scaffold
No full textFe(II) hydrido carbonyl complexes
supported by PNP pincer ligands
based on the 2,6-diaminopyridine scaffold were studied as homogeneous,
non-precious-metal-based catalysts for selective formic acid dehydrogenation
to hydrogen and carbon dioxide, reaching quantitative yields and high
TONs under mild reaction conditions
Selective Formic Acid Dehydrogenation Catalyzed by Fe-PNP Pincer Complexes Based on the 2,6-Diaminopyridine Scaffold
No full textFe(II) hydrido carbonyl complexes
supported by PNP pincer ligands
based on the 2,6-diaminopyridine scaffold were studied as homogeneous,
non-precious-metal-based catalysts for selective formic acid dehydrogenation
to hydrogen and carbon dioxide, reaching quantitative yields and high
TONs under mild reaction conditions
Selective Formic Acid Dehydrogenation Catalyzed by Fe-PNP Pincer Complexes Based on the 2,6-Diaminopyridine Scaffold
No full textFe(II) hydrido carbonyl complexes
supported by PNP pincer ligands
based on the 2,6-diaminopyridine scaffold were studied as homogeneous,
non-precious-metal-based catalysts for selective formic acid dehydrogenation
to hydrogen and carbon dioxide, reaching quantitative yields and high
TONs under mild reaction conditions
Inner- versus Outer-Sphere Ru-Catalyzed Formic Acid Dehydrogenation: A Computational Study
No full textA detailed
hybrid density functional theory study was carried out
to clarify the mechanism of Ru-catalyzed dehydrogenation of formic
acid in the presence of the octahedral complexes [Ru(κ<sup>4</sup>-NP<sub>3</sub>)Cl<sub>2</sub>] (<b>1</b>) and
[Ru(κ<sup>3</sup>-triphos)(MeCN)<sub>3</sub>](PF<sub>6</sub>)<sub>2</sub> (<b>2·PF</b><sub><b>6</b></sub>) [NP<sub>3</sub> = N(CH<sub>2</sub>CH<sub>2</sub>PPh<sub>2</sub>)<sub>3</sub>, triphos = MeC(CH<sub>2</sub>PPh<sub>2</sub>)<sub>3</sub>]. It was shown that Ru-hydrido vs Ru-formato
species are pivotal to bringing about the efficient release of H<sub>2</sub> and CO<sub>2</sub> following either a metal-centered (inner-sphere)
or a ligand-centered (outer-sphere) pathway, respectively
Inner- versus Outer-Sphere Ru-Catalyzed Formic Acid Dehydrogenation: A Computational Study
No full textA detailed
hybrid density functional theory study was carried out
to clarify the mechanism of Ru-catalyzed dehydrogenation of formic
acid in the presence of the octahedral complexes [Ru(κ<sup>4</sup>-NP<sub>3</sub>)Cl<sub>2</sub>] (<b>1</b>) and
[Ru(κ<sup>3</sup>-triphos)(MeCN)<sub>3</sub>](PF<sub>6</sub>)<sub>2</sub> (<b>2·PF</b><sub><b>6</b></sub>) [NP<sub>3</sub> = N(CH<sub>2</sub>CH<sub>2</sub>PPh<sub>2</sub>)<sub>3</sub>, triphos = MeC(CH<sub>2</sub>PPh<sub>2</sub>)<sub>3</sub>]. It was shown that Ru-hydrido vs Ru-formato
species are pivotal to bringing about the efficient release of H<sub>2</sub> and CO<sub>2</sub> following either a metal-centered (inner-sphere)
or a ligand-centered (outer-sphere) pathway, respectively
Inner- versus Outer-Sphere Ru-Catalyzed Formic Acid Dehydrogenation: A Computational Study
No full textA detailed
hybrid density functional theory study was carried out
to clarify the mechanism of Ru-catalyzed dehydrogenation of formic
acid in the presence of the octahedral complexes [Ru(κ<sup>4</sup>-NP<sub>3</sub>)Cl<sub>2</sub>] (<b>1</b>) and
[Ru(κ<sup>3</sup>-triphos)(MeCN)<sub>3</sub>](PF<sub>6</sub>)<sub>2</sub> (<b>2·PF</b><sub><b>6</b></sub>) [NP<sub>3</sub> = N(CH<sub>2</sub>CH<sub>2</sub>PPh<sub>2</sub>)<sub>3</sub>, triphos = MeC(CH<sub>2</sub>PPh<sub>2</sub>)<sub>3</sub>]. It was shown that Ru-hydrido vs Ru-formato
species are pivotal to bringing about the efficient release of H<sub>2</sub> and CO<sub>2</sub> following either a metal-centered (inner-sphere)
or a ligand-centered (outer-sphere) pathway, respectively
