Hydrogenation of CO2, carbonyl and imine substrates catalyzed by [IrH3(PhPNHP)] complex

Ayyappan, Ramaraj; Nethaji, Munirathinam; Jagirdar, Balaji R.

doi:10.1016/j.jorganchem.2018.12.017

Cited by 8 publications

(9 citation statements)

References 78 publications

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“…127 Highly active Ir-PNP catalysts for the hydrogenation of CO 2 in basic medium have been also developed. 128 Trihydrideiridium(III) complexes IrH 3 {k 3 -P,N,P-[py(CH 2 P i Pr 2 ) 2 ]} (56) 129 and IrH 3 {k 3 -P,N,P-[HN(CH 2 CH 2 PPh 2 ) 2 ]} (57), 123 bearing neutral P,N,P-pincer ligands, also promote the hydrogenation of CO 2 to potassium formate, in KOH solutions in water containing tetrahydrofuran. Scheme 22 shows the proposed cycle for the reaction catalyzed by 56.…”

Section: Hydrogenation Of Comentioning

confidence: 99%

“…Although some complexes resulting from very particular C-F ruptures have been isolated, 220 polyhydride catalysts for this interesting class of reactions are limited to a family of half-sandwich ruthenium-trihydrides derivatives studied by Nikonov and coworkers. 210 Complexes RuH 3 (Z 5 -C 5 R 5 )L (R = H, L = IPr (58), IMes (117), P i Pr 3 (116), PPh 3 (123); R = Me,…”

Section: Hydrodefluorination Of Aromatic Compoundsmentioning

confidence: 99%

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Homogeneous catalysis with polyhydride complexes

2022

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Section: Hydrogenation Of Comentioning

confidence: 99%

Section: Hydrodefluorination Of Aromatic Compoundsmentioning

confidence: 99%

Homogeneous catalysis with polyhydride complexes

2022

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“…In particular, pincer ligands of the type R PN H P [HN(CH 2 CH 2 PR 2 ) 2 , where R = Et, i Pr, Cy, t Bu, or Ph] have attracted significant interest because of their ability to support highly active catalysts for a wide variety of transformations . For example, R PN H P-supported complexes have been extensively utilized to perform dehydrogenation and hydrogenation reactions relevant to both renewable energy storage − and the synthesis of fine and commodity chemicals. − Notably, the complex Ru-MACHO [( Ph PN H P)RuHCl(CO)] is used commercially in the hydrogenation of esters . As a result of the high activity and versatility of catalysts supported by R PN H P ligands, a large amount of research has been performed to understand the effects of varying the substituents on the phosphine donors of R PN H P-type ligands, and there is considerable understanding about how to optimize these substituents to maximize catalytic activity. ,,,,,,,,,,,− ,, Conversely, there are few reports exploring the consequences of changing the substituent on the nitrogen donor, and there is little knowledge about how this impacts catalytic performance (Figure a).…”

Section: Introductionmentioning

confidence: 99%

Control of Catalyst Isomers Using an N-Phenyl-Substituted RN(CH₂CH₂PⁱPr₂)₂ Pincer Ligand in CO₂ Hydrogenation and Formic Acid Dehydrogenation

et al. 2021

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2 ) 2 ], was synthesized and characterized. The ligand was coordinated to ruthenium, and a series of hydride-containing complexes were isolated and characterized by NMR and IR spectroscopies, as well as X-ray diffraction. Comparisons to previously published analogues ligated by iPr PN H P and iPr PN Me P [CH 3 N(CH 2 CH 2 P i Pr 2 ) 2 ] illustrate that there are large changes in the coordination chemistry that occur when the nitrogen substituent of the pincer ligand is altered. For example, ruthenium hydrides supported by the iPr PN Ph P ligand always form the syn isomer (where syn/anti refer to the relative orientation of the group on nitrogen and the hydride ligand on ruthenium), whereas complexes supported by iPr PN H P form the anti isomer and complexes supported by iPr PN Me P form a mixture of syn and anti isomers. We evaluated the impact of the nitrogen substituent of the pincer ligand in catalysis by comparing a series of iPr PN R P (R = H, Me, Ph)-ligated ruthenium hydride complexes as catalysts for formic acid dehydrogenation and carbon dioxide (CO 2 ) hydrogenation to formate. The iPr PN Ph P-ligated species is the most active for formic acid dehydrogenation, and mechanistic studies suggest that this is likely because there are kinetic advantages for catalysts that operate via the syn isomer. In CO 2 hydrogenation, the iPr PN Ph P-ligated species is again the most active under our optimal conditions, and we report some of the highest turnover frequencies for homogeneous catalysts. Experimental and theoretical insights into the turnover-limiting step of catalysis provide a basis for the observed trends in catalytic activity. Additionally, the stability of our complexes enabled us to detect a previously unobserved autocatalytic effect involving the base that is added to drive the reaction. Overall, by modifying the nitrogen substituent on the MACHO ligand, we have developed highly active catalysts for formic acid dehydrogenation and CO 2 hydrogenation and also provided a framework for future catalyst development.

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“…A TON of 144 was afforded at 100 °C for 14 h or 25 °C for 19 h. The highest TOF of 47 h −1 was obtained at 80 °C. In 2019, Jagirdar showed the iridium trihydride complex [IrH 3 (PN H P)] 87 (Scheme 74) as an active catalyst for the hydrogenation of CO 2 to formate [650]. The reaction was carried out in aqueous 1 M KOH solution, with 0.2 mol% of 87, at 14 bar of H 2 and CO 2 (1:1).…”

Section: Scheme 73 Co2 Hydrogenation Catalyzed By Fe-pnp Isonitrile Complexes Proposed By Bernskoettermentioning

confidence: 99%

Recent Progress with Pincer Transition Metal Catalysts for Sustainability

2020

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Our planet urgently needs sustainable solutions to alleviate the anthropogenic global warming and climate change. Homogeneous catalysis has the potential to play a fundamental role in this process, providing novel, efficient, and at the same time eco-friendly routes for both chemicals and energy production. In particular, pincer-type ligation shows promising properties in terms of long-term stability and selectivity, as well as allowing for mild reaction conditions and low catalyst loading. Indeed, pincer complexes have been applied to a plethora of sustainable chemical processes, such as hydrogen release, CO2 capture and conversion, N2 fixation, and biomass valorization for the synthesis of high-value chemicals and fuels. In this work, we show the main advances of the last five years in the use of pincer transition metal complexes in key catalytic processes aiming for a more sustainable chemical and energy production.

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Hydrogenation of CO2, carbonyl and imine substrates catalyzed by [IrH3(PhPNHP)] complex

Cited by 8 publications

References 78 publications

Homogeneous catalysis with polyhydride complexes

Homogeneous catalysis with polyhydride complexes

Control of Catalyst Isomers Using an N-Phenyl-Substituted RN(CH₂CH₂PⁱPr₂)₂ Pincer Ligand in CO₂ Hydrogenation and Formic Acid Dehydrogenation

Recent Progress with Pincer Transition Metal Catalysts for Sustainability

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Hydrogenation of CO2, carbonyl and imine substrates catalyzed by [IrH3(PhPNHP)] complex

Cited by 8 publications

References 78 publications

Homogeneous catalysis with polyhydride complexes

Homogeneous catalysis with polyhydride complexes

Control of Catalyst Isomers Using an N-Phenyl-Substituted RN(CH2CH2PiPr2)2 Pincer Ligand in CO2 Hydrogenation and Formic Acid Dehydrogenation

Recent Progress with Pincer Transition Metal Catalysts for Sustainability

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Control of Catalyst Isomers Using an N-Phenyl-Substituted RN(CH₂CH₂PⁱPr₂)₂ Pincer Ligand in CO₂ Hydrogenation and Formic Acid Dehydrogenation