Methyl Effects on the Stereochemistry and Reactivity of PPP-Ligated Iron Hydride Complexes

Pandey, Bedraj; Krause, Jeanette A.; Guan, Huashi

doi:10.1021/acs.inorgchem.2c03803

Cited by 3 publications

(2 citation statements)

References 52 publications

(43 reference statements)

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“…Iron hydrides have been recognized as highly reactive intermediates in synthetic, biological, and industrial catalytic transformations. − To gain a deeper understanding and model these reactive entities, molecular iron hydrides have been synthesized as focal points for research. These hydrides are stabilized by a range of ligand frameworks, including carbon monoxide, , β-diketiminates, , phosphines, NHC carbenes, , pincer-type ligands, ,,,− and other types of ligands. During synthesis, monomeric iron hydrido complexes with these ligands often lead to the formation of clusters, with hydride-bridged dimers being a common occurrence.…”

Section: Introductionmentioning

confidence: 99%

A Bis-Cyclopentadienyl Ligand-Supported Di-Iron Trihydride Motif as a Synthon for Access to Heterobimetallic Trinuclear Complexes

Tseng,

Ding,

Chen

et al. 2024

Inorg. Chem.

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Herein, we report the synthesis of a flexible bis-cyclopentadienyl ligand L (the doubly deprotonated form of H 2 L (1,3-bis(2,4-di-tert-butylcyclopentadienyldimethylsilyl)benzene)), demonstrating its ability to stabilize a series of di-iron hydrido complexes. Notably, this ligand facilitates the isolation of an unprecedented anionic cyclopentadienyl ligand-supported di-iron trihydride complex, LFe 2 (μ-H) 3 Li(THF) (2), functioning as a synthon for the [Fe 2 (μ-H) 3 ] − core and providing access to heterobimetallic complexes 4−6 with coinage metals.

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Section: Introductionmentioning

confidence: 99%

A Bis-Cyclopentadienyl Ligand-Supported Di-Iron Trihydride Motif as a Synthon for Access to Heterobimetallic Trinuclear Complexes

Tseng,

Ding,

Chen

et al. 2024

Inorg. Chem.

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“…Early studies of iron catalysts for formic acid dehydrogenation relied on simple salts such as FeCl 2 and FeCl 3 or a mixture of Fe 3 (CO) 12 , terpyridine, and a monophosphine ligand . More recent catalyst design has been focused on well-defined iron complexes supported by a phosphorus-based, tridentate/pincer, or tetradentate ligand. Of particular note is ( i Pr PN H P)FeH(CO)(OCHO) [ i Pr PN H P = ( i Pr 2 PCH 2 CH 2 ) 2 NH (see Chart for the structure)] developed by Bernskoetter, Hazari, and Schneider, which catalyzes the release of H 2 from formic acid with turnover numbers (TONs) as high as 983 642 .…”

Section: Introductionmentioning

confidence: 99%

On the Demise of PPP-Ligated Iron Catalysts in the Formic Acid Dehydrogenation Reaction

Pandey,

Krause,

Guan

2023

Inorg. Chem.

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The PPP-ligated iron complexes, cis-( i PrPPRP)FeH2(CO) [ i PrPPRP = (o- i Pr2PC6H4)2PR (R = H or Me)], catalyze the dehydrogenation of formic acid to carbon dioxide but lose their catalytic activity over time. This study focuses on the analysis of the species formed from the degradation of cis-( i PrPPMeP)FeH2(CO) over its course of catalyzing the dehydrogenation reaction. These degradation products include species both soluble and insoluble in the reaction medium. The soluble component of the decomposed catalyst is a mixture of cis-[( i PrPPMeP)FeH(CO)2][(HCO2)(HCO2H) x ], protonated i PrPPMeP, and oxidation products resulting from adventitious O2. The precipitate is solvated Fe(OCHO)2. Further mechanistic investigation suggests that cis-[( i PrPPMeP)FeH(CO)2][(HCO2)(HCO2H) x ] displays diminished but measurable catalytic activity, likely through the displacement of a CO ligand by the formate ion. The formation of Fe(OCHO)2 along with the dissociation of i PrPPMeP is responsible for the eventual loss of catalytic activity.

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Transition metal pincer catalysts for formic acid dehydrogenation: a mechanistic perspective

Kumar,

Adhikary

2024

Front. Chem.

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The storage and transportation of hydrogen gas, a non-polluting alternative to carbon-based fuels, have always been challenging due to its extreme flammability. In this regard, formic acid (FA) is a promising liquid organic hydrogen carrier (LOHC), and over the past decades, significant progress has been made in dehydrogenating FA through transition metal catalysis. In this review, our goal is to provide a detailed insight into the existing processes to expose various mechanistic challenges associated with FA dehydrogenation (FAD). Specifically, methodologies catalyzed by pincer-ligated metal complexes were chosen. Pincer ligands are preferred as they provide structural rigidity to the complexes, making the isolation and analysis of reaction intermediates less challenging and consequently providing a better mechanistic understanding. In this perspective, the catalytic activity of the reported pincer complexes in FAD was overviewed, and more importantly, the catalytic cycles were examined in detail. Further attention was given to the structural modifications, role of additives, reaction medium, and their crucial effects on the outcome.

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Methyl Effects on the Stereochemistry and Reactivity of PPP-Ligated Iron Hydride Complexes

Cited by 3 publications

References 52 publications

A Bis-Cyclopentadienyl Ligand-Supported Di-Iron Trihydride Motif as a Synthon for Access to Heterobimetallic Trinuclear Complexes

A Bis-Cyclopentadienyl Ligand-Supported Di-Iron Trihydride Motif as a Synthon for Access to Heterobimetallic Trinuclear Complexes

On the Demise of PPP-Ligated Iron Catalysts in the Formic Acid Dehydrogenation Reaction

Transition metal pincer catalysts for formic acid dehydrogenation: a mechanistic perspective

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