Cyclopentadienone Iron Tricarbonyl Complexes-Catalyzed Hydrogen Transfer in Water

Ndiaye, Daouda; Coufourier, Sébastien; Mbaye, Mbaye Diagne; Gaillard, Sylvain; Renaud, Jean‐Luc

doi:10.3390/molecules25020421

Cited by 12 publications

(10 citation statements)

References 50 publications

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“…Similarly, Renaud et al reported an N′N′-dimethyl-3,4ethyleneamino-substituted cyclopentadienone iron complex featuring phenyl groups flanking the C�O double bond in the ligand, which also performed better than the TMSsubstituted Knolker complex. 31−34 Furthermore, Coufourier et al 12 and Ndiaye et al 11 reported the use of doubly positively charged complexes for CO 2 hydrogenation and C�X (X = N, O) double bond reduction, respectively, both with aryl groups flanking the C�O double of the ligand, for which it was found that these complexes also perform better than the TMSsubstituted derivatives.…”

Section: Synthesis and Characteristicsmentioning

confidence: 99%

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Cyclopentadienone Iron Complex-Catalyzed Hydrogenation of Ketones: An Operando Spectrometric Study Using Pressurized Sample Infusion-Electrospray Ionization-Mass Spectrometry

Bütikofer

Chen

2022

Organometallics

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The sulfonate charge-tagged cyclopentadienone iron complexes [Fe R (MeCN)(CO) 2 -SO 3 ]Na (R = TMS, t Bu) were prepared and used for mechanistic investigations using pressurized sample infusion-electrospray ionization-mass spectrometry in the hydrogenation of acetophenone. Reactions were conducted in a mixed aqueous/alcoholic solvent. Based on kinetic and mass spectrometric experiments, information about the operating reaction mechanism was obtained. Furthermore, analysis of the kinetic profiles and mass spectra indicated catalyst decomposition. By analysis of the mass spectrometric results, the decomposition cascade was found to start by solvolysis of the trimethylsilyl (TMS) groups flanking the carbonyl group in the cyclopentadienone ligand of the catalyst. Subsequent dimerization, comproportionation to form Fe(I) radical species, and formation of catalytically inactive iron tricarbonyl species were observed, limiting the catalyst lifetime. Replacement of the TMS groups by non-hydrolyzable tert-butyl groups leads to a significant increase in the observed turnover frequency and catalyst longevity. The turnover number, determined to be approximately 65 under standardized reaction conditions, could be increased to >1000 by the mechanism-guided structural change in the catalyst. No compounds corresponding to Fe(I) species or dimerization products could be identified in this case. The present study suggests that for hydrogenations with cyclopentadienone iron complexes, the use of alkyl groups flanking the C�O double bond in the ligand is beneficial over the use of silyl groups when conducted in aqueous media.

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Section: Synthesis and Characteristicsmentioning

confidence: 99%

“…The charge was introduced to enhance solubility. An improved version of this complex was described in 2020, also by Renaud and co-workers. , It features a doubly charged structure and was used as a transfer hydrogenation catalyst in aqueous solution. Its structure is also shown in Chart .…”

Section: Introductionmentioning

confidence: 99%

Cyclopentadienone Iron Complex-Catalyzed Hydrogenation of Ketones: An Operando Spectrometric Study Using Pressurized Sample Infusion-Electrospray Ionization-Mass Spectrometry

Bütikofer

Chen

2022

Organometallics

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“…Instead, the active catalyst is generated either by chemical decarboxylation of the corresponding CPD iron tricarbonyl complex, typically by trimethylamine- N -oxide, , or by thermal dissociation of a weakly coordinating ligand such as a nitrile . Based on this mode of activation, numerous CPD iron precatalysts were introduced, e.g., tetracyclone complexes such as II , or bicyclic systems such as III with amino substituents in the 3,4-positions. − The ability of these and related complexes to serve as hydrogenation ,,,,− as well as dehydrogenation ,,− catalysts also enabled their use in several “hydrogen-borrowing” reactions such as reductive amination ,,− or alkylation reactions. ,− Asymmetric CPD iron complexes were also introduced and employed for the asymmetric hydrogenation of ketones. ,,,− …”

Section: Introductionmentioning

confidence: 99%

Tetraaminocyclopentadienone Iron Complexes as Hydrogenation Catalysts

Hackl

Bockhardt

et al. 2022

Organometallics

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A series of symmetric and asymmetric tetraaminocyclopentadienone iron tricarbonyl complexes were prepared from Fe(CO)5 and the diaminoacetylenes (DAA) R2NCCNR2 (NR2 = piperidinyl, 4-methylpiperidinyl, homopiperidinyl) via intermediate ferracyclobutenone complexes. In the presence of trimethylamine-N-oxide, the reactions with acetonitrile afforded the corresponding iron dicarbonyl acetonitrile complexes, which served as highly active precatalysts for the transfer hydrogenation of aldehydes, ketones, and imines with isopropanol as the hydrogen source and for the hydrogenation of aldehydes and ketones with dihydrogen under comparatively mild reaction conditions (3 bar H2 pressure, room temperature). Density functional theory (DFT) calculations were performed to reveal the mechanism of the isopropanol-mediated transfer hydrogenation of benzaldehyde and acetophenone, which is likely to involve a catalytically active hydroxycyclopentadienyl iron dicarbonyl hydride species. Dihydrogen transfer from the latter onto benzaldehyde and acetophenone occurs in a concerted manner with exceptionally low activation barriers following the established outer-sphere mechanism.

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“…Simultaneously, they have successfully demonstrated their catalytic activity in reductive amination and transfer hydrogenation of aldehydes in water (Scheme 20B−C) [88] . To avoid the use of large amount of hydride and concomitant formation of waste, they developed a catalytic system in which formate derivatives have been used as hydride donor.…”

Section: Hydrogenation and Transfer Hydrogenationmentioning

confidence: 99%

(Cyclopentadienone)iron Complexes: Synthesis, Mechanism and Applications in Organic Synthesis

Akter

Anbarasan

2021

Chemistry An Asian Journal

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(Cyclopentadienone)iron tricarbonyl complexes are catalytically active, inexpensive, easily accessible and air‐stable that are extensively studied as an active pre‐catalyst in homogeneous catalysis. Its versatile catalytic activity arises exclusively due to the presence of a non‐innocent ligand, which can trigger its unique redox properties effectively. These complexes have been employed widely in (transfer)hydrogenation (e. g., reduction of polar multiple bonds, Oppenauer‐type oxidation of alcohols), C−C and C−N bond formation (e. g., reductive aminations, α‐alkylation of ketones) and other synthetic transformations. In this review, we discuss the remarkable advancement of its various synthetic applications along with synthesis and mechanistic studies, until February 2021.

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Cyclopentadienone Iron Tricarbonyl Complexes-Catalyzed Hydrogen Transfer in Water

Cited by 12 publications

References 50 publications

Cyclopentadienone Iron Complex-Catalyzed Hydrogenation of Ketones: An Operando Spectrometric Study Using Pressurized Sample Infusion-Electrospray Ionization-Mass Spectrometry

Cyclopentadienone Iron Complex-Catalyzed Hydrogenation of Ketones: An Operando Spectrometric Study Using Pressurized Sample Infusion-Electrospray Ionization-Mass Spectrometry

Tetraaminocyclopentadienone Iron Complexes as Hydrogenation Catalysts

(Cyclopentadienone)iron Complexes: Synthesis, Mechanism and Applications in Organic Synthesis

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