Propane activation by MC5H+5 (M=Ni and Co): An experimental and theoretical work

Innorta, G.; Torroni, Sandro

doi:10.1016/j.jorganchem.2007.09.011

Cited by 5 publications

(4 citation statements)

References 39 publications

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“…It was anticipated that results would provide guidance for subsequent studies of the cyclic amines piperidine, pyrrolidine and N -methylpyrrolidine. Previous studies of the electronic structure for the reagent cations [CpM] + (M = Fe, Co, Ni) ,, illustrate the occurrence of open-shell configurations, e.g., doublet for Co and triplet for Ni. Application of our computational procedure to this system confirmed these assignments, and for singlet [CpFe(benzene)] + , and doublet [CpCo(benzene)] + . , Thus, all organometallic species studied herein were examined as singlets, triplets and quintets for d 6 Fe II , doublets and quartets for d 7 Co II , and singlets and triplets for d 8 Ni II .…”

Section: Resultsmentioning

confidence: 98%

“…In a reaction with cyclohexane, it formed cyclohexene, cyclohexadiene, and benzene complexes (Scheme ). Innorta and Torroni also examined reactions of [CpNi] + and [CpCo] + with propane, which resulted in dehydrogenation without the production of methane as a cracking product. Ridge and co-workers studied reactions of [CpCo] + and [CpNi] + with multiple alkanes and found that they promote their dehydrogenation and cracking. , All three [CpM] + (M = Ni, Co, Fe) were shown to dehydrogenate silicon-substituted cyclohexanes resulting in elimination of one, two, and three hydrogen molecules in various proportions .…”

Section: Introductionmentioning

confidence: 99%

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Catalytic Dehydrogenation of Liquid Organic Hydrogen Carrier Model Compounds by CpM⁺ (M = Fe, Co, Ni) in the Gas Phase

et al. 2022

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Although there is much interest in developing liquid organic hydrogen carriers (LOHCs) and new metal catalysts to release hydrogen on demand for application in energy generation, few studies have provided mechanistic insights into the crucial metal-catalyzed dehydrogenation reactions. Here we use multistage mass spectrometry experiments and DFT calculations to examine the dehydrogenation of the LOHC model compounds cyclohexane, pyrrolidine, N-methylpyrrolidine, and piperidine by the half-sandwich cyclopentadienyl cations, [CpM]+ (M = Fe, Co, and Ni). The [CpM]+ ions were generated via collision-induced dissociation (CID) of precursor ions generated via electrospray ionization (ESI) of solutions of the compounds CpFe(CO)2I, Cp2Ni, and Cp2Co. The [CpFe]+ ion was found to catalyze triple dehydrogenation of cyclohexane to benzene via a combination of ion–molecule reactions (IMR) and CID experiments. Reactions of [CpM]+ (M = Co, Ni) were found to be more complex as dehydrogenation was accompanied by significant cyclohexane ring cleavage. Reactions of [CpFe]+ with the N-heterocyclic model compounds showed catalytic double dehydrogenation of pyrrolidine/N-methylpyrrolidine and triple dehydrogenation of piperidine. However, multiple side reactions were found, especially in the case of N-methylpyrrolidine and piperidine. They included proton transfer/hydride abstraction to/from the LOHC model methyl loss from the N-methylpyrrolidine complex, and NH2/NH3 extrusion from the piperidine complex. DFT calculations shed light on the structure of the key intermediates in all these systems.

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Section: Resultsmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

Catalytic Dehydrogenation of Liquid Organic Hydrogen Carrier Model Compounds by CpM⁺ (M = Fe, Co, Ni) in the Gas Phase

et al. 2022

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“…Cationic nickel atoms react at about a 10 % efficiency with simple alkanes via C−H and C−C activation . Ligated transition metal cations have been studied extensively in the gas phase and give a variety of reactivities . The dehydrogenation mechanism of alkanes by complex I is depicted in Figure .…”

Section: Methodsmentioning

confidence: 99%

“…[30][31][32][33] Ligated transition metal cations have been studied extensively in the gas phase and give av ariety of reactivities. [32,[34][35][36][37][38] Thed ehydrogenation mechanism of alkanes by complex I is depicted in Figure 4. While we are unable to introduce gaseous neutral reagents into the ion trap using our experimental setup,D FT calculations suggest complex I would display similar dehydrogenation reactivity with smaller, gaseous alkanes,s uch as ethane and butane ( Figures S8 and S9).…”

Section: Angewandte Chemiementioning

confidence: 99%

Gas‐Phase Dehydrogenation of Alkanes: C−H Activation by a Graphene‐Supported Nickel Single‐Atom Catalyst Model

Borrome

Gronert

2019

Angewandte Chemie

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Ag as-phase anionic nickel(0) fluorenyl complex is shown to effect the dehydrogenation of linear,b ranched, and cyclic alkanes via CÀHa ctivation. It performs dehydrogenations via aC ÀHinsertion followed by b-hydride elimination. When given energy via collision-induced dissociation, the system is capable of second and thirdd ehydrogenations to form dienes and aromatics such as benzene.K inetic isotope effects and DFT calculations completed at the M06/6-311+ +G** level support the proposed mechanism. The metal complex can act as an experimental model for graphenesupported nickel single-atom catalysts and suggests that these catalysts are capable of alkane dehydrogenation via CÀH activation. Scheme 1. Gas-phase synthesis of complex I.

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Gas‐Phase Dehydrogenation of Alkanes: C−H Activation by a Graphene‐Supported Nickel Single‐Atom Catalyst Model

Borrome

Gronert

2019

Angew Chem Int Ed

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Propane activation by MC5H+5 (M=Ni and Co): An experimental and theoretical work

Cited by 5 publications

References 39 publications

Catalytic Dehydrogenation of Liquid Organic Hydrogen Carrier Model Compounds by CpM⁺ (M = Fe, Co, Ni) in the Gas Phase

Catalytic Dehydrogenation of Liquid Organic Hydrogen Carrier Model Compounds by CpM⁺ (M = Fe, Co, Ni) in the Gas Phase

Gas‐Phase Dehydrogenation of Alkanes: C−H Activation by a Graphene‐Supported Nickel Single‐Atom Catalyst Model

Gas‐Phase Dehydrogenation of Alkanes: C−H Activation by a Graphene‐Supported Nickel Single‐Atom Catalyst Model

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Propane activation by MC5H+5 (M=Ni and Co): An experimental and theoretical work

Cited by 5 publications

References 39 publications

Catalytic Dehydrogenation of Liquid Organic Hydrogen Carrier Model Compounds by CpM+ (M = Fe, Co, Ni) in the Gas Phase

Catalytic Dehydrogenation of Liquid Organic Hydrogen Carrier Model Compounds by CpM+ (M = Fe, Co, Ni) in the Gas Phase

Gas‐Phase Dehydrogenation of Alkanes: C−H Activation by a Graphene‐Supported Nickel Single‐Atom Catalyst Model

Gas‐Phase Dehydrogenation of Alkanes: C−H Activation by a Graphene‐Supported Nickel Single‐Atom Catalyst Model

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Product

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Catalytic Dehydrogenation of Liquid Organic Hydrogen Carrier Model Compounds by CpM⁺ (M = Fe, Co, Ni) in the Gas Phase

Catalytic Dehydrogenation of Liquid Organic Hydrogen Carrier Model Compounds by CpM⁺ (M = Fe, Co, Ni) in the Gas Phase