Patricio González‐Navarrete

On the Role of the Electronic Structure of the Heteronuclear Oxide Cluster [Ga2Mg2O5].+ in the Thermal Activation of Methane and Ethane: An Unusual Doping Effect

The reactivity of the heteronuclear oxide cluster [Ga2 Mg2 O5 ](.+) , bearing an unpaired electron at a bridging oxygen atom (Ob (.-) ), towards methane and ethane has been studied using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Hydrogen-atom transfer (HAT) from both methane and ethane to the cluster ion is identified experimentally. The reaction mechanisms of these reactions are elucidated by state-of-the-art quantum chemical calculations. The roles of spin density and charge distributions in HAT processes, as revealed by theory, not only deepen our mechanistic understanding of CH bond activation but also provide important guidance for the rational design of catalysts by pointing to the particular role of doping effects.

Penetrating the Elusive Mechanism of Copper-Mediated Fluoromethylation in the Presence of Oxygen through the Gas-Phase Reactivity of Well-Defined [LCuO]+ Complexes with Fluoromethanes (CH(4–n)Fn, n = 1–3)

Traveling wave ion mobility spectrometry (TWIMS) isomer separation was exploited to react the particularly well-defined ionic species [LCuO](+) (L = 1,10-phenanthroline) with the neutral fluoromethane substrates CH(4-n)Fn (n = 1-3) in the gas phase. Experimentally, the monofluoromethane substrate (n = 1) undergoes both hydrogen-atom transfer, forming the copper hydroxide complex [LCuOH](•+) and concomitantly a CH2F(•) radical, and oxygen-atom transfer, yielding the observable ionic product [LCu](+) plus the neutral oxidized substrate [C,H3,O,F]. DFT calculations reveal that the mechanism for both product channels relies on the initial C-H bond activation of the substrate. Compared to nonfluorinated methane, the addition of fluorine to the substrate assists the reactivity through a lowering of the C-H bond energy and reaction preorganization (through noncovalent interaction in the encounter complex). A two-state reactivity scenario is mandatory for the oxidation, which competitively results in the unusual fluoromethanol product, CH2FOH, or the decomposed products, CH2O and HF, with the latter channel being kinetically disfavored. Difluoromethane (n = 2) is predicted to undergo the analogous reactions at room temperature, although the reactions are less favored than those of monofluoromethane. The reaction of trifluoromethane (n = 3, fluoroform) through C-H activation is kinetically hindered under ambient conditions but might be expected to occur in the condensed phase upon heating or with further lowering of reaction barriers through templation with counterions, such as potassium. Overall, formation of CH(3-n)Fn(•) and CH(3-n)FnOH occurs under relatively gentle energetic conditions, which sheds light on their potential as reactive intermediates in fluoromethylation reactions mediated by copper in the presence of oxygen.

On the Activation of Methane and Carbon Dioxide by [HTaO]+ and [TaOH]+ in the Gas Phase: A Mechanistic Study

The thermal reactions of [Ta,O,H](+) with methane and carbon dioxide have been investigated experimentally and theoretically by using electrospray ionization mass spectrometry (ESI MS) and density functional theory calculations. Although the activation of methane proceeds by liberation of H2 , the activation of CO2 gives rise to the formation of [OTa(OH)](+) under the elimination of CO. Computational studies of the reactions of methane and carbon dioxide with the two isomers of [Ta,O,H](+) , namely, [HTaO](+) and [Ta(OH)](+) , have been performed to elucidate mechanistic aspects and to explain characteristic reaction patterns.

Striking Doping Effects on Thermal Methane Activation Mediated by the Heteronuclear Metal Oxides [XAlO4].+ (X=V, Nb, and Ta)

The thermal reactivity of the heteronuclear metal-oxide cluster cations [XAlO4 ].+ (X=V, Nb, and Ta) towards methane has been studied by using mass spectrometry in conjunction with quantum mechanical calculations. Experimentally, a hydrogen-atom transfer (HAT) from methane is mediated by all the three oxide clusters at ambient conditions. However, [VAlO4 ].+ is unique in that this cluster directly transforms methane into formaldehyde. The absence of this reaction for the Nb and Ta analogues demonstrates a striking doping effect on the chemoselectivity in the conversion of methane. Mechanistic aspects of the two reactions have been elucidated by quantum-chemical calculations. The HAT reactivity can be attributed to the significant spin density localized at the terminal oxygen atom (Ot.- ) of the cluster ions, while the ionic/covalent character of the Lewis acid-base unit [X-Ob ] plays a crucial role for the generation of formaldehyde. The mechanistic insight derived from this combined experimental/computational investigation may provide guidance for a more rational design of catalysts.

Unravelling Mechanistic Aspects of the Gas-Phase Ethanol Conversion: An Experimental and Computational Study on the Thermal Reactions of MO2 (+) (M=Mo, W) with Ethanol.

The ion/molecule reactions of molybdenum and tungsten dioxide cations with ethanol have been studied by Fourier transform ion-cyclotron resonance mass spectrometry (FT-ICR MS) and density functional theory (DFT) calculations. Dehydration of ethanol has been found as the dominant reaction channel, while generation of the ethyl cation corresponds to a minor product. Cleary, the reactions are mainly governed by the Lewis acidity of the metal center. Computational results, together with isotopic labeling experiments, show that the dehydration of ethanol can proceed either through a conventional concerted [1,2]-elimination mechanism or a step-wise process; the latter occurs via a hydroxyethoxy intermediate. Formation of C2 H5 (+) takes place by transfer of OH(-) from ethanol to the metal center of MO2 (+) . The molybdenum and tungsten dioxide cations exhibit comparable reactivities toward ethanol, and this is reflected in similar reaction rate constants and branching ratios.

Gas-phase reactions of cationic molybdenum and tungsten monoxide with ethanol: a combined experimental/computational exercise

The ion/molecule reactions of molybdenum and tungsten monoxide cations MO+ (M═Mo, W) with ethanol have been studied by Fourier transform ion-cyclotron resonance mass spectrometry (FT-ICR MS) and density functional theory (DFT) calculations. As observed in the previously reported reactions of MO2+ (M═Mo, W) towards ethanol, the dehydration of ethanol to give rise to the elimination of neutral C2H4 constitutes also the dominating reaction channel for the monoxides. Likewise, both systems result in a combined dehydrogenation/dehydration process, thus forming the ionic product MOC2H2+; moreover, the tungsten system presents two additional reaction channels: double dehydrogenation of ethanol with concomitant formation of the ionic product WO2C2H2+ and the generation of C2H5+ which takes place by OH− transfer from ethanol to the tungsten atom. This combined experimental/computational study of gas-phase ion molecule reactions may shed some new light on the mechanisms that occur in complex catalytic systems.

Metal‐Dependent Strengthening and Weakening of M−H and M−C Bonds by an Oxo Ligand: Thermal Gas‐Phase Activation of Methane by [OMH]+ and [MH]+ (M=Mo, Ti)

The thermal gas-phase reactions of methane with [OMoH]+ and [MoH]+ were investigated by using electrospray-ionization mass spectrometry (ESI-MS) complemented by quantum-chemical calculations. In contrast to the inertness of [MoH]+ towards methane, [OMoH]+ activates the C-H bond to form the ionic product [OMo(CH3 )]+ concomitantly with the liberation of H2 . The origin of the varying reactivities is traced back to a different influence of the oxo ligand on the Mo-C and Mo-H bonds. While the presence of this ligand weakens both the Ti-H and the Ti-CH3 bonds, both the Mo-H and Mo-CH3 bonds are strengthened. The more pronounced strengthening of the Mo-CH3 bond compared to the Mo-H bond favors the exothermicity of the reaction of [OMoH]+ with CH4 .