Chemistry - A European Journal
Chemistry - A European Journal
5 years ago

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)

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)
Martin Kaupp, Patricio González-Navarrete, Helmut Schwarz, Shaodong Zhou, Marjan Firouzbakht, Maria Schlangen
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. A combined experimental/theoretical investigation shows that while [MoH]+ is inert towards methane, [OMoH]+ activates this substrate under ambient conditions. Their different reactivities are attributed to the differential strengthening of the Mo−C bond compared to the Mo−H bond. This finding contrasts to the previously reported oxo-ligand effect for [OTiH]+.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201701615

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