Activated Methane on Small Cationic Platinum Clusters

Harding, Dan J.; Kerpal, Christian; Meijer, Gerard; Fielicke, André

doi:10.1002/anie.201107042

Cited by 72 publications

(58 citation statements)

References 39 publications

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“…For example, it was shown that the [Pt n (CH 4 )Ar m ] + complexes give rise to IR spectra which suggest that, in contrast to the bulk surface of platinum, methane is only molecularly adsorbed to the platinum cluster in ab identate configuration ( Figure 11); activation of the CÀHb ond has not taken place. [130] In contrast, adsorption of CH 4 to [Au n ] + clusterc ations (n = 2-4) provides spectral features which uncover the existence of two isomers: one corresponding to ac omplex with an intact, non-dissociated CH 4 molecule and the other to ah ydrido methyl intermediate, [H-Au n -CH 3 ] + . [131] The co-existence of two isomersa nd the observation that only one CÀHb ondo fm ethane has been activated find their explanation in the reaction profile, Figure 12.…”

Section: Probing Other Highly Reactive Gas-phase Speciesmentioning

confidence: 99%

Identification of Active Sites and Structural Characterization of Reactive Ionic Intermediates by Cryogenic Ion Trap Vibrational Spectroscopy

Schwarz

Asmis

2019

Chemistry A European J

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Cryogenic ion trap vibrational spectroscopy paired with quantum chemistry currently represents the most generally applicable approach for the structural investigation of gaseous cluster ions that are not amenable to direct absorption spectroscopy. Here, we give an overview of the most popular variants of infrared action spectroscopy and describe the advantages of using cryogenic ion traps in combination with messenger tagging and vibrational predissociation spectroscopy. We then highlight a few recent studies that apply this technique to identify highly reactive ionic intermediates and to characterize their reactive sites. We conclude by commenting on future challenges and potential developments in the field.

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Section: Probing Other Highly Reactive Gas-phase Speciesmentioning

confidence: 99%

Identification of Active Sites and Structural Characterization of Reactive Ionic Intermediates by Cryogenic Ion Trap Vibrational Spectroscopy

Schwarz

Asmis

2019

Chemistry A European J

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“…175,233 The introduction of noble metal atoms into 3d metal oxide clusters can also enhance cluster reactivity 83,85 and promote the participation of reactive oxygen species O 2 2− and O 2 •− in CO oxidation and C-H activation. 244,245 With regard to negatively charged metal clusters, there is an additional advantage that the photoelectron spectroscopy and its extension of photoelectron imaging spectroscopy can be used to probe their electronic and vibrational structures. 93 Similar exceptional properties of reactive bare metal cluster anions, anionic metal oxide, carbide, and nitride clusters have also been explicitly presented in the perspective.…”

Section: Discussionmentioning

confidence: 99%

Reactions of metal cluster anions with inorganic and organic molecules in the gas phase

et al. 2016

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The study of gas phase ion-molecule reactions by state-of-the-art mass spectrometric experiments in conjunction with quantum chemistry calculations offers an opportunity to clarify the elementary steps and mechanistic details of bond activation and conversion processes. In the past few decades, a considerable number of publications have been devoted to the ion-molecule reactions of metal clusters, the experimentally and theoretically tractable models for the active phase of condensed phase systems. The focus of this perspective concerns progress on activation and transformation of important inorganic and organic molecules by negatively charged metal clusters. The metal cluster anions cover bare metal clusters as well as ligated systems with oxygen, carbon, and nitrogen, among others. The following important issues have been summarized and discussed: (i) dependence of chemical reactivity and selectivity on cluster structures and sizes, metals and metal oxidation states, odd-even electron numbers, etc. and (ii) effects of doping, ligation, and pre-adsorption on the reactivity of metal clusters toward rather inert molecules.

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“…Spectroscopic investigation using IR‐MPD can then provide details about the structure of the cluster complex, including the state of the adsorbed molecule, information about its binding site on the cluster, and the degree of bond activation. Figure 7 shows example spectra for Pt n CH 4 Ar m + complexes 86. Comparison with calculated spectra shows methane to be molecularly adsorbed under these conditions, in a bidentate configuration different to that observed on bulk platinum surfaces.…”

Section: Reactive Intermediatesmentioning

confidence: 93%

Platinum Group Metal Clusters: From Gas‐Phase Structures and Reactivities towards Model Catalysts

Harding

Fielicke

2014

Chemistry A European J

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Transition-metal clusters have long been proposed as model systems to study heterogeneous catalysts. In this Concept article we show how advanced spectroscopic techniques can be used to determine the structures of gas-phase transition-metal clusters and their complexes with small molecules. Combined with computational studies, this can help to develop an understanding of the reactivity of these catalytic models.

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Activated Methane on Small Cationic Platinum Clusters

Cited by 72 publications

References 39 publications

Identification of Active Sites and Structural Characterization of Reactive Ionic Intermediates by Cryogenic Ion Trap Vibrational Spectroscopy

Identification of Active Sites and Structural Characterization of Reactive Ionic Intermediates by Cryogenic Ion Trap Vibrational Spectroscopy

Reactions of metal cluster anions with inorganic and organic molecules in the gas phase

Platinum Group Metal Clusters: From Gas‐Phase Structures and Reactivities towards Model Catalysts

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