Dataset Information

Gas-Phase Reactivity Studies of Small Molybdenum Cluster Ions with Dimethyl Disulfide.

ABSTRACT: Molybdenum sulfide is a potent hydrogen evolution catalyst, and is discussed as a replacement of platinum in large-scale electrochemical hydrogen production. To learn more about the elementary steps of MoS2 production by sputtering in the presence of dimethyl disulfide (DMDS), the reactions of Mox +, x?=?1-3, with DMDS are studied by Fourier transform ion cyclotron resonance mass spectrometry and density functional theory calculations. A rich variety of products composed of molybdenum, sulfur, carbon and hydrogen was observed. MoxSy + species are formed in the first reaction step, together with products containing carbon and hydrogen. The calculations indicate that the strong Mo-S bonds are formed preferentially, followed by Mo-C bonds. Hydrogen is exclusively bound to carbon atoms, i.e. no insertion of a molybdenum atom into a C-H bond is observed. The reactions are efficient and highly exothermic, explaining the rich chemistry observed in the experiment.

SUBMITTER: Baloglou A

PROVIDER: S-EPMC6566215 | biostudies-literature | 2018

REPOSITORIES: biostudies-literature

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Gas-Phase Reactivity Studies of Small Molybdenum Cluster Ions with Dimethyl Disulfide.

Baloglou Aristeidis A Ončák Milan M van der Linde Christian C Beyer Martin K MK

Topics in catalysis 20171127 1

Molybdenum sulfide is a potent hydrogen evolution catalyst, and is discussed as a replacement of platinum in large-scale electrochemical hydrogen production. To learn more about the elementary steps of MoS2 production by sputtering in the presence of dimethyl disulfide (DMDS), the reactions of Mox +, x = 1-3, with DMDS are studied by Fourier transform ion cyclotron resonance mass spectrometry and density functional theory calculations. A rich variety of products ...[more]

PMID: 31258300

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Project description:The intramolecular gas-phase reactivity of four oxoiron(IV) complexes supported by tetradentate N(4) ligands (L) has been studied by means of tandem mass spectrometry measurements in which the gas-phase ions [Fe(IV)(O)(L)(OTf)](+) (OTf = trifluoromethanesulfonate) and [Fe(IV) (O)(L)](2+) were isolated and then allowed to fragment by collision-induced decay (CID). CID fragmentation of cations derived from oxoiron(IV) complexes of 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane (tmc) and N,N'-bis(2-pyridylmethyl)-1,5-diazacyclooctane (L(8)Py(2)) afforded the same predominant products irrespective of whether they were hexacoordinate or pentacoordinate. These products resulted from the loss of water by dehydrogenation of ethylene or propylene linkers on the tetradentate ligand. In contrast, CID fragmentation of ions derived from oxoiron(IV) complexes of linear tetradentate ligands N,N'-bis(2-pyridylmethyl)-1,2-diaminoethane (bpmen) and N,N'-bis(2-pyridylmethyl)-1,3-diaminopropane (bpmpn) showed predominant oxidative N-dealkylation for the hexacoordinate [Fe(IV)(O)(L)(OTf)](+) cations and predominant dehydrogenation of the diaminoethane/propane backbone for the pentacoordinate [Fe(IV)(O)(L)](2+) cations. DFT calculations on [Fe(IV)(O)(bpmen)] ions showed that the experimentally observed preference for oxidative N-dealkylation versus dehydrogenation of the diaminoethane linker for the hexa- and pentacoordinate ions, respectively, is dictated by the proximity of the target C-H bond to the oxoiron(IV) moiety and the reactive spin state. Therefore, there must be a difference in ligand topology between the two ions. More importantly, despite the constraints on the geometries of the TS that prohibit the usual upright ? trajectory and prevent optimal ?(CH)-?*(z2) overlap, all the reactions still proceed preferentially on the quintet (S = 2) state surface, which increases the number of exchange interactions in the d block of iron and leads thereby to exchange enhanced reactivity (EER). As such, EER is responsible for the dominance of the S = 2 reactions for both hexa- and pentacoordinate complexes.

Dataset Information

Gas-Phase Reactivity Studies of Small Molybdenum Cluster Ions with Dimethyl Disulfide.

Publications

Gas-Phase Reactivity Studies of Small Molybdenum Cluster Ions with Dimethyl Disulfide.

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