Synthesis, Structure, Gas-Phase Reactivity, and Catalytic Relevance of Trinuclear Mo3S4 Clusters Bearing Terminal Hydroxo and Hydrosulfido Groups
| Autor: | Marta Feliz, Vicent S. Safont, Rosa Llusar, Tomás F. Beltrán, Cristian Vicent |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2013 |
| Předmět: |
chemistry.chemical_classification
Molybdenum Mass spectrometry chemistry.chemical_element Crystal structure Aldehyde Medicinal chemistry Dissociation (chemistry) Catalysis Inorganic Chemistry Metal Density functional calculations chemistry visual_art Gas-phase reactions visual_art.visual_art_medium Molecule Cluster compounds |
| Zdroj: | RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia instname |
| Popis: | Molybdenum(IV) hydroxo [Mo3S4(dmpe)3(OH)3]+ (1+) and hydrosulfido [Mo3S4(dmpe)3(SH)3]+ (2+) [dmpe = 1,2-bis(dimethylphosphanyl)ethane] trimetallic cuboidal cluster complexes have been isolated in high yields by treating their chloride precursors with sodium hydroxide or sodium hydrosulfide, respectively. The crystal structures of [1]BPh4 and [2]PF6 confirm that QH (Q = O, S) groups are coordinated to metal centers. Both hydroxo and hydrosulfido Mo3S4 cluster complexes are fully characterized by spectroscopic, mass spectrometric, and X-ray techniques. A comparative study of the gas-phase dissociation of 1+ and 2+ cations using ESI tandem mass spectrometry is presented, and the results are compared with those already reported for the hydroxo tungsten analogue. The gas-phase reactivity of 1+ and 2+ species towards ethanol and 1-penthanethiol have been explored. The gas-phase-generated [Mo3S4(dmpe)2(O)(OH)]+ cation activates ethanol molecules through a similar mechanism to that proposed for its tungsten congener. The main differences in aldehyde elimination under collision-induced dissociation (CID) conditions between molybdenum and tungsten cluster sulfides are discussed. The financial support of the Spanish Ministerio de Economia y Competitividad (MEC) (grant number CTQ2011-23157, research project MAT2011-28009), Fundacio Bancaixa-UJI (research project P1.1B2010-46), Universitat Politecnica de Valencia (PAID-06-12/SP20120740), and the Generalitat Valenciana (Prometeo/2009/053 and ACOMP/2013/2013/215) is gratefully acknowledged. The authors also thank the Serveis Central d'Instrumentacio Cientifica (SCIC) of the Universitat Jaume I for providing mass spectrometry, NMR spectroscopy, infrared, and X-ray facilities. T. B. thanks the Spanish Ministerio de Ciencia e Innovacion (MICINN) for a doctoral fellowship (FPI). |
| Databáze: | OpenAIRE |
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