Selective synthesis of triangular cluster oxido-sulfidocomplexes of Mo and W: High yield preparations of [Mo3O2S2(H2O)9]4+, [W3O2S2(H2O)9]4+, [W2MoO2S2(H2O)9]4+ and their derivatization
| Autor: | Pedro Gili, Pavel A. Abramov, Rita Hernández-Molina, Javier González-Platas, Vladimir P. Fedin, Cristian Vicent, Alexander V. Virovets, Maxim N. Sokolov, Dmitry Yu. Naumov |
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| Jazyk: | angličtina |
| Rok vydání: | 2010 |
| Předmět: |
Molybdenum
Electrospray ionization chemistry.chemical_element Crystal structure Tungsten Adduct Inorganic Chemistry Metal Crystallography chemistry Yield (chemistry) visual_art Materials Chemistry Proton NMR visual_art.visual_art_medium Physical and Theoretical Chemistry Sulfide clusters Aqua complexes Single crystal |
| Popis: | Reaction of [Mo 2 O 2 (μ-S) 2 (H 2 O) 6 ] 2+ with Mo(CO) 6 or metallic Mo under hydrothermal conditions (140 °C, 4 M HCl) gives oxido-sulfido cluster aqua complex [Mo 3 (μ 3 -S)(μ-O) 2 (μ-S)(H 2 O) 9 ] 4+ ( 1 ). Similarly, [W 3 (μ 3 -S)(μ-O) 2 (μ-S)(H 2 O) 9 ] 4+ ( 2 ) is obtained from [W 2 O 2 (μ-S) 2 (H 2 O) 6 ] 2+ and W(CO) 6 . While reaction of [Mo 2 O 2 (μ-S) 2 (H 2 O) 6 ] 2+ with W(CO) 6 mainly proceeds as simple reduction to give 1 , [W 2 O 2 (μ-S) 2 (H 2 O) 6 ] 2+ with Mo(CO) 6 produces new mixed-metal cluster [W 2 Mo(μ 3 -S)(μ-O) 2 (μ-S)(H 2 O) 9 ] 4+ ( 3 ) as main product. From solutions of 1 in HCl supramolecular adduct with cucurbit[6]uril (CB[6]) {[Mo 3 O 2 S 2 (H 2 O) 6 Cl 3 ] 2 CB[6]}Cl 2 ⋅18H 2 O ( 4 ) was isolated and structurally characterized. The aqua complexes were converted into acetylacetonates [M 3 O 2 S 2 (acac) 3 (py) 3 ]PF 6 (M 3 = Mo 3 , W 3 , W 2 Mo; 5a – c ), which were characterized by X-ray single crystal analysis, electrospray ionization mass spectrometry and 1 H NMR spectroscopy. Crystal structure of (H 5 O 2 )(Me 4 N) 4 [W 3 (μ 3 -S)(μ 2 -S)(μ 2 -O) 2 (NCS) 9 ] ( 6 ), obtained from 2 , is also reported. |
| Databáze: | OpenAIRE |
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