Cleavage of an aryl carbon–sulfur bond in hydride–thiolate complexes of molybdenum and tungsten. Crystal structures of [{Mo(SC6H2Pri3-2,4,6)(OMe)(PMePh2)}2(µ-S)2] and [{Mo(SC6H2Pri3-2,4,6)(OEt)(PEtPh2)}2(µ-S)2]
| Autor: | Timothy E. Burrow, Alan J. Lough, Raymond L. Richards, David L. Hughes, Michael J. Maguire, Robert H. Morris |
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| Rok vydání: | 1995 |
| Předmět: | |
| Zdroj: | J. Chem. Soc., Dalton Trans.. :2583-2589 |
| ISSN: | 1364-5447 0300-9246 |
| DOI: | 10.1039/dt9950002583 |
| Popis: | The complexes [MoH(SC6H2Pri3-2,4,6)3(Pr1Ph2)]1(R1= Me or Et) in tetrahydrofuran (thf)–R2OH decomposed via cleavage of an aryl carbon–sulfur bond to give C6H3Pri3-1,3,5 and the complexes [{Mo(SC6H2Pri3-2,4,6)(OR2)(PR1Ph2)}2(µ-S)2]2(R2= Me or Et). Compounds 2a(R1= R2= Me) and 2b(R1= R2= Et) have been structurally characterised by X-ray diffraction and shown to be dimers with (µ-S)2 bridging ligands derived from the thiolate ligands of the precursor complexes. The arene produced in these reactions has been detected by 2H NMR spectroscopy and by GC–mass spectrometry; C6H2(2H)Pri3-1,3,5 was observed from [MoH(SC6H2Pri3-2,4,6)3(PR1Ph2)] in thf–MeO2H. The thermal reactivity of the complex [WH(SC6H2Me3-2,4,6)3(PMe2Ph)2]3 was studied by combined TGA–mass spectrometry. The temperature for TGA started at 50 °C and was increased at 3° min–1 until 500 °C. Three events were seen at 200, 260 and 320 °C. At each, mesitylene, the hydrodesulfurisation product, was the major species detected by mass spectrometry; PMe2Ph was also detected during the first event and HSC6H2Me3-2,4,6 during the second and third events at low levels. |
| Databáze: | OpenAIRE |
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