New cyclopentadienyl molybdenum polynuclear clusters from ring opening of Woollins’ reagent via phosphorus–selenium bond scission, phosphorus–phosphorus coupling and deselenation pathways
| Autor: | Richard C.S. Wong, Mei Lee Ooi, Ward T. Robinson |
|---|---|
| Rok vydání: | 2016 |
| Předmět: |
010405 organic chemistry
Stereochemistry chemistry.chemical_element 010402 general chemistry 01 natural sciences Medicinal chemistry Toluene 0104 chemical sciences Inorganic Chemistry chemistry.chemical_compound Cyclopentadienyl complex chemistry Molybdenum Reagent Materials Chemistry Proton NMR Physical and Theoretical Chemistry Woollins' reagent Bond cleavage Free-radical addition |
| Zdroj: | Inorganica Chimica Acta. 440:1-8 |
| ISSN: | 0020-1693 |
| DOI: | 10.1016/j.ica.2015.09.035 |
| Popis: | Cothermolysis of [(Ph)P(Se)(μ-Se)] 2 or Woollins’ reagent (WR) with Cp 2 Mo 2 (CO) 4 ( 2 ) in toluene at 110 °C led to the isolation of three different metal clusters, [Cp 2 Mo 2 {(μ-Se) 2 (PPh(Se))}{(μ-Se)(PPh) 3 ] ( 3 ), Cp 4 Mo 4 (CO) 3 (μ-Se) 4 ( 4 ) and a pair of isomer complexes of Cp 3 Mo 3 (CO) 4 [Se 3 (PPh) 2 ] ( 5a and 5 b ) in 17.5%, 3.1% and 4.9% yields, respectively. A similar reaction at 70 °C gave only 5a and 5 b in 2.0% and 4.9% yields, respectively. All complexes have been fully characterized via NMR, IR and ESI mass spectroscopy. Molecular structures of 3 , 4 and 5a were confirmed by single crystal X-ray diffraction analyses. A variable temperature 1 H NMR study of 4 was carried out. Finally, a free-radical addition pathway by selenation of WR was postulated. |
| Databáze: | OpenAIRE |
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