Insight into the mechanism of diazocompounds transformation catalyzed by hetero cuboidal clusters [Mo3CuQ4(MeBPE)3X4]+, (Q=S, Se; X=Cl, Br): The catalytically active species
| Autor: | Eva Guillamón, Rosa Llusar, Salah-Eddine Stiriba, Julia Pérez-Prieto |
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| Rok vydání: | 2008 |
| Předmět: |
Bromine
Carbene dimerization Cyclopropanation Stereochemistry Organic Chemistry Phosphane chemistry.chemical_element Chalcogene Biochemistry Medicinal chemistry Catalysis Inorganic Chemistry chemistry.chemical_compound Stereospecificity chemistry Ethyl diazoacetate Chiral Yield (chemistry) Materials Chemistry Physical and Theoretical Chemistry Diazo ester Copper Derivative (chemistry) |
| Zdroj: | Journal of Organometallic Chemistry. 693:1723-1727 |
| ISSN: | 0022-328X |
| DOI: | 10.1016/j.jorganchem.2007.12.029 |
| Popis: | Two enantiomerically pure trinuclear compounds of formula (P)-[Mo3S4{(R,R)-Me–BPE}3Br3]Br and (P)-[Mo3Se4{(R,R)-Me–BPE}3Cl3]Cl, (P)-1b.Br and (P)-1c.Cl, respectively, have been synthesized in a good yield and a stereospecific manner by excision of polymeric [Mo3Q7X4]n (Q = S or Se, X = Cl or Br) phases with (R,R)-Me–BPE{1,2-bis[(2R,5R)-2,5-(dimethylphospholan-1-yl)]ethane}. They have been transformed into chiral hetereo cuboidal compounds [Mo3S4{(R,R)-Me–BPE}3Br3]PF6, (P)-2b.PF6, and [Mo3Se4{(R,R)-Me–BPE}3Cl3]PF6, (P)-2c.PF6, by reaction with copper salts. All these compounds have been characterized by 31P NMR, IR, UV–Vis, mass spectrometry, elemental analysis, and chiral dichroism. The catalytic potential of tetranuclear cuboidal compounds has been assessed in the paradigm intermolecular cyclopropanation reaction of styrene with ethyl diazoacetate. Results are compared with those obtained for the analogue [Mo3S4{(R,R)-Me–BPE}3Cl3]PF6, (P)-2a.PF6. The catalytic data demonstrate that the Se derivative (P)-2c.PF6 is less reactive than the S analogues, but it leads to a similar product distribution as the sulfide analogue (P)-2a.PF6. By contrast, exchange of chlorine by the bulky bromine gives rise to a catalyst which makes the carbene dimerization more competitive. These data agree with temporal breaking of one of the Cu–Q bonds to generate an active catalytic species. |
| Databáze: | OpenAIRE |
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