Enhanced reactivity of 2-rhodaoxetanes through a labile acetonitrile ligand.
New cationic, square-planar, ethene complexes [(Rbpa)RhI(C2H4)]+ [2a]--[2c]+ (Rbpa = N-alkyl-N,N-di(2-pyridylmethyl)amine; [2a]+: alkyl =R=Me; [2b]+: R = Bu; [2c]+: R = Bz) have been selectively oxygenated in acetonitrile by aqueous hydrogen peroxide to 2-rhoda(III)oxetanes with a labile acetonitrile ligand, [(Rbpa)RhIII(kappa2-C,O-CH2CH2O-)(MeCN)]+, [3a]+-[3c]+. The rate of elimination of acetaldehyde from [(Rbpa)RhIII(kappa2-C,O-CH2CH2O-)(MeCN)]+ increases in the order R = Me< R = Bu< R = Bz. Elimination of acetaldehyde from [(Bzbpa)RhIII(kappa2-C,O-CH2CH2O)(MeCN)]+ [3c]+, in the presence of ethene results in regeneration of ethene complex [(Bzbpa)RhI(C2H4)]+ [2c]+, and closes a catalytic cycle. In the presence of Z,Z-1,5-cyclooctadiene (cod) the corresponding cod complex [(Bzbpa)RhI(cod)]+ [6c]+ is formed. Further oxidation of [3c]+ by H2O2 results in the transient formylmethyl-hydroxy complex [(Bzbpa)RhIII(OH)[kappa1-C-CH2C(O)H]]+ [5c]+.
Department of Inorganic Chemistry, University of Nijmegen, The Netherlands.
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de Bruin
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Verhagen
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Schouten
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Gal
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Feichtinger
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Plattner