Published in
Wiley, Chemistry - A European Journal, 2(7), p. 416-422, 2001
DOI: 10.1002/1521-3765(20010119)7:2<416::aid-chem416>3.0.co;2-q
Wiley, Chemistry - A European Journal, 2(7), p. 416-422
DOI: 10.1002/1521-3765(20010119)7:2<416::aid-chem416>3.3.co;2-h
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Enhanced Reactivity of 2-Rhodaoxetanes through a Labile Acetonitrile Ligand
,
Johanna A. W. Verhagen,
Caroline H. J. Schouten,
Anton W. Gal,
Derek Feichtinger,
Dietmar A. Plattner
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Abstract
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]+.