The reactions of copper(I) oxide with the carboxylic acids CH3nXnCOOH (X/Cl, Br, n/1, 2; X/I, n/1) and dioxygen give the corresponding haloacetates of copper(II) Cu(CH3nXnCOO)2 or Cu(CH3nXnCOO)2L, L/RCOOH, H2O. Lewis base adducts of general formula Cu2(CH3nXnCOO)4L2 (X/Cl, n/1, L/THF; X/Cl, n/2, L/CH3CN; X/Br, n/1, L/py) have been obtained and structurally characterized. They are dinuclear compounds showing the typical paddle-wheel dinuclear structure, i.e., with four bridging haloacetato groups and two axial ligands. Monohaloacetato complexes of copper(I) have been prepared by reacting Cu2O with CH2ClCOOH or by haloacetato exchange from Cu(CF3COO) in excellent (X/Cl, Br) or low (X/ I) yields. The copper(I) derivatives Cu(CH2XCOO) reversibly bind carbon monoxide both in the solid state and in toluene, the carbonyl derivative Cu(CH2ClCOO)(CO) being quantitatively obtained by carbonylation of Cu(CH2ClCOO) in the solid state.
Synthesis, Reactivity and Structures of Mono- and Dihaloacetato Derivatives of Copper(I) and Copper(II)
CALDERAZZO, FAUSTO;MARCHETTI, FABIO;PAMPALONI, GUIDO;
2003-01-01
Abstract
The reactions of copper(I) oxide with the carboxylic acids CH3nXnCOOH (X/Cl, Br, n/1, 2; X/I, n/1) and dioxygen give the corresponding haloacetates of copper(II) Cu(CH3nXnCOO)2 or Cu(CH3nXnCOO)2L, L/RCOOH, H2O. Lewis base adducts of general formula Cu2(CH3nXnCOO)4L2 (X/Cl, n/1, L/THF; X/Cl, n/2, L/CH3CN; X/Br, n/1, L/py) have been obtained and structurally characterized. They are dinuclear compounds showing the typical paddle-wheel dinuclear structure, i.e., with four bridging haloacetato groups and two axial ligands. Monohaloacetato complexes of copper(I) have been prepared by reacting Cu2O with CH2ClCOOH or by haloacetato exchange from Cu(CF3COO) in excellent (X/Cl, Br) or low (X/ I) yields. The copper(I) derivatives Cu(CH2XCOO) reversibly bind carbon monoxide both in the solid state and in toluene, the carbonyl derivative Cu(CH2ClCOO)(CO) being quantitatively obtained by carbonylation of Cu(CH2ClCOO) in the solid state.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
