Vincenzo Passarelli

Synthesis and Structural Characterization of Iron(II) Derivatives of Heterocyclic Tridentate Amines

Abstract Compounds of general formula FeX2(L) {L=2,6-bis(3,5-dimethyl-N-pyrazolyl)pyridine, C15H17N5; bis[3,5-dimethyl-N-pyrazolyl)methyl]-isopropylamine, C15H25N5; bis(benzimidazol-2-yl-methyl)amine, C16H15N5, 1,3-bis(benzimidazolyl)propane, C17H16N4; bis(benzimidazolyl-2-methyl)ether, C16H14N4O; bis(benzimidazolyl-2-methyl)thioether, C16H14N4S} have been synthesized by reacting the amine with Fe4Cl8(THF)6 or FeI2(CO)4 in toluene. The complexes FeCl2(C15H17N5)·MeCN and FeCl2(C16H15N5)(MeOH) have been characterized by single crystal X-ray diffraction together with the parent triamines, C15H17N5 and C16H15N5, for comparison. The reaction of FeI2(CO)4 with bis(benzimidazolyl-2-methyl)thioether, C16H14N4S, led to the product of partial carbonyl substitution FeI2(CO)2(C16H14N4S).

Synthesis, reactivity and structures of mono- and dihaloacetato complexes of copper(I) and copper(II)

The reactions of copper(I) oxide with the carboxylic acids CH 3 - n X n COOH (X = Cl, Br, n = 1, 2; X = I, n = 1) and dioxygen give the corresponding haloacetates of copper(II) Cu(CH 3 - n X n COO) 2 or Cu(CH 3 - n X n COO) 2 L,L=RCOOH, H 2 O. Lewis base adducts of general formula Cu 2 (CH 3 - n X n COO) 4 L 2 (X = Cl, n = 1, L = THF; X = Cl, n = 2, L = CH 3 CN; 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 Cu 2 O with CH 2 ClCOOH or by haloacetato exchange from Cu(CF 3 COO) in excellent (X = Cl, Br) or low (X = I) yields. The copper(I) derivatives Cu(CH 2 XCOO) reversibly bind carbon monoxide both in the solid state and in toluene, the carbonyl derivative Cu(CH 2 ClCOO)(CO) being quantitatively obtained by carbonylation of Cu(CH 2 ClCOO) in the solid state.