Copper(II) and triphenylphosphine copper(I) ethylene glycol carboxylates: synthesis, characterisation and copper nanoparticle generation.

Ethylene glycol-functionalised copper(II) carboxylates Cu[O2CCR2(OC2H4)nOCH3]2 (n = 0-3; R = H, Me) (2a-e) have been prepared by the reaction of [Cu2(OAc)4·2H2O] with CH3O(C2H4O)nCR2CO2H (1a-e). Upon reduction of 2a-e with triphenylphosphine, the corresponding tris(triphenylphosphine)copper(I) complexes 3a-e were obtained, which could be converted to the bis(triphenylphosphine)copper(I) complexes 4a-e by removal of one phosphine ligand. Based on IR spectroscopy and single crystal X-ray structure analysis the binding motif of the carboxylato group on the copper ion is discussed. DSC, TG and TG-MS experiments were performed to analyse the thermal decomposition mechanism of 2-4. Complex 4c was used as a precursor for the generation of copper nanoparticles by thermal decomposition in hexadecylamine without the need of any further reactants. Depending on the precursor concentration, spherical copper nanoparticles with a mean diameter ranging from 10 to 85 nm as well as nanorods with a length of up to 1.3 μm (aspect ratios ranging between 2 and 32) were obtained. Electron diffraction analysis of the rods suggested that they consist of five domains which are arranged around a fivefold rotational axis.