Copper(ii) and triphenylphosphine copper(i) ethylene glycol carboxylates: synthesis, characterisation and copper nanoparticle generation

Abstract

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.

Crystal structure of bis[tetrakis(triphenylphosphane-κP)silver(I)] (nitrilotriacetato-κ4N,O,O′,O′′)(triphenylphosphane-κP)argentate(I) with an unknown amount of methanol as solvate

“…This is caused by the size and shape-dependent properties of the nanoparticles (Wilcoxon & Abrams, 2006). The formation of nanoparticles requires a metal source, reducing as well as stabilizing agents, and can be achieved by the decomposition of precursors either by heat (Adner et al, 2013) or light (Schliebe et al, 2013). However, to combine the metal source and reducing agents in one molecule, silver (I) carboxylates are convenient compounds.…”

Surprisingly high sensitivity of copper nanoparticles toward coordinating ligands: consequences for the hydride reduction of benzaldehyde

“…In order to obtain pure Cu(0) nanoparticles, colloidal syntheses are of interest as they allow working in an organic solvent with a large variety of ligands, enabling the tuning of the capping species at the surface of the nanoparticles. [12][13][14][15][16][17] The reactivity of the nanoparticles can be controlled by the interaction between the ligand and the metallic center. [18][19][20][21][22] In some cases, ligands can be detrimental to the integrity of the NPs due to the leaching of metal-ligand complexes into the medium, as it has been thoroughly studied for Pd-based catalytic systems.…”

Controlled Self‐Assembly of Mesoporous CuO Networks Guided by Organic Interlinking

“…Therefore, in a second step, multitopic polycarboxylic acids were added to the TODA@CuO NPs ethanol dispersion to maintain interparticle space during aggregation. The molecular formula of essayed organics is shown in Table 1 together with the estimated molecular size …”