Bimetallic nanoparticles represent attractive catalytic systems thanks to the synergy between both partners at the atomic level, mainly induced by electronic effects which in turn are associated with the corresponding structures (alloy, core-shell, hetero-dimer). This type of engineered material can trigger changes in the kinetics of catalyzed processes by variations on the electrophilicity/nucleophilicity of the metal centers involved and also promote cooperative effects to foster organic transformations, including multi-component and multi-step processes. Solvents become a crucial factor in the conception of catalytic processes, not only due to their environmental impact, but also because they can preserve the bimetallic structure during the catalytic reaction and therefore increase the catalyst lifetime. In this frame, the present review focuses on the recent works described in the literature concerning the synthesis of bimetallic nanoparticles in non-conventional solvents, i.e., other than common volatile compounds, for catalytic applications.

Dedicatedt ot he Laboratoire HØtØrochimieF ondamentale et AppliquØeo nt he occasiono fi ts 50 th anniversary.Supporting information for this article is availableunder https://doi.org/10.1002/adsc.201700535.Abstract: Small zero-valent copper nanoparticles (CuNPs) have been straightforwardly preparedf rom Cu(I) andC u(II) precursors in glycerol andi nt he presence of polyvinylpyrrolidone as stabilizer. Thanks to the negligible vaporp ressure of the solvent, these original nano-systems could be directly characterized in glycerol as well as in the solids tate, exhibiting relevantly homogeneous colloidal dispersions,a lso evena fter catalysis. CuNPs coming from the well-defined coordinationc omplex di-m-hydroxobis[(N,N,N',N'-tetramethylethylenediamine)copper(II)] chloride {[Cu(k 2 -N,N-TMEDA)(m-OH)] 2 Cl 2 } have been highly efficient in C-C andC -heteroatom bond formation processes. This newc atalytic system has proved its performance in C-Nc ouplings and in the synthesis of differently substitutedp ropargylic amines throughc ross-dehydrogenative couplings, multi-component reactions such as A 3 (aldehydealkyne-amine) and KA 2 (ketone-alkyne-amine) couplings,a sw ell as in the formationo fh eterocycles such as benzofurans,i ndolizines,a nd quinolines under smoothc onditions.N os ignificant copper amount was detected in the extracted organic compounds from the catalytic phase by inductively coupled plasma-atomic emission spectroscopic (ICP-AES)analyses,p roving ah ighly efficient immobilization of copper nanoparticles in glycerol. From am echanisticp oint of view,s pectroscopic data (infrareda nd ultraviolet-visible spectra) agreew ith asurface-like catalytic reactivity.