Electrochemistry has been an increasingly useful tool for organic synthesis, as it can selectively generate reactive intermediates under mild conditions using an applied potential. Concurrently, synergistic activity of a metal and a ligand has been used in thermal catalysis and electrocatalytic renewable fuel generation for substrate selectivity and improved catalyst activity. Combining these synthetic strategies is an attractive approach for mild, selective, and sustainable electrosynthesis. This perspective discusses examples of metal-ligand synergistic catalysis in electrochemical applications in organic and organometallic synthesis. The range of reactions and ligand design principles illustrates many opportunities for further discovery in this area and the potential for far-reaching synthetic benefits.
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http://dx.doi.org/10.1016/j.checat.2024.100922 | DOI Listing |
Dalton Trans
December 2024
Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan.
Effective activation of small molecules (alcohol, phenol, ketones, amine, .) by a hydrogen-bridged bis(silylene) complex, which has two adjacent Lewis acidic centers and a hydridic bridging hydrogen with weak Si⋯H bonds, is described, along with product characterization by NMR and X-ray diffraction studies.
View Article and Find Full Text PDFJ Org Chem
December 2024
Department of Chemistry, Indian Institute of Technology Jodhpur, Karwar, Jodhpur, Rajasthan 342037, India.
An Earth-abundant Mn-PNP pincer complex-catalyzed terpenylation of cyclic and acyclic ketones and secondary alcohol 1-phenylethanol using isoprenoid derivatives prenol, nerol, phytol, solanesol, and E-farnesol as allyl surrogates is reported. The C-C coupling reactions are green and atom-economic, proceeding via dehydrogenation of alcohols following a hydrogen autotransfer methodology aided by metal-ligand cooperation.
View Article and Find Full Text PDFChem Sci
December 2024
School of Materials Science and Engineering, PCFM Lab, the Key Laboratory of Low-carbon Chemistry & Energy Conservation of Guangdong Province, Sun Yat-sen University Guangzhou 510006 P. R. China
Metal-ligand cooperation (MLC) is an essential strategy in transition metal catalysis. Traditional NH-based and OH-based MLC catalysts, as well as the later developed (de)aromatization strategy, have been widely applied in atom-economic borrowing hydrogen/hydrogen auto-transfer (BH/HA) reactions. However, these conventional MLC approaches are challenging for low-coordination and low-activity coinage metal complexes, arising from the instability during (de)protonation on the coordination atom, the constraint in linear coordination, and possible poisoning due to extra functional sites.
View Article and Find Full Text PDFDalton Trans
November 2024
Department of Chemistry, Indian Institute of Technology Jodhpur, Karwar, Jodhpur, 342037, Rajasthan, India.
The synthesis of a novel phosphine-based pincer chromium(II) complex CrCl(PONN) (Cr-1) is reported in this study. The complex exhibited promising catalytic performance in C-C and C-N bond formation using the borrowing hydrogen methodology. Cr-1 catalyzed the α-alkylation of ketones using primary alcohols as alkyl surrogates in the presence of catalytic amount of a base.
View Article and Find Full Text PDFInorg Chem
December 2024
Centro de Química Estrutura, Institute of Molecular Sciences, Instituto Superior Técnico, Universidade de Lisboa, Avenida Rovisco Pais, 1049-001 Lisboa, Portugal.
In this study, we report the synthesis and full characterization of five novel ruthenium(II) cymene complexes with the general formula [Ru(cym)(L')Cl], featuring N,O- and N,N-coordinating pyrazolone-based hydrazone ligands. We have characterized these complexes using single X-ray crystallography, Fourier-transform infrared spectroscopy (FT-IR), Nuclear magnetic resonance (NMR), elemental analysis, and Electrospray Ionization Mass Spectroscopy (ESI-MS). Crystallographic analysis confirmed that all of the complexes have a similar type of half-sandwich, pseudo-octahedral "three-legged piano-stool" geometry where the cymene moiety displays the typical η-coordination mode and the hydrazone ligands coordinate to the Ru(II) center in a bidentate fashion.
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