A portfolio of value-added chemicals, fuels and building block compounds can be envisioned from CO on an industrial scale. The high kinetic and thermodynamic stabilities of CO, however, present a significant barrier to its utilisation as a C1 source. In this context, metal-ligand cooperation methodologies have emerged as one of the most dominant strategies for the transformation of the CO molecule over the last decade or so. This review focuses on the advancements in CO transformation using these cooperative methodologies. Different and well-studied ligand cooperation methodologies, such as dearomatisation-aromatisation type cooperation, bimetallic cooperation (M⋯M'; M' = main group or transition metal) and other related strategies are also discussed. Furthermore, the cooperative bond activations are subdivided based on the number of atoms connecting the reactive centre in the ligand framework (spacer/linker length) and the transition metal. Several similarities across these seemingly distinct cooperative methodologies are emphasised. Finally, this review brings out the challenges ahead in developing catalytic systems from these CO transformations.
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http://dx.doi.org/10.1039/d2dt01609e | DOI Listing |
Chemistry
January 2025
Soochow University, College of Chemistry, Chemical Engineering and Materials Science, 199 Ren-ai Road, 215123, Suzhou, CHINA.
Research on CO activation and homologation is pivotal for promoting sustainable chemistry and the construction of Cn molecular blocks. This work reports the nickel-catalyzed reduction of CO by magnesium alkyl compounds utilizing a bimetallic Mg/Ni synergistic strategy. The exposure of β-diketiminato ligand-supported magnesium monoalkyl compounds LMgR (L = [(DippNCMe)2CH]-, Dipp = 2,6-iPr2C6H3; R = nBu, CH3, C5H9) to 1 bar of CO in the presence of 10 mol% Ni(COD)2 (COD: 1,5-cyclooctadiene) selectively afforded the CO single-insertion product [LMg(CHO)C5H8], the dimerization product [(LMg)2(μ-C2O2)(CH3)2], and the linear trimerization product [(LMg)2(μ-C3O3)(nBu)2], respectively, depending on the R group.
View Article and Find Full Text PDFActa Biomater
January 2025
Hengyang Medical School, Hunan Province Cooperative Innovation Center for Molecular Target New Drug Study, School of Pharmaceutical Science, MOE Key Lab of Rare Pediatric Disease, University of South China, Hengyang 421001, China. Electronic address:
Immune checkpoint blockers (ICBs)-based immunotherapy is a favorable approach for efficient triple-negative breast cancer (TNBC) treatment. However, the therapeutic efficacy of ICBs is greatly compromised by immunosuppressive tumor microenvironments (TMEs) and low expression levels of programmed cell death ligand-1 (PD-L1). Herein, we constructed an amphiphilic prodrug by linking a hydrophobic STING agonist, MSA-2 and a hydrophilic chemotherapeutic drug, gemcitabine (GEM) via an ester bond, which can self-assemble into GEM-MSA-2 (G-M) nanoparticles (NPs) with a tumor growth inhibition (TGI) value of 87.
View Article and Find Full Text PDFChemistry
January 2025
National & Kapodistrian University of Athens, Chemistry, Panepistimiopolis, Zografou, 15771, Athens, GREECE.
The prominence of binuclear catalysts underlines the need for the design and development of diverse bifunctional ligand frameworks that exhibit tunable electronic and structural properties. Such strategies enable metal-metal and ligand-metal cooperation towards catalytic applications, improve catalytic activity, and are essential for advancing multi-electron transfers for catalytic application. Hereby, we present the synthesis, crystal structure, and photocatalytic properties of a binuclear Ni(II) complex, [Ni2(1,10-phenanthroline)2(2-sulfidophenolate)2] (1), which crystallizes in the centrosymmetric triclinic system (P-1) showing extensive intra- and inter- non-coordinated interactions.
View Article and Find Full Text PDFJ Colloid Interface Sci
January 2025
Key Laboratory of Eco-chemical Engineering, International Science and Technology Cooperation Base of Eco-chemical Engineering and Green Manufacturing, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042 China. Electronic address:
It is imperative to investigate more cost-effective, long-lasting, efficient, and reliable non-noble metal electrocatalysts for the oxygen evolution reaction (OER) in hydrogen production via water splitting. Metal-organic complexes have been extensively researched and utilized for this purpose, yet their transformation in this process remains intriguing and underexplored. To enable a comprehensive comparison, we synthesized three types of metal-organic complexes with varying morphologies using the same raw material.
View Article and Find Full Text PDFPharmaceutics
January 2025
Key Laboratory of Molecular Biophysics, Institute of Biophysics, School of Health Sciences & Biomedical Engineering, Hebei University of Technology, Tianjin 300401, China.
Brain diseases pose significant treatment challenges due to the restrictive nature of the blood-brain barrier (BBB). Recent advances in targeting macromolecules offer promising avenues for overcoming these obstacles through receptor-mediated transcytosis (RMT). We summarize the current progress in targeting brain drug delivery with macromolecules for brain diseases.
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