A family of chelating aryl-functionalized germylene ligands has been developed and employed in the synthesis of their corresponding 16-electron Ni complexes (DippGeAr·Ni·IPr; Dipp = {[PhPCHSi(Pr)](Dipp)N}; IPr = [{(H)CN(Dipp)}C:]; Dipp = 2,6-PrCH). These complexes demonstrate the ability to cooperatively and reversibly activate dihydrogen at the germylene-nickel interface under mild conditions (1.5 atm H, 298 K). We show that the thermodynamics of the dihydrogen activation process can be modulated by tuning the electronic nature of the germylene ligands, with an increase in the electron-withdrawing character displaying more exergonic Δ values, as ascertained through NMR spectroscopic Van't Hoff analyses for all systems. This is also shown to correlate with experimental P NMR and UV/vis absorption data as well as with computationally derived parameters such as Ge-Ni bond order and Ni/Ge NPA charge, giving a thorough understanding of the modulating effect of ligand design on this reversible, cooperative bond activation reaction. Finally, the utility of this modulation was demonstrated in the catalytic dehydrocoupling of phenylsilane, whereby systems that disfavor dihydrogen activation are more efficient catalysts, aligning with H-elimination being the rate-limiting step. A density functional theory analysis supports cooperative activation of the Si-H moiety in PhSiH.
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http://dx.doi.org/10.1021/jacs.4c08297 | DOI Listing |
Appl Microbiol Biotechnol
January 2025
Key Laboratory of Industrial Biotechnology, Ministry of Education, Jiangnan University, 1800 Lihu Avenue, Wuxi, 214122, China.
The enzyme D-sorbitol dehydrogenase (SLDH) facilitates the conversion of D-sorbitol to L-sorbose. While current knowledge of this enzyme class predominantly centers on Gluconobacter oxydans, the catalytic properties of enzymes from alternative sources, particularly their substrate specificity and coenzyme dependency, remain ambiguous. In this investigation, we conducted BLASTp analysis and screened out a novel SLDH (Fpsldh) from Faunimonas pinastri A52C2.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Sichuan University, School of Chemical Engineering, No.24 South Section 1, Yihuan Road, 610065, Chengdu, CHINA.
Covalent organic frameworks (COFs) are often employed in oxygen reduction reactions (ORR) for hydrogen peroxide production due to their tunable structures and compositions. However, COF electrocatalysts require precise structural engineering, such as heteroatoms or metal site doping, to modulate the reaction pathway during the ORR process. In this work, we designed a tetraphenyl-p-phenylenediamine based COF electrocatalyst, namely TPDA-BDA, which exhibited excellent two-electron (2e) ORR performance with high H2O2 selectivity of 89.
View Article and Find Full Text PDFAcc Chem Res
January 2025
The Department of Chemistry, State University of New York at Binghamton, Binghamton, New York 13902, United States.
ConspectusIn the search for efficient and selective electrocatalysts capable of converting greenhouse gases to value-added products, enzymes found in naturally existing bacteria provide the basis for most approaches toward electrocatalyst design. Ni,Fe-carbon monoxide dehydrogenase (Ni,Fe-CODH) is one such enzyme, with a nickel-iron-sulfur cluster named the C-cluster, where CO binds and is converted to CO at high rates near the thermodynamic potential. In this Account, we divide the enzyme's catalytic contributions into three categories based on location and function.
View Article and Find Full Text PDFNanoscale Horiz
January 2025
Department of Chemical Engineering, Hampton University, Hampton, VA 23668, USA.
In this work, we use experimental and theoretical techniques to study the origin of the boosted hydrogen evolution reaction (HER) catalytic activity of two pyridyl-pyrrolidine functionalized C fullerenes. Notably, the mono-(pyridyl-pyrrolidine) penta-adduct of C has exhibited a remarkable HER catalytic activity as a metal-free catalyst, delivering an overpotential () of 75 mV RHE and a very low onset potential of -45 mV RHE. This work addresses fundamental questions about how functionalization on C changes the electron density on fullerene cages for high-performance HER electrocatalysis.
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.
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