Molecular Catalysis最新文献

{"title":"Efficient biosynthesis of Pro-Xylane through semi-rational engineering of carbonyl reductase from Canariomyces notabilis","authors":"Jian Lu ,&nbsp;Zhentao Jiang ,&nbsp;Xiubing Xie ,&nbsp;Zhiwen Xi ,&nbsp;Wenchi Zhang ,&nbsp;Rongzhen Zhang","doi":"10.1016/j.mcat.2025.115020","DOIUrl":"10.1016/j.mcat.2025.115020","url":null,"abstract":"<div><div>Pro-Xylane (boseine), a key cosmetic ingredient renowned for its anti-wrinkle effects and bioaffinity, has drawn considerable attention for its efficient biosynthesis. In this study, a NADP(H)-dependent carbonyl reductase from <em>Canariomyces notabilis</em> (<em>Cn</em>CR) was identified through <em>in silico</em> screening. Using alanine scanning and semi-saturation mutagenesis, the double mutant Y98K/N208Q was obtained, exhibiting a 15.8-fold increase in specific activity (60.11 U mg⁻¹) and an 11.5-fold improvement in catalytic efficiency (<em>k</em>_cat/<em>K</em>_m = 0.25 mM⁻¹ s⁻¹) compared to the wild-type enzyme. Mechanistic insights into the improved performance of Y98K/N208Q were revealed through molecular docking. In the enzyme-β-acetone xyloside complex, Y98K/N208Q showed enhanced hydrogen bonding and a refined active site, which improving substrate binding and anchoring. The shorter distance to NADPH and stronger interactions with the substrate boosted the mutant's catalytic efficiency compared to the wild-type. To enable efficient cofactor regeneration, glucose dehydrogenase from <em>Bacillus amyloliquefaciens</em> was integrated into the Y98K/N208Q-mediated Pro-Xylane biosynthetic pathway. Under optimized conditions (30 °C, pH 7.5, 40 g L⁻¹ cells, and a co-substrate-to-substrate ratio of 1.5 : 1), the coupled system produced Pro-Xylane at a titer of 160 g L⁻¹ within 10 h, achieving a conversion rate and diastereomeric excess (<em>S</em>-enantiomer) of ≥99 %. To our knowledge, this is the highest reported Pro-Xylane production to date. This study highlights the discovery and semi-rational engineering of a novel enzyme for efficient Pro-Xylane biosynthesis, offering a robust platform for industrial-scale production of this valuable compound.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115020"},"PeriodicalIF":3.9,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143686307","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Green and efficient epoxide fixation and CO2 separation using halogen-decorated Zr-based UiO-67 MOFs","authors":"Majed S. AlFayi ,&nbsp;Farag M.A. Altalbawy ,&nbsp;Viralkumar Mandaliya ,&nbsp;Suhas Ballal ,&nbsp;Jameel M.A. Sulaiman ,&nbsp;Deepak Bhanot ,&nbsp;Girish Chandra Sharma ,&nbsp;Subhash Chandra ,&nbsp;Iskandar Shernazarov ,&nbsp;Fadhel F. Sead","doi":"10.1016/j.mcat.2025.115045","DOIUrl":"10.1016/j.mcat.2025.115045","url":null,"abstract":"<div><div>This study reports the synthesis and characterization of novel halogen-functionalized UiO-67 MOFs for CO₂ capture and conversion. Three mixed-linker Zr-UiO-67 MOFs, [Zr₆O₄(OH)₄(L₁L₂)₁₂], were synthesized, incorporating 2,2′-bipyridine-5,5′-dicarboxylic acid (L₁) and halogen-substituted 4,4′-biphenyl dicarboxylic acids (L₂) with chlorine (<strong>MOF-1</strong>), bromine (<strong>MOF-2</strong>), or iodine (<strong>MOF-3</strong>). Comprehensive characterization confirmed successful MOF synthesis and halogen incorporation. Gas adsorption studies showed selective CO₂ adsorption over N₂ and CH₄. Critically, these MOFs exhibited exceptional catalytic activity for solvent-free CO₂ conversion to cyclic carbonates at ambient temperature and pressure. The Lewis acidic Zr centers facilitated heterogeneous catalysis of CO₂ fixation with epoxides, yielding cyclic carbonates with TBAB as a cocatalyst. High conversion (91–99 %) of epichlorohydrin to 4-(chloromethyl)-1,3-dioxolan-2-one was achieved within 12 h at room temperature and 1 bar CO₂ pressure. A structure-activity relationship was established, revealing a direct correlation between halogen electronegativity and catalytic performance. CO₂ uptake and epoxide conversion rates increased across the halogen series from chlorine to iodine, attributed to the synergistic effect of the Lewis acidic Zr centers and the increasing polarizability of the halogen substituents. Moreover, the MOFs demonstrated robust recyclability, retaining substantial catalytic activity for at least five cycles. These findings underscore the potential of halogen-functionalized UiO-67 MOFs as promising candidates for sustainable CO₂ capture and utilization strategies.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115045"},"PeriodicalIF":3.9,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143686828","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Engineering mandelate dehydrogenase for the efficient biosynthesis of salvianic acid A","authors":"Kangping Huang ,&nbsp;Wei Song ,&nbsp;Wanqing Wei ,&nbsp;Guipeng Hu ,&nbsp;Xiaomin Li ,&nbsp;Cong Gao ,&nbsp;Jing Wu","doi":"10.1016/j.mcat.2025.115051","DOIUrl":"10.1016/j.mcat.2025.115051","url":null,"abstract":"<div><div>Salvianic acid A (SAA), a bioactive compound from <em>Salvia miltiorrhiza</em>, has attracted significant attention for its therapeutic properties, including antitumor and antioxidant activities. However, its large-scale application is limited by the conventional production methods, which rely primarily on physical extraction and chemical synthesis. In this study, we constructed a de novo biosynthetic pathway for SAA by integrating two key modules: the HPPA hydroxylation module HpaBC (4-hydroxyphenylacetate 3-monooxygenase from <em>Escherichia coli</em>) and the DHPPA reductase module <em>Rg</em>MDH (D-mandelic acid dehydrogenase from <em>Rhodotorula graminis</em>) into a high-yield tyrosine-producing strain, <em>Tyr0</em>, generating the engineered strain Dps01. Metabolic analysis identified the low catalytic efficiency of <em>Rg</em>MDH as the critical bottleneck. To address this, structure-guided protein engineering of <em>Rg</em>MDH was performed. Molecular dynamics (MD) simulations revealed that the optimal mutant <em>Rg</em>MDH^M4 (T312A/F316S/T255I/A59H) exhibited a 10.3-fold increase in catalytic conformation occupancy compared to the wild-type (4.74% vs 0.46%), indicating enhanced substrate channel dynamics. This mutant exhibited a 295% increase in activity toward DHPPA, with enhanced substrate affinity and a 5.76-fold improvement in catalytic efficiency (<em>k_cat</em>/<em>K</em>_m). When integrated into strain Dps02, the engineered system achieved a maximum SAA production of 6.82 g/L within 34 hours, with a productivity of 0.21 g/L·h⁻¹ in a 5 L fed-batch fermentation. These results represent a significant advancement in the biosynthesis of SAA.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115051"},"PeriodicalIF":3.9,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143686811","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Harnessing visible light for alkenylation reactions: A promising strategy in organic synthesis","authors":"M Manod ,&nbsp;Archana Vijayakumar ,&nbsp;TS Abhinav ,&nbsp;R Bharath Krishna ,&nbsp;Chithra Mohan","doi":"10.1016/j.mcat.2025.115028","DOIUrl":"10.1016/j.mcat.2025.115028","url":null,"abstract":"<div><div>The development of green and streamlined methods for alkenylation reactions has long been a longstanding challenge in organic synthesis. Recently, visible light-mediated alkenylation has emerged as a potent strategy for the efficient and sustainable synthesis of diverse carbon-carbon double bonds. This approach offers a more effective and environmentally friendly alternative to traditional synthetic approaches. This review highlights the latest advancements in visible light-mediated alkenylation reactions, with a focus on novel photocatalytic systems, alkene sources, and applications in complex molecule synthesis. Mechanistic insights into the role of visible light in facilitating efficient and selective alkenylation are also provided.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115028"},"PeriodicalIF":3.9,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143686352","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"In-situ controlled synthesis of BiOI/Bi2S3 Z-scheme heterostructure with enriched oxygen vacancies for efficient photocatalytic removal of hexavalent chromium","authors":"Meng Lan,&nbsp;Xiaoli Dong,&nbsp;Nan Zheng,&nbsp;Yujun Liu","doi":"10.1016/j.mcat.2025.115023","DOIUrl":"10.1016/j.mcat.2025.115023","url":null,"abstract":"<div><div>The continuous increase of heavy metal pollution has seriously affected the ecological environment and human health, and photocatalysis technology is considered to be one of the most effective and environmentally friendly treatment methods. Herein, BiOI/Bi₂S₃ Z-scheme heterostructure photocatalyst with abundant oxygen vacancies was fabricated and applied for the removal of hexavalent chromium (Cr(VI)). The tightly contact interface of in situ heterostructure and abundant oxygen vacancies can accelerate charge transport and improve the photogenerated carrier separation efficiency. The unique charge transmission path of the Z-scheme heterostructure endows the material with superior redox ability. BiOI/Bi₂S₃ with optimized ratio can achieve effective reduction of Cr(VI) with the efficiency of 95.6 % under 10 min visible light illumination This work offers a promising photocatalyst for promoting the disposal of chromium-containing wastewater.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115023"},"PeriodicalIF":3.9,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143686313","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"One-step direct immobilization of engineered prenyltransferase on polystyrene for prenylated flavonoid production","authors":"Wenbo Li ,&nbsp;Xin Yan ,&nbsp;Wenli Xia ,&nbsp;Linguo Zhao ,&nbsp;Jianjun Pei","doi":"10.1016/j.mcat.2025.115047","DOIUrl":"10.1016/j.mcat.2025.115047","url":null,"abstract":"<div><div>Enzymes are highly efficient and specific biocatalysts. However, they are unstable and prone to deactivation, which limits their practical applications. To address these challenges, immobilization technology has been developed. Traditional immobilization methods typically require purified enzymes, but enzyme purification is often time-consuming and labor-intensive. Therefore, this study aims to develop a one-step method that directly purifies, adsorbs, and immobilizes enzymes from crude extracts, while simultaneously enhancing their activity. In this work, we examined the importance of the location of anchoring peptide (LCI) in fused enzyme functionality and binding affinity across various materials. LCI was fused with <em>Aspergillus fumigatiaffinis</em> prenyltransferase (AfPT) at the N-terminus to obtain the fusion enzyme LCI-AfPT, which displayed maximum load (38.9 mg/g) and highest activity recovery (92.7%) on polystyrene (PS). The free enzyme LCI-AfPT exhibited highest activity at pH 8.0 and 40°C. The highest activity of LCI-AfPT@PS was achieved at pH 7.5 and 55°C, with over 70% residual activity after 4 hours of incubation at 55°C. The tolerance of LCI-AfPT@PS to ethanol and methanol was significantly higher than that of LCI-AfPT. Immobilization significantly improved substrate affinity (<em>Km</em> reduced from 0.273 mM to 0.09 mM) and organic solvent tolerance, with no activity loss in ≤10% ethanol/methanol, highlighting its potential for industrial biocatalysis of hydrophobic flavonoids. The <em>Kcat/Km</em> value of LCI-AfPT@PS reached 0.072 s^-1· mM^-1, which was higher than that of LCI-AfPT and AfPT. LCI-AfPT was directly immobilized on PS from crude enzymes without purification, with a high adsorption selectivity of 80.5%, which was about 8-fold higher than that of AfPT. LCI-AfPT@PS retained 70% of its original activity after 10 cycles of reuse, resulting in a total of 4.4 mM of 3’-C-prenylnaringenin. This study represents the first investigation on the one-step purification and immobilization of prenyltransferase using an anchoring peptide, and its application in the efficient production of prenylated flavonoids.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115047"},"PeriodicalIF":3.9,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143686304","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The ring-opening polymerization of cyclic ester and carbonate catalyzed by trimethyl glycine and catalyst design: A DFT study","authors":"Shuang Li ,&nbsp;Xiaowei Xu ,&nbsp;Ziqiang Li ,&nbsp;Lijuan Ding ,&nbsp;Ying Peng ,&nbsp;Xiaohui Kang ,&nbsp;Yi Luo","doi":"10.1016/j.mcat.2025.115050","DOIUrl":"10.1016/j.mcat.2025.115050","url":null,"abstract":"<div><div>Organic catalytic ring-opening polymerization (ROP) of cyclic esters and carbonates is an effective strategy for obtaining biodegradable and biocompatible aliphatic polyesters and polycarbonates. The challenge is to develop highly active and green organocatalysts in this domain. Herein, the zwitterionic carboxybetaine catalyzed the ROP mechanism of trimethylene carbonate (TMC) cyclic ester and lactide (LA) was investigated by density functional theory (DFT). By comparing the ROP of TMC catalyzed by natural trimethyl glycine (TMG) and unnatural tetramethylammonium acetate (TMAA), we found the proton-accepting ability of the anion part in zwitterionic carboxybetaine is the main influencing factor of polymerization activity. Based on this finding, it is proposed to enhance the proton-accepting ability of the anion part in TMG by extending carbon spacer lengths between CH₃COO^‒ and N(CH₃)₄⁺ of TMG. Among them zwitterionic carboxybetaine molecules ((CH₃)₃N⁺(CH₂)_nCOO^‒ (n = 1–5)), the (CH₃)₃N⁺(CH₂)₄COO^‒ shows the highest catalytic activity in the ROP of TMC. Moreover, the ROP of LA catalyzed by (CH₃)₃N⁺(CH₂)₄COO^‒ showed very high catalytic activity compared to the TMG in both theoretical calculation and experiment. This work will inspire the future development of natural organocatalysts with high catalytic performance.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115050"},"PeriodicalIF":3.9,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143686312","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nickel phthalocyanine based porous bimetallic catalysts for high activity CO2 electroreduction over wide potential window","authors":"Liang Chen ,&nbsp;Ling Gao ,&nbsp;Xinai Zhang ,&nbsp;Xueling Liu ,&nbsp;Qin Chen ,&nbsp;Jinchao Li ,&nbsp;Yaping Zhang ,&nbsp;Tianxia Liu","doi":"10.1016/j.mcat.2025.115039","DOIUrl":"10.1016/j.mcat.2025.115039","url":null,"abstract":"<div><div>Robust electrocatalyst with high catalytic activity and high selectivity over wide potential window is a crucial element for CO₂ electroreduction. In this study, combining the advantages of metal-nitrogen-carbon catalyst and bimetallic atomic catalyst, nickel phthalocyanine based porous bimetallic catalyst was synthesized using various porous carbon supports. Benefit from the complementary and synergistic effect of dual active metals derived from nickel and copper, prepared bimetallic catalyst achieved high selectivity and CO Faradaic efficiency (FE_CO) exceeding 90% over a wide cathodic potential range (-0.57 V to -1.07 V), along with high current density and good long-term stability in CO₂ reduction (ECR) under low overpotential conditions of 464 millivolts. Besides, different carbon source carriers (citric acid, carbon, and ZIF-8) supported bimetallic catalyst were detailed, and the citric acid derived carbon source carrier fabricated bimetallic catalyst exhibited best performances with a highest current density (114.2 mA cm⁻² at -1.1 V) and a wide cathodic potential range (-0.57 V to -1.07 V) for FE_CO&gt;90%. This work provides a cost-effective, extendable, and efficient strategy to fabricate electrocatalyst for CO₂ reduction to CO, which can meaningfully extend the CO₂ electroreduction in practical application.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115039"},"PeriodicalIF":3.9,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143686308","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Engineered nanoporous HPM@NH2−MIL-101(Fe) catalyst for efficient oxidative desulfurization: Anchoring, electron channel, and valence state","authors":"Qinyi Li,&nbsp;Chunfeng Mao,&nbsp;Ziyi Wang,&nbsp;Haojie Sun,&nbsp;Jingxuan Xu,&nbsp;Menghua Li,&nbsp;Pengxu Yan","doi":"10.1016/j.mcat.2025.115046","DOIUrl":"10.1016/j.mcat.2025.115046","url":null,"abstract":"<div><div>Supported metal catalysts frequently experience diminished catalytic activity, attributed to the loss of active sites and impaired electron transport efficiency during reactions. From the perspective of structure-activity relationships, developing composite multivalent metal catalysts and elucidating the key role of synergistic effects are crucial for enhancing electron transport and ultimately improving oxidative desulfurization(ODS) performance. In this study, core-shell nanostructure based on Phosphomolybdic acid(HPM) and amino-functionalized MIL-101(Fe)(NH₂₋MIL-101(Fe)) was successfully synthesized through a facile and controllable impregnation method. The phosphate groups in HPM not only regulate the acidity of the catalytic environment but also maintain the overall structural stability. The enhanced mobility of lattice oxygen in HPM promotes the formation of oxygen vacancies during its interaction with NH₂₋MIL-101(Fe). The abundance of directional anchor sites for HPM can be provided by coordination via empty orbitals in Mo-O clusters with lone pairs of electrons on the nitrogen atoms in the amino group of NH₂₋MIL-101(Fe). The variable valence states of Fe and Mo efficiently activate hydrogen peroxide(H₂O₂). Furthermore, the mass transfer can be facilitated by carefully design pore windows, which matching the size of sulfur compounds. These synergistic effects collectively achieved 99.8 % ODS performance under optimal conditions(V(Ionic liquids, ILs)=1 mL, V(H₂O₂)=0.15 mL, catalyst: model oil (0.02:5, g/mL), 50 °C), while also demonstrating excellent recyclability. The reaction activation energy (45.25 kJ/mol) is calculated and the dual-pathway synergistic catalytic reaction mechanism was proposed by experiment and characterization. This study provides a promising design strategy for the research of advanced functional catalysts.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115046"},"PeriodicalIF":3.9,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143686315","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Development of ruthenium(II) bis(N-Heterocyclic Carbene) complexes for homogeneous catalysis","authors":"Filippo Campagnolo,&nbsp;Eleonora Aneggi,&nbsp;Walter Baratta,&nbsp;Daniele Zuccaccia","doi":"10.1016/j.mcat.2025.115032","DOIUrl":"10.1016/j.mcat.2025.115032","url":null,"abstract":"<div><div>A tetrakis(acetonitrile) complex bearing a bidentate bis(N-Heterocyclic Carbene) ligand was synthesized, and its formation was extensively studied. Triethylamine played a pivotal role in the reaction, initially forming a ruthenium(II)-triethylamino complex with the precursor. It then functioned as a base to produce the ruthenium(II) bis(NHC) complex, which was found to be very active in catalyzing the direct ortho-arylation of 2-phenylpyridine, with loadings as low as 2 % (a significant result considering that most reported examples in the literature require loadings as high as 10 % and are typically limited to monoarylations). Additionally, the reactive complex was successfully functionalized with various bidentate ligands of the amino, pyridine, and phosphine types, yielding a series of novel ruthenium(II) bis(NHC) dicationic organonitrile complexes. These complexes were evaluated in the catalytic transfer hydrogenation reaction, demonstrating notable activity (TOF of 50,000 h^-1). It is notable that within the pool of reported ruthenium(II) complexes featuring bidentate bis(NHC) ligands, cis- [Ru(CH₃CN)₂(1,1′-bis(3-methyl-imidazol-2-ylidene)methylene))(2–2′Bipyridine)](PF₆)₂ demonstrates exceptional high rate, marking it as one of the fastest known. Overall, the synthesized tetrakis(acetonitrile) complex proves to be a promising platform for the development of future catalysts.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"578 ","pages":"Article 115032"},"PeriodicalIF":3.9,"publicationDate":"2025-03-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143684659","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}