Pub Date : 2025-10-16DOI: 10.1016/j.jorganchem.2025.123899
Manali Dutta
This review article chronicles a brief account of the oxidative carbon-carbon multiple bond cleavage reaction, the conventional and catalytic approaches and the drawbacks associated with these reactions. In this connection, the synthesis and characterization of various reported high-valent ruthenium-oxo/dioxo complexes and the indispensable roles played by these complexes in the oxidative transformation of alcohols, alkenes, alkynes and alkyl arenes have been described. The detailed mechanistic aspects of various ligand bound well defined high-valent ruthenium-oxo/dioxo intermediates and their utility as oxidant for variety of organic transformations have been discussed.
{"title":"High-valent ruthenium oxo/dioxo complexes and their mechanistic insights","authors":"Manali Dutta","doi":"10.1016/j.jorganchem.2025.123899","DOIUrl":"10.1016/j.jorganchem.2025.123899","url":null,"abstract":"<div><div>This review article chronicles a brief account of the oxidative carbon-carbon multiple bond cleavage reaction, the conventional and catalytic approaches and the drawbacks associated with these reactions. In this connection, the synthesis and characterization of various reported high-valent ruthenium-oxo/dioxo complexes and the indispensable roles played by these complexes in the oxidative transformation of alcohols, alkenes, alkynes and alkyl arenes have been described. The detailed mechanistic aspects of various ligand bound well defined high-valent ruthenium-oxo/dioxo intermediates and their utility as oxidant for variety of organic transformations have been discussed.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1042 ","pages":"Article 123899"},"PeriodicalIF":2.1,"publicationDate":"2025-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145359049","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-14DOI: 10.1016/j.jorganchem.2025.123897
J.W. Faller, Nikos Sarantopoulos, Jonathan Parr
The ions [(η6-cymene)Ru(μ-Cl)3]− and [L2(X)Ru(μ-Cl)3]1-/2− are direct analogs of the Kläui ligands and we have used these ligands as components in preparing ruthenium dimers, including (η6-cymene)Ru(μ-Cl)3Ru(BIPHEP)Cl. The conformations of the BIPHEP ligands in [NH2Et2][{RuCl(BIPHEP)}2(μ-Cl)3], however, have the potential of producing either homochiral (R,R) or (S,S) dimers or the (R,S) heterodimer. The crystal structure of this BIPHEP ruthenium complex shows a racemic mixture of (R,R) and (S,S) dimers, suggesting that the chirality in one half of the dimer strongly influences the stability of the chirality in the other half.
{"title":"Homochirality and chiral recognition in ruthenium complexes of the type [NH2Et2][{RuCl(P-P)}2(μ-Cl)3] where P-P = bidentate phosphine","authors":"J.W. Faller, Nikos Sarantopoulos, Jonathan Parr","doi":"10.1016/j.jorganchem.2025.123897","DOIUrl":"10.1016/j.jorganchem.2025.123897","url":null,"abstract":"<div><div>The ions [(η<sup>6</sup>-cymene)Ru(μ-Cl)<sub>3</sub>]<sup>−</sup> and [L<sub>2</sub>(X)Ru(μ-Cl)<sub>3</sub>]<sup>1-/2−</sup> are direct analogs of the Kläui ligands and we have used these ligands as components in preparing ruthenium dimers, including (η<sup>6</sup>-cymene)Ru(μ-Cl)<sub>3</sub>Ru(BIPHEP)Cl. The conformations of the BIPHEP ligands in [NH<sub>2</sub>Et<sub>2</sub>][{RuCl(BIPHEP)}<sub>2</sub>(μ-Cl)<sub>3</sub>], however, have the potential of producing either homochiral (<em>R,R</em>) or (<em>S,S</em>) dimers or the (<em>R,S</em>) heterodimer. The crystal structure of this BIPHEP ruthenium complex shows a racemic mixture of (<em>R,R</em>) and (<em>S,S</em>) dimers, suggesting that the chirality in one half of the dimer strongly influences the stability of the chirality in the other half.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1043 ","pages":"Article 123897"},"PeriodicalIF":2.1,"publicationDate":"2025-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145361308","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-13DOI: 10.1016/j.jorganchem.2025.123892
Amira Masoud , M.A. Ahmed , Fritz Kühn , Ghada Bassioni
Bi2WO6g-C3N4, displaying a binary hetero-structure can be prepared by an ultrasonic chemical method. The photocatalytic characteristics of X% (X = 5, 10, 15) Bi2WO6g-C3N4 nanocomposites are investigated for Rhodamine-B (Rh-B(degradation under ultraviolet irradiation. The photocatalytic performance of the Bi₂WO₆/g-C₃N₄ heterojunction was found to strongly depend on the Bi₂WO₆ loading. Among the investigated composites, the 10 % Bi₂WO₆/g-C₃N₄ heterojunction demonstrated the most efficient activity, showing a remarkable ability to degrade 90.1 % of Rhodamine B (Rh-B) within 120 min under UV irradiation. This performance is significantly superior not only to the pristine g-C₃N₄ and Bi₂WO₆ but also to the other heterostructures containing 5 % and 15 % Bi₂WO₆. For instance, pure g-C₃N₄ achieved only 28.99 % degradation of Rh-B under identical conditions, which clearly highlights the enhanced charge separation and improved interfacial interaction in the 10 % Bi₂WO₆/g-C₃N₄ composite. These findings confirm that the optimized 10 % loading provides the best balance between the active surface area, light-harvesting capability, and charge transfer efficiency, leading to a substantial enhancement in photocatalytic activity compared with both the bare components and the other composite ratios. The Z-scheme pathway of the 10 % Bi2WO6g-C3N4 heterojunction demonstrates that this combination able to transfer charges efficiently and that the photogenerated carriers' recombination is suppressed. According to a radical trapping experiment, •O2– and holes (h+) account for the most important reactive species in the Rh-B photolysis. Moreover, the 10 % Bi2WO6g-C3N4 nanocomposite reveals elevated reusability and stability for at least four successive cycles.
{"title":"g-C3N4 nanosheet-loaded Bi2WO6 nanoplates for improving photocatalytic degradation of organic pollutants","authors":"Amira Masoud , M.A. Ahmed , Fritz Kühn , Ghada Bassioni","doi":"10.1016/j.jorganchem.2025.123892","DOIUrl":"10.1016/j.jorganchem.2025.123892","url":null,"abstract":"<div><div>Bi<sub>2</sub>WO<sub>6</sub>g-C<sub>3</sub>N<sub>4</sub>, displaying a binary hetero-structure can be prepared by an ultrasonic chemical method. The photocatalytic characteristics of X% (<em>X</em> = 5, 10, 15) Bi<sub>2</sub>WO<sub>6</sub>g-C<sub>3</sub>N<sub>4</sub> nanocomposites are investigated for Rhodamine-B (Rh-B(degradation under ultraviolet irradiation. The photocatalytic performance of the Bi₂WO₆/g-C₃N₄ heterojunction was found to strongly depend on the Bi₂WO₆ loading. Among the investigated composites, the 10 % Bi₂WO₆/g-C₃N₄ heterojunction demonstrated the most efficient activity, showing a remarkable ability to degrade 90.1 % of Rhodamine B (Rh-B) within 120 min under UV irradiation. This performance is significantly superior not only to the pristine g-C₃N₄ and Bi₂WO₆ but also to the other heterostructures containing 5 % and 15 % Bi₂WO₆. For instance, pure g-C₃N₄ achieved only 28.99 % degradation of Rh-B under identical conditions, which clearly highlights the enhanced charge separation and improved interfacial interaction in the 10 % Bi₂WO₆/g-C₃N₄ composite. These findings confirm that the optimized 10 % loading provides the best balance between the active surface area, light-harvesting capability, and charge transfer efficiency, leading to a substantial enhancement in photocatalytic activity compared with both the bare components and the other composite ratios. The Z-scheme pathway of the 10 % Bi<sub>2</sub>WO<sub>6</sub>g-C<sub>3</sub>N<sub>4</sub> heterojunction demonstrates that this combination able to transfer charges efficiently and that the photogenerated carriers' recombination is suppressed. According to a radical trapping experiment, <sup>•</sup>O<sub>2</sub><sup>–</sup> and holes (h<sup>+</sup>) account for the most important reactive species in the Rh-B photolysis. Moreover, the 10 % Bi<sub>2</sub>WO<sub>6</sub>g-C<sub>3</sub>N<sub>4</sub> nanocomposite reveals elevated reusability and stability for at least four successive cycles.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1042 ","pages":"Article 123892"},"PeriodicalIF":2.1,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145326282","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-13DOI: 10.1016/j.jorganchem.2025.123898
Archana Rajmane, Arjun Kumbhar
A new biobased BMIM-Alginate ionic liquid (BioIL) was synthesized by stirring an aqueous solution of [BMIM]OH and Alginic acid. The in situ generated palladium nanoparticles (PdNPs) dispersed in BMIM-Alginate (PdNPs-BioIL) was used for the synthesis of biaryls via Suzuki-Miyaura coupling reactions. The TEM and XPS analysis confirmed the formation of PdNPs. TEM images of the catalyst showed that PdNPs (50-80 nm) were evenly dispersed in the bio-ionic polymeric matrix. The in situ generated PdNPs showed good to excellent catalytic activity for coupling aryl bromides with arylboronic acids in the presence of K2CO3 as a base in ethanol at RT. For comparison, PdNPs were also generated in situ and dispersed in a Na-Alginate matrix under similar reaction conditions. The catalytic behavior of the PdNPs in the two materials was notably different. PdNPs stabilized by [BMIM]-Alginate proved to be more active than those by Na-Alginate. Additionally, the PdNPs stabilized by [BMIM]-Alginate demonstrated at least five reuses with only a slight decrease in catalytic activity.
{"title":"Palladium nanoparticles stabilized by [BMIM]-Alginate BioIL for ligand-free Suzuki-Miyaura cross-coupling reaction at room temperature","authors":"Archana Rajmane, Arjun Kumbhar","doi":"10.1016/j.jorganchem.2025.123898","DOIUrl":"10.1016/j.jorganchem.2025.123898","url":null,"abstract":"<div><div>A new biobased BMIM-Alginate ionic liquid (BioIL) was synthesized by stirring an aqueous solution of [BMIM]OH and Alginic acid. The <em>in situ</em> generated palladium nanoparticles (PdNPs) dispersed in BMIM-Alginate (PdNPs-BioIL) was used for the synthesis of biaryls <em>via</em> Suzuki-Miyaura coupling reactions. The TEM and XPS analysis confirmed the formation of PdNPs. TEM images of the catalyst showed that PdNPs (50-80 nm) were evenly dispersed in the bio-ionic polymeric matrix. The <em>in situ</em> generated PdNPs showed good to excellent catalytic activity for coupling aryl bromides with arylboronic acids in the presence of K<sub>2</sub>CO<sub>3</sub> as a base in ethanol at RT. For comparison, PdNPs were also generated <em>in situ</em> and dispersed in a Na-Alginate matrix under similar reaction conditions. The catalytic behavior of the PdNPs in the two materials was notably different. PdNPs stabilized by [BMIM]-Alginate proved to be more active than those by Na-Alginate. Additionally, the PdNPs stabilized by [BMIM]-Alginate demonstrated at least five reuses with only a slight decrease in catalytic activity.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1042 ","pages":"Article 123898"},"PeriodicalIF":2.1,"publicationDate":"2025-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145326283","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-12DOI: 10.1016/j.jorganchem.2025.123896
Hatice Kübra Akyol , Nuray Yılmaz Baran , Talat Baran
Water/wastewater treatment is crucial for protecting the ecosystem and ensuring the adequate use of freshwater resources due to the depletion of water resources worldwide. Freshwater resources is at risk due to the presence of toxic pollutants such as nitroaromatics and organic dyes, which contribute to water pollution. Thus, the removal of these pollutants is of great importance to human health. In this study, we developed an innovative hybrid catalyst by decorating palladium nanoparticles onto carboxymethyl cellulose–activated carbon hydrogel beads (Pd@NaCMC/AC), which serve as the support material (NaCMC/AC), and characterized its structure using FTIR, XRD, EDS, FE-SEM, and TEM analyses. Then, its performance was assessed against reduction of nitroaromatics (4-nitro-o-phenylenediamine (4-PDA), 2-nitroaniline (2-NA), 4-nitrophenol (4-NP), and 4-nitroaniline (4-NA)), organic dyes (methyl orange (MO), methylene blue (MB), and rhodamine B (RhB)), as well as mixed pollutants. Pd@NaCMC/AC efficiently reduced 4-PDA, 2-NA, 4-NP, and 4-NA in 52, 40, 90, and 48 s, respectively, with corresponding rate constants of 0.018, 0.032, 0.014, and 0.030 s⁻¹. Additionally, MO was reduced with rate constant of in 30 s with 0.024 s⁻¹ and RhB in - 80 s with 0.025 s⁻¹, while MB was removed instantly. Pd@NaCMC/AC also exhibited good performance against the mixed 4-NP+MB pollutant, successfully reducing both contaminants. Moreover, for the 2-NA reduction catalyzed by Pd@NaCMC/AC, the activation energy was determined to be 20.095 kj/mol. The Pd@NaCMC/AC demonstrated good recyclability, maintaining its performance over six cycles.
{"title":"Construction of green, sustainable, and versatile hybrid catalyst using Pd-loaded carboxymethyl cellulose–activated carbon beads for efficient reduction of environmental pollutants","authors":"Hatice Kübra Akyol , Nuray Yılmaz Baran , Talat Baran","doi":"10.1016/j.jorganchem.2025.123896","DOIUrl":"10.1016/j.jorganchem.2025.123896","url":null,"abstract":"<div><div>Water/wastewater treatment is crucial for protecting the ecosystem and ensuring the adequate use of freshwater resources due to the depletion of water resources worldwide. Freshwater resources is at risk due to the presence of toxic pollutants such as nitroaromatics and organic dyes, which contribute to water pollution. Thus, the removal of these pollutants is of great importance to human health. In this study, we developed an innovative hybrid catalyst by decorating palladium nanoparticles onto carboxymethyl cellulose–activated carbon hydrogel beads (Pd@NaCMC/AC), which serve as the support material (NaCMC/AC), and characterized its structure using FTIR, XRD, EDS, FE-SEM, and TEM analyses. Then, its performance was assessed against reduction of nitroaromatics (4-nitro-<em>o</em>-phenylenediamine (4-PDA), 2-nitroaniline (2-NA), 4-nitrophenol (4-NP), and 4-nitroaniline (4-NA)), organic dyes (methyl orange (MO), methylene blue (MB), and rhodamine B (RhB)), as well as mixed pollutants. Pd@NaCMC/AC efficiently reduced 4-PDA, 2-NA, 4-NP, and 4-NA in 52, 40, 90, and 48 s, respectively, with corresponding rate constants of 0.018, 0.032, 0.014, and 0.030 s⁻¹. Additionally, MO was reduced with rate constant of in 30 s with 0.024 s⁻¹ and RhB in - 80 s with 0.025 s⁻¹, while MB was removed instantly. Pd@NaCMC/AC also exhibited good performance against the mixed 4-NP+MB pollutant, successfully reducing both contaminants. Moreover, for the 2-NA reduction catalyzed by Pd@NaCMC/AC, the activation energy was determined to be 20.095 kj/mol. The Pd@NaCMC/AC demonstrated good recyclability, maintaining its performance over six cycles.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1042 ","pages":"Article 123896"},"PeriodicalIF":2.1,"publicationDate":"2025-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145326278","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-12DOI: 10.1016/j.jorganchem.2025.123895
Thomas Strassner, Richard D. Adams
{"title":"Biosketch - Thomas Strassner","authors":"Thomas Strassner, Richard D. Adams","doi":"10.1016/j.jorganchem.2025.123895","DOIUrl":"10.1016/j.jorganchem.2025.123895","url":null,"abstract":"","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1042 ","pages":"Article 123895"},"PeriodicalIF":2.1,"publicationDate":"2025-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145413282","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-10DOI: 10.1016/j.jorganchem.2025.123889
Simon Stifel, Wolfgang R.E. Büchele, Leon F. Richter, Christian Jandl, Fritz E. Kühn
The synthesis and characterization of group 10 (NiII, PdII, PtII) and group 11 (CuI, AgI, AuI, AuIII) N–heterocyclic carbene (NHC) complexes supported by a methyl–substituted macrocyclic ligand is reported. NMR, ESI–MS, elemental analysis, and single–crystal X–ray diffraction (SC–XRD) confirm their structure. The d8 metals adopt square–planar geometries, with M–C bond lengths increasing from Ni to Pt and reduced backbone distortion. The d10 series forms tetranuclear Cu4L2, Ag4L2, and Au4L2 species featuring cuprophilic, argentophilic, and aurophilic interactions stabilized by the rigid macrocyclic scaffold. Comparative analysis reveals that methyl substitution enhances σ–donor character at the carbene center, promoting close metal–metal contacts. Hirshfeld surface and void analyses further confirm that crystal packing is dominated by H⋯H and C–H⋯F contacts, with minimal π–π stacking or intermolecular metallophilic interactions, and that packing efficiency varies from nearly space–filling (Ni3-OTf, Pd3-OTf, Pt3-OTf) to more open frameworks (Ag4(3)2-PF6, Au4(3)2-PF6). These structural and electronic insights underline the potential of macrocyclic NHCs for future applications.
{"title":"Elucidation of coordination geometries and intermetallic interactions in electronically modified NHC complexes of group 10 and 11","authors":"Simon Stifel, Wolfgang R.E. Büchele, Leon F. Richter, Christian Jandl, Fritz E. Kühn","doi":"10.1016/j.jorganchem.2025.123889","DOIUrl":"10.1016/j.jorganchem.2025.123889","url":null,"abstract":"<div><div>The synthesis and characterization of group 10 (Ni<sup>II</sup>, Pd<sup>II</sup>, Pt<sup>II</sup>) and group 11 (Cu<sup>I</sup>, Ag<sup>I</sup>, Au<sup>I</sup>, Au<sup>III</sup>) <em>N</em>–heterocyclic carbene (NHC) complexes supported by a methyl–substituted macrocyclic ligand is reported. NMR, ESI–MS, elemental analysis, and single–crystal X–ray diffraction (SC–XRD) confirm their structure. The <em>d</em><sup>8</sup> metals adopt square–planar geometries, with M–C bond lengths increasing from Ni to Pt and reduced backbone distortion. The <em>d</em><sup>10</sup> series forms tetranuclear Cu<sub>4</sub>L<sub>2</sub>, Ag<sub>4</sub>L<sub>2</sub>, and Au<sub>4</sub>L<sub>2</sub> species featuring cuprophilic, argentophilic, and aurophilic interactions stabilized by the rigid macrocyclic scaffold. Comparative analysis reveals that methyl substitution enhances <em>σ</em>–donor character at the carbene center, promoting close metal–metal contacts. Hirshfeld surface and void analyses further confirm that crystal packing is dominated by H⋯H and C–H⋯F contacts, with minimal <em>π–π</em> stacking or intermolecular metallophilic interactions, and that packing efficiency varies from nearly space–filling (<strong>Ni3-OTf, Pd3-OTf, Pt3-OTf</strong>) to more open frameworks (<strong>Ag<sub>4</sub>(3)<sub>2</sub>-PF<sub>6</sub>, Au<sub>4</sub>(3)<sub>2</sub>-PF<sub>6</sub></strong>). These structural and electronic insights underline the potential of macrocyclic NHCs for future applications.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1043 ","pages":"Article 123889"},"PeriodicalIF":2.1,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145361306","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-10DOI: 10.1016/j.jorganchem.2025.123894
Khilesh C. Dwivedi, Gazal Sabharwal, Maravanji S. Balakrishna
In this study, we report the synthesis and structural characterization of a series of pincer complexes derived from two pincer-type ligands: {(o-Ph2P)C6H4N(H)C9H6N} (1) and {(o-PPh2)C6H4C(O)N(H)C9H6N} (2). Treatment of 1 with various metal precursors afforded pincer complexes [MX{(o-PPh2)C6H4N(C9H6N)}κ3-P,N,N] {M = Ni, X = Cl, 3; M = Pd, X = Cl, 4; M = Pd, X = OAc; 5, M = Pt, X = Cl; 6, M = Rh, X = CO, 7}. Similar reactions of 2 also resulted in the pincer complexes [MX{(o-PPh2)C6H4C(O)N(C9H6N)}κ3-P,N,N] {M = Ni, X = Cl, 8; M = Pd, X = Cl, 9; M = Pd, X = OAc; 10, M = Pt, X = Cl; 11}. The NiII pincer complex 8 exhibited remarkable catalytic efficiency in the Markovnikov-selective hydroboration of styrene derivatives under mild reaction conditions. The catalytic system demonstrated excellent tolerance toward electron-donating substituents; however, its activity was notably diminished in the presence of electron-withdrawing or sterically encumbered alkenes.
在本研究中，我们报道了由两个钳型配体{(O - ph2p)C6H4N(H)C9H6N}(1)和{(O - pph2)C6H4C(O)N(H)C9H6N}(2)衍生的一系列钳形配合物的合成和结构表征。不同金属前驱体处理1得到钳形配合物[MX{(o-PPh2)C6H4N(C9H6N)}κ3-P，N,N] {M = Ni, X = Cl, 3；M = Pd, X = Cl, 4；M = Pd, X = OAc；5、M = Pt, X = Cl；6、M = Rh, X = CO, 7}。2的类似反应也产生钳形配合物[MX{(O - pph2)C6H4C(O)N(C9H6N)}κ3-P，N,N] {M = Ni, X = Cl, 8；M = Pd, X = Cl, 9；M = Pd, X = OAc；10、M = Pt, X = Cl；11}。NiII螯合物8在温和反应条件下对苯乙烯衍生物的马尔可夫尼科夫选择性硼氢化反应表现出显著的催化效率。该催化体系对供电子取代基表现出良好的耐受性；然而，它的活性在吸电子或位阻烯烃的存在下明显降低。
{"title":"Pincer complexes of PNN ligands and NiII catalyzed Markovnikov-selective hydroboration of styrene","authors":"Khilesh C. Dwivedi, Gazal Sabharwal, Maravanji S. Balakrishna","doi":"10.1016/j.jorganchem.2025.123894","DOIUrl":"10.1016/j.jorganchem.2025.123894","url":null,"abstract":"<div><div>In this study, we report the synthesis and structural characterization of a series of pincer complexes derived from two pincer-type ligands: {(<em>o</em>-Ph<sub>2</sub>P)C<sub>6</sub>H<sub>4</sub>N(H)C<sub>9</sub>H<sub>6</sub>N} (<strong>1</strong>) and {(<em>o</em>-PPh<sub>2</sub>)C<sub>6</sub>H<sub>4</sub>C(O)N(H)C<sub>9</sub>H<sub>6</sub>N} (<strong>2</strong>). Treatment of <strong>1</strong> with various metal precursors afforded pincer complexes [MX{(<em>o</em>-PPh<sub>2</sub>)C<sub>6</sub>H<sub>4</sub>N(C<sub>9</sub>H<sub>6</sub>N)}κ<sup>3</sup>-<em>P,N,N</em>] {<em>M</em> = Ni, <em>X</em> = Cl, <strong>3</strong>; <em>M</em> = Pd, <em>X</em> = Cl, <strong>4</strong>; <em>M</em> = Pd, <em>X</em> = OAc; <strong>5</strong>, <em>M</em> = Pt, <em>X</em> = Cl; <strong>6</strong>, <em>M</em> = Rh, <em>X</em> = CO, <strong>7</strong>}. Similar reactions of <strong>2</strong> also resulted in the pincer complexes [MX{(<em>o</em>-PPh<sub>2</sub>)C<sub>6</sub>H<sub>4</sub>C(O)N(C<sub>9</sub>H<sub>6</sub>N)}κ<sup>3</sup>-<em>P,N,N</em>] {<em>M</em> = Ni, <em>X</em> = Cl, <strong>8</strong>; <em>M</em> = Pd, <em>X</em> = Cl, <strong>9</strong>; <em>M</em> = Pd, <em>X</em> = OAc; <strong>10</strong>, <em>M</em> = Pt, <em>X</em> = Cl; <strong>11</strong>}. The Ni<sup>II</sup> pincer complex <strong>8</strong> exhibited remarkable catalytic efficiency in the Markovnikov-selective hydroboration of styrene derivatives under mild reaction conditions. The catalytic system demonstrated excellent tolerance toward electron-donating substituents; however, its activity was notably diminished in the presence of electron-withdrawing or sterically encumbered alkenes.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1042 ","pages":"Article 123894"},"PeriodicalIF":2.1,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145326281","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-08DOI: 10.1016/j.jorganchem.2025.123893
Fariba Alimola, Nasser Arsalani, Robab Aslani
In this study, three nanocomposites based on polymer dots and molybdenum oxide with alpha and beta phases, and reduced graphene oxide were synthesized. The effect of increasing the surface functional groups of polymer dots by adding polyethylene glycol diacid was investigated. Polyethylene glycol diacid not only the CO2H, CHO, and NH2 on the polymer dots increase (to improve the supercapacitor behavior) but also to the phases of the molybdenum oxide converted from beta to alpha. Since the morphology of the alpha phase is plate-shaped, the performance of the supercapacitor was improved. Finally, reduced graphene oxide was added to the nanocomposite structure to improve the electrical conductivity. The supercapacitor behavior of nanocomposites was investigated as an electrode material, and a symmetric device was manufactured of optimized nanocomposite (PDPJ-α-MoO3-rGO). The PDPJ-α-MoO3-rGO showed specific capacitance of 200 F g-1 at 1A g-1. The PEG diacid 600 improved ionic conductivity, and the addition of reduced graphene oxide in the nanocomposite (PDPJA-α-MoO3-rGO) enhanced electrical conductivity.
在这项研究中，合成了三种基于聚合物点和具有α和β相的氧化钼以及还原氧化石墨烯的纳米复合材料。研究了添加聚乙二醇二酸对提高聚合物点表面官能团的影响。聚乙二醇二酸不仅增加了聚合物点上的CO2H， CHO和NH2（以改善超级电容器的行为），而且还增加了从β到α的钼氧化物相。由于α相的形态呈片状，因此提高了超级电容器的性能。最后，将还原氧化石墨烯加入到纳米复合材料结构中，以提高其导电性。研究了纳米复合材料作为电极材料的超级电容器性能，并用优化后的纳米复合材料（PDPJ-α-MoO3-rGO）制作了对称器件。PDPJ-α-MoO3-rGO在1A g-1时的比电容为200 F -1。聚乙二醇二酸600提高了离子电导率，在纳米复合材料中加入还原氧化石墨烯（PDPJA-α-MoO3-rGO）增强了电导率。
{"title":"Synthesis and performance assessment of β-MoO3 and α-MoO3 decorated by reduced graphene oxide/polymer dot for energy storage applications","authors":"Fariba Alimola, Nasser Arsalani, Robab Aslani","doi":"10.1016/j.jorganchem.2025.123893","DOIUrl":"10.1016/j.jorganchem.2025.123893","url":null,"abstract":"<div><div>In this study, three nanocomposites based on polymer dots and molybdenum oxide with alpha and beta phases, and reduced graphene oxide were synthesized. The effect of increasing the surface functional groups of polymer dots by adding polyethylene glycol diacid was investigated. Polyethylene glycol diacid not only the CO<sub>2</sub>H, CHO, and NH<sub>2</sub> on the polymer dots increase (to improve the supercapacitor behavior) but also to the phases of the molybdenum oxide converted from beta to alpha. Since the morphology of the alpha phase is plate-shaped, the performance of the supercapacitor was improved. Finally, reduced graphene oxide was added to the nanocomposite structure to improve the electrical conductivity. The supercapacitor behavior of nanocomposites was investigated as an electrode material, and a symmetric device was manufactured of optimized nanocomposite (PD<sub>PJ</sub>-α-MoO<sub>3</sub>-rGO). The PD<sub>PJ</sub>-α-MoO<sub>3</sub>-rGO showed specific capacitance of 200 F g<sup>-1</sup> at 1A g<sup>-1</sup>. The PEG diacid 600 improved ionic conductivity, and the addition of reduced graphene oxide in the nanocomposite (PD<sub>PJA</sub>-α-MoO<sub>3</sub>-rGO) enhanced electrical conductivity.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1042 ","pages":"Article 123893"},"PeriodicalIF":2.1,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145326279","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-08DOI: 10.1016/j.jorganchem.2025.123888
Marcel Annereau , Anne Le Mire , Geoffrey Gontard , Michèle Salmain , Vincent Corcé
A new family of water-soluble photoinduced CO-releasing molecules (PhotoCORMs) having the general structure fac-[Mn(CO)3(Rbpy)(NH3)]Br (bpy= 2,2′-bipyridine; R= -H, -Me, -tBu, -OMe, -NO2, -CF3, -CONH2) has been synthesized in good yield by reaction between the corresponding [Mn(CO)3(Rbpy)Br] complexes and methanolic ammonia. Photolysis experiments and myoglobin assay were performed on all the complexes and unambiguously demonstrated that they rapidly release from one to three CO molecules upon blue light irradiation.
{"title":"Cationization of fac-[Mn(CO)3(Rbpy)Br] complexes with ammonia: direct access to water-soluble photoinduced CO releasing molecules","authors":"Marcel Annereau , Anne Le Mire , Geoffrey Gontard , Michèle Salmain , Vincent Corcé","doi":"10.1016/j.jorganchem.2025.123888","DOIUrl":"10.1016/j.jorganchem.2025.123888","url":null,"abstract":"<div><div>A new family of water-soluble photoinduced CO-releasing molecules (PhotoCORMs) having the general structure <em>fac</em>-[Mn(CO)<sub>3</sub>(<sup>R</sup>bpy)(NH<sub>3</sub>)]Br (bpy= 2,2′-bipyridine; <em>R</em>= -H, -Me, -tBu, -OMe, -NO<sub>2</sub>, -CF<sub>3</sub>, -CONH<sub>2</sub>) has been synthesized in good yield by reaction between the corresponding [Mn(CO)<sub>3</sub>(<sup>R</sup>bpy)Br] complexes and methanolic ammonia. Photolysis experiments and myoglobin assay were performed on all the complexes and unambiguously demonstrated that they rapidly release from one to three CO molecules upon blue light irradiation.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1042 ","pages":"Article 123888"},"PeriodicalIF":2.1,"publicationDate":"2025-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145326284","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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