Pub Date : 2025-02-24DOI: 10.1016/j.jorganchem.2025.123589
Eva M. Gulotty , Gregory D. Kortman , Nicole E. Proctor , Richard J. Staples , Shannon M. Biros , Matthias Bremer , William R. Winchester
The delocalization of electrons across a vinylbis(trimethylsilyl)silyl anion has been studied with both lithium and potassium as counterions. The reaction of vinyl tris(trimethylsilyl)silane with potassium tert-butoxide forms the potassium salt while reaction with methyllithium produces the lithium salt, both by nucleophilic displacement of a trimethylsilyl group. The anion formed has been studied by 1H, 13C and 29Si NMR spectroscopy. A crystal structure of the 12-crown-4 complex of the lithium salt of the vinylbis(trimethylsilyl)silyl anion has been obtained. Reactions of the anion with acetic acid, Ph3SiCl, Ph2MeSiCl, PhCH2Cl and BrCH2CH2Br have been studied and the crystal structure of the product from reaction with Ph3SiCl is reported. Finally, we have studied the anion delocalization for these species using density functional theory and report the calculated rotational barrier for the vinyl silicon bond.
{"title":"Synthesis, characterization and reactions of the Vinylbis(trimethylsilyl)silyl anion","authors":"Eva M. Gulotty , Gregory D. Kortman , Nicole E. Proctor , Richard J. Staples , Shannon M. Biros , Matthias Bremer , William R. Winchester","doi":"10.1016/j.jorganchem.2025.123589","DOIUrl":"10.1016/j.jorganchem.2025.123589","url":null,"abstract":"<div><div>The delocalization of electrons across a vinylbis(trimethylsilyl)silyl anion has been studied with both lithium and potassium as counterions. The reaction of vinyl tris(trimethylsilyl)silane with potassium <em>tert</em>-butoxide forms the potassium salt while reaction with methyllithium produces the lithium salt, both by nucleophilic displacement of a trimethylsilyl group. The anion formed has been studied by <sup>1</sup>H, <sup>13</sup>C and <sup>29</sup>Si NMR spectroscopy. A crystal structure of the 12-crown-4 complex of the lithium salt of the vinylbis(trimethylsilyl)silyl anion has been obtained. Reactions of the anion with acetic acid, Ph<sub>3</sub>SiCl, Ph<sub>2</sub>MeSiCl, PhCH<sub>2</sub>Cl and BrCH<sub>2</sub>CH<sub>2</sub>Br have been studied and the crystal structure of the product from reaction with Ph<sub>3</sub>SiCl is reported. Finally, we have studied the anion delocalization for these species using density functional theory and report the calculated rotational barrier for the vinyl silicon bond.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1031 ","pages":"Article 123589"},"PeriodicalIF":2.1,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143548192","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 : 2025-02-23DOI: 10.1016/j.jorganchem.2025.123576
Satyanarayana Battula , Mahesh K. Zilla , Jigar Y. Soni
Here, we report an efficient and simple application of hyper valent iodine-based benzyne precursor, phenyl(mesityl)iodonium tosylate salt in the facile and metal free synthesis of 9-aryldihydrophenanthrenes, wherein the base induced ortho CH deprotonation of the iodonium salt followed by elimination of leaving group (LG) generates benzyne intermediate, and that react with diverse styrenes at ambient temperatures in situ by a tandem protocol to achieve substituted 9,10-dihydrophenanthrines with moderate to appreciable yields.
{"title":"Hypervalent iodine salt as an aryne synthon: An easy access to a tandem synthesis of 9-aryldihydrophenanthrenes with styrenes","authors":"Satyanarayana Battula , Mahesh K. Zilla , Jigar Y. Soni","doi":"10.1016/j.jorganchem.2025.123576","DOIUrl":"10.1016/j.jorganchem.2025.123576","url":null,"abstract":"<div><div>Here, we report an efficient and simple application of hyper valent iodine-based benzyne precursor, phenyl(mesityl)iodonium tosylate salt in the facile and metal free synthesis of 9-aryldihydrophenanthrenes, wherein the base induced ortho C<img>H deprotonation of the iodonium salt followed by elimination of leaving group (LG) generates benzyne intermediate, and that react with diverse styrenes at ambient temperatures in situ by a tandem protocol to achieve substituted 9,10-dihydrophenanthrines with moderate to appreciable yields.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1031 ","pages":"Article 123576"},"PeriodicalIF":2.1,"publicationDate":"2025-02-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143509455","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 : 2025-02-21DOI: 10.1016/j.jorganchem.2025.123579
Enock D. Amoateng, Evans Fosu, T. Keith Hollis
A highly selective hydrosilylation of alkenes at room temperature, catalyzed by well-defined CCC–NHC pincer Rh complexes, [(BuCiCiCBu)RhCl2Py] (1), [(BuCiCiCBu)RhCl2(NHMe2)] (2), [(BuCiCiCBu)RhCl(µ-Cl)2Rh(COD)] (3), and [(BuCiCiCBu)RhCl(µ-Cl)]2 (4), (BuCiCiCBu = 2-(1,3-bis(N-butylimidazol-2-ylidene)phenylene) has been achieved. The catalytic system exhibits excellent regioselectivity, affording anti-Markovnikov products in moderate to excellent conversions (48–100 %). Precatalyst [(BuCiCiCBu)RhCl(µ-Cl)2Rh(COD)] (3) demonstrated the highest efficiency in promoting the anti-Markovnikov hydrosilylation of both aryl and alkyl alkenes with excellent selectivity (>99 %) when Et3SiH is used as silane source in acetonitrile. Notably, the system tolerates straight chain alkyl alkenes without inducing isomerization, a commonly encountered limitation with many hydrosilylation catalytic systems.
{"title":"Highly regioselective anti-Markovnikov hydrosilylation of alkenes under mild conditions: Application of CCC-NHC pincer Rh complexes","authors":"Enock D. Amoateng, Evans Fosu, T. Keith Hollis","doi":"10.1016/j.jorganchem.2025.123579","DOIUrl":"10.1016/j.jorganchem.2025.123579","url":null,"abstract":"<div><div>A highly selective hydrosilylation of alkenes at room temperature, catalyzed by well-defined CCC–NHC pincer Rh complexes, [(<sup>Bu</sup>C<sup>i</sup>C<sup>i</sup>C<sup>Bu</sup>)RhCl<sub>2</sub>Py] (<strong>1</strong>), [(<sup>Bu</sup>C<sup>i</sup>C<sup>i</sup>C<sup>Bu</sup>)RhCl<sub>2</sub>(NHMe<sub>2</sub>)] (<strong>2</strong>), [(<sup>Bu</sup>C<sup>i</sup>C<sup>i</sup>C<sup>Bu</sup>)RhCl(µ-Cl)<sub>2</sub>Rh(COD)] (<strong>3</strong>), and [(<sup>Bu</sup>C<sup>i</sup>C<sup>i</sup>C<sup>Bu</sup>)RhCl(µ-Cl)]<sub>2</sub> (<strong>4</strong>), (<sup>Bu</sup>C<sup>i</sup>C<sup>i</sup>C<sup>Bu</sup> = 2-(1,3-bis(N-butylimidazol-2-ylidene)phenylene) has been achieved. The catalytic system exhibits excellent regioselectivity, affording anti-Markovnikov products in moderate to excellent conversions (48–100 %). Precatalyst [(<sup>Bu</sup>C<sup>i</sup>C<sup>i</sup>C<sup>Bu</sup>)RhCl(µ-Cl)<sub>2</sub>Rh(COD)] (<strong>3</strong>) demonstrated the highest efficiency in promoting the anti-Markovnikov hydrosilylation of both aryl and alkyl alkenes with excellent selectivity (>99 %) when Et<sub>3</sub>SiH is used as silane source in acetonitrile. Notably, the system tolerates straight chain alkyl alkenes without inducing isomerization, a commonly encountered limitation with many hydrosilylation catalytic systems.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1031 ","pages":"Article 123579"},"PeriodicalIF":2.1,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143519921","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}
Herein, we intend to develop the facile and scalable synthesis of graphene oxide (GO) using an improved Hummer's method by optimizing the temperatures at 55 °C (GO-1) and 40°C (GO-2) without using a reducing agent. The structural and morphology of the exfoliated graphene oxide were characterized using XRD, FTIR, RAMAN, SEM with EDAX, and TEM. The structural and morphological investigation indicates that GO-1 exhibits significantly fewer surface defects on the graphene oxide basal plane than GO-2. Moreover, the temperature of 55 °C, produces very few GO layers while achieving a significantly high yield, thereby boosting scalability. The electrochemical performance of GO-1 and GO-2 was performed in KOH electrolyte using three electrode configurations. GO-1 achieves a specific capacitance of approximately 134 F/g higher than GO-2 due to the impregnation of electrolytic ions inside the exfoliated structure. This work will give new insight into developing the prototype to control time consumption for the production of a few layers of GO with a minimal surface defect during the exfoliation process.
{"title":"Optimized hummer's method for graphene oxide: Structural properties and electrochemical applications","authors":"Saraswathi M Vanumamalai , Sabarinathan Venkatachalam , Nagarajan Srinivasan , Gnanaprakasam Dhinakar","doi":"10.1016/j.jorganchem.2025.123577","DOIUrl":"10.1016/j.jorganchem.2025.123577","url":null,"abstract":"<div><div>Herein, we intend to develop the facile and scalable synthesis of graphene oxide (GO) using an improved Hummer's method by optimizing the temperatures at 55 °C (GO-1) and 40°C (GO-2) without using a reducing agent. The structural and morphology of the exfoliated graphene oxide were characterized using XRD, FTIR, RAMAN, SEM with EDAX, and TEM. The structural and morphological investigation indicates that GO-1 exhibits significantly fewer surface defects on the graphene oxide basal plane than GO-2. Moreover, the temperature of 55 °C, produces very few GO layers while achieving a significantly high yield, thereby boosting scalability. The electrochemical performance of GO-1 and GO-2 was performed in KOH electrolyte using three electrode configurations. GO-1 achieves a specific capacitance of approximately 134 F/g higher than GO-2 due to the impregnation of electrolytic ions inside the exfoliated structure. This work will give new insight into developing the prototype to control time consumption for the production of a few layers of GO with a minimal surface defect during the exfoliation process.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1031 ","pages":"Article 123577"},"PeriodicalIF":2.1,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143578413","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 : 2025-02-19DOI: 10.1016/j.jorganchem.2025.123574
Ganesh M. Kumbhar, Ashwini S. Patil, Sanjay S. Chavan
A series of Cu(I)/Fe(II) hybrid complexes with the formula [Cu(Fc-CHNC9H6N)(PPh3)2]X (2–5) and [Cu(Fc-CHNC9H6N)(dppe)]X(6–9) [where Fc=Ferrocene, PPh3 = triphenylphosphine, dppe = 1,2-bis(diphenylphosphino)ethane, and X = NO3-, ClO4-, BF4-, and PF6-] have been prepared and characterized on the basis of elemental analyses, IR, UV–visible, 1H NMR,13P NMR and Mass spectral studies. Thermal stability of 2–5 and 6–9 has been investigated by using thermogravimetric analysis (TGA). Cyclic voltammetry of the all complexes revealed quasireversible redox behavior for the Cu(I)/Cu(II) and Fe(II)/Fe(III) pairs and it is sensitive to phosphine ligand. Red shifted emission in all complexes attributed to ligand-ligand charge transfer (LLCT), metal-ligand charge transfer (MLCT), or both and vary markedly with size of the counter anion and nature of phosphine ligand. All the complexes were tested for catalytic activity and it reveals that complexes with dppe ancillary ligand shows greater activity for the CC coupling of phenylacetylene with aryl iodides as compared to PPh3 ligand. Additionally, the counter ions significantly affected the yield of the coupling product.
{"title":"Synthesis, characterization, luminescence and catalytic properties of heterobimetallic quinoline based Cu(I)/Fe(II) hybrid complexes","authors":"Ganesh M. Kumbhar, Ashwini S. Patil, Sanjay S. Chavan","doi":"10.1016/j.jorganchem.2025.123574","DOIUrl":"10.1016/j.jorganchem.2025.123574","url":null,"abstract":"<div><div>A series of Cu(I)/Fe(II) hybrid complexes with the formula [Cu(Fc-CH<img>NC<sub>9</sub>H<sub>6</sub>N)(PPh<sub>3</sub>)<sub>2</sub>]X <strong>(2–5)</strong> and [Cu(Fc-CH<img>NC<sub>9</sub>H<sub>6</sub>N)(dppe)]X<strong>(6–9)</strong> [where Fc=Ferrocene, PPh<sub>3</sub> = triphenylphosphine, dppe = 1,2-bis(diphenylphosphino)ethane, and <em>X</em> = NO<sub>3</sub><sup>-</sup>, ClO<sub>4</sub><sup>-</sup>, BF<sub>4</sub><sup>-</sup>, and PF<sub>6</sub><sup>-</sup>] have been prepared and characterized on the basis of elemental analyses, IR, UV–visible, <sup>1</sup>H NMR,<sup>13</sup>P NMR and Mass spectral studies. Thermal stability of <strong>2–5</strong> and <strong>6–9</strong> has been investigated by using thermogravimetric analysis (TGA). Cyclic voltammetry of the all complexes revealed quasireversible redox behavior for the Cu(I)/Cu(II) and Fe(II)/Fe(III) pairs and it is sensitive to phosphine ligand. Red shifted emission in all complexes attributed to ligand-ligand charge transfer (LLCT), metal-ligand charge transfer (MLCT), or both and vary markedly with size of the counter anion and nature of phosphine ligand. All the complexes were tested for catalytic activity and it reveals that complexes with dppe ancillary ligand shows greater activity for the C<img>C coupling of phenylacetylene with aryl iodides as compared to PPh<sub>3</sub> ligand. Additionally, the counter ions significantly affected the yield of the coupling product.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1031 ","pages":"Article 123574"},"PeriodicalIF":2.1,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143519922","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}
The preparation of gold(I) complexes with benzothiazolin-2-ylidene ligands is described herein. These previously unreported complexes can be conveniently prepared from the corresponding benzothiazolium precursors using the so-called weak base route and have been spectroscopically and structurally characterized. Combined structural and computational analysis confirms enhanced π-accepting character of benzothiazolin-2-ylidine ligands in comparison with conventional (benz)imidazolin-based NHCs. The obtained complexes are reasonably stable and have been used as precursors for ligand-stabilized gold nanoparticles by controlled reduction with potassium hydride. The reaction produces 3 nm sized gold nanoparticles that are stable in solution as well as in the solid state and can be characterized both spectroscopically (NMR, UV–Vis) and by transmission electron microscopy (TEM).
{"title":"Benzothiazolin-2-ylidene gold(I) complexes as precursors for gold nanoparticles","authors":"Matteo Bevilacqua , Giulia Saggiotti , Piermaria Pinter , Bernd Morgenstern , Dominik Munz , Andrea Biffis","doi":"10.1016/j.jorganchem.2025.123575","DOIUrl":"10.1016/j.jorganchem.2025.123575","url":null,"abstract":"<div><div>The preparation of gold(I) complexes with benzothiazolin-2-ylidene ligands is described herein. These previously unreported complexes can be conveniently prepared from the corresponding benzothiazolium precursors using the so-called weak base route and have been spectroscopically and structurally characterized. Combined structural and computational analysis confirms enhanced π-accepting character of benzothiazolin-2-ylidine ligands in comparison with conventional (benz)imidazolin-based NHCs. The obtained complexes are reasonably stable and have been used as precursors for ligand-stabilized gold nanoparticles by controlled reduction with potassium hydride. The reaction produces 3 nm sized gold nanoparticles that are stable in solution as well as in the solid state and can be characterized both spectroscopically (NMR, UV–Vis) and by transmission electron microscopy (TEM).</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1030 ","pages":"Article 123575"},"PeriodicalIF":2.1,"publicationDate":"2025-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143474074","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Metal-organic frameworks (MOFs) are promising materials for photocatalytic applications, particularly in degrading organic dyes in wastewater. This review focuses on zinc-based MOFs (Zn-MOFs), emphasizing their synthesis, characterization, and photocatalytic mechanisms in pollutant degradation. A detailed examination of Zn-MOFs photocatalytic degradation mechanisms highlights critical steps, including light absorption, electron-hole pair formation, charge separation, and reactive radical generation, which collectively drive efficient pollutant breakdown. The unique structural and chemical properties of Zn-MOFs, such as their high surface area, tunable bandgap, and coordinated action of organic linkers and metal nodes, are explored in the context of their photocatalytic efficiency. Key synthetic methods–hydrothermal, solvothermal, and microwave-assisted techniques–are discussed alongside characterization approaches like X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) analysis, and UV–Vis spectroscopy, which elucidate the structural, surface, and optical properties of Zn-MOFs. Factors influencing photocatalytic performance, such as dye concentration, pH, photocatalyst dosage, and temperature, are analyzed to optimize their application. A comparative analysis with other MOFs underscores the strengths and limitations of Zn-MOFs, while the conclusion addresses current challenges and future directions, emphasizing their potential in sustainable water purification and environmental remediation.
{"title":"Innovative pathways in Zn-based metal-organic frameworks: Synthesis, characterization, and photocatalytic efficiency for organic dye degradation","authors":"Nadhir N.A. Jafar , Rafid Jihad Albadr , Waam Mohammed Taher , Vicky Jain , Subhash Chandra , Rekha M M , Mayank Kundlas , Girish Chandra Sharma , Anita Devi , Mariem Alwan , Mahmood Jasem Jawad , Hiba Mushtaq , Khursheed Muzammil , Aseel Smerat","doi":"10.1016/j.jorganchem.2025.123572","DOIUrl":"10.1016/j.jorganchem.2025.123572","url":null,"abstract":"<div><div>Metal-organic frameworks (MOFs) are promising materials for photocatalytic applications, particularly in degrading organic dyes in wastewater. This review focuses on zinc-based MOFs (Zn-MOFs), emphasizing their synthesis, characterization, and photocatalytic mechanisms in pollutant degradation. A detailed examination of Zn-MOFs photocatalytic degradation mechanisms highlights critical steps, including light absorption, electron-hole pair formation, charge separation, and reactive radical generation, which collectively drive efficient pollutant breakdown. The unique structural and chemical properties of Zn-MOFs, such as their high surface area, tunable bandgap, and coordinated action of organic linkers and metal nodes, are explored in the context of their photocatalytic efficiency. Key synthetic methods–hydrothermal, solvothermal, and microwave-assisted techniques–are discussed alongside characterization approaches like X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) analysis, and UV–Vis spectroscopy, which elucidate the structural, surface, and optical properties of Zn-MOFs. Factors influencing photocatalytic performance, such as dye concentration, pH, photocatalyst dosage, and temperature, are analyzed to optimize their application. A comparative analysis with other MOFs underscores the strengths and limitations of Zn-MOFs, while the conclusion addresses current challenges and future directions, emphasizing their potential in sustainable water purification and environmental remediation.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1030 ","pages":"Article 123572"},"PeriodicalIF":2.1,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143453615","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 : 2025-02-15DOI: 10.1016/j.jorganchem.2025.123568
Li Xiang, Beibei Mao, Dan Lv, Wensheng Fu
Two new bis(β-diketiminato) ligands, bridged by flexible linkers (1,2-ethylene and 1,3-propylene), were designed and synthesized. Using these ligands, divalent ytterbium complex L1Yb (1; L1 = [μ-(1,2–CH2CH2)][N(Me)CH2CH2NC(Me)CHC(Me)NDipp]22−, Dipp = 2,6-(iPr)2C6H3) and divalent samarium complexes L1Sm (2) and L2Sm (3; L2 = [μ-(1,3-CH2CH2CH2)][N(Me)CH2CH2NC(Me)CHC(Me)NDipp]22−) were synthesized and structurally characterized. The divalent samarium complexes 2 and 3 exhibited efficient catalytic activity with 0.1 mol% loading in the guanylation reactions. A systematic study revealed that the reactivity of these complexes is influenced by both the central metal and the nature of the bridging ligands.
{"title":"Divalent rare-earth metal complexes supported by new alkylene bridged bis(β-diketiminato) ligands: Synthesis, structure and catalytic guanylation of carbodiimides","authors":"Li Xiang, Beibei Mao, Dan Lv, Wensheng Fu","doi":"10.1016/j.jorganchem.2025.123568","DOIUrl":"10.1016/j.jorganchem.2025.123568","url":null,"abstract":"<div><div>Two new bis(<em>β</em>-diketiminato) ligands, bridged by flexible linkers (1,2-ethylene and 1,3-propylene), were designed and synthesized. Using these ligands, divalent ytterbium complex <strong>L1Yb</strong> (<strong>1</strong>; L1 = [<em>μ</em>-(1,2–CH<sub>2</sub>CH<sub>2</sub>)][N(Me)CH<sub>2</sub>CH<sub>2</sub>NC(Me)CHC(Me)NDipp]<sub>2</sub><sup>2−</sup>, Dipp = 2,6-(<em><sup>i</sup></em>Pr)<sub>2</sub>C<sub>6</sub>H<sub>3</sub>) and divalent samarium complexes <strong>L1Sm</strong> (<strong>2</strong>) and <strong>L2Sm</strong> (<strong>3</strong>; L2 = [<em>μ</em>-(1,3-CH<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>)][N(Me)CH<sub>2</sub>CH<sub>2</sub>NC(Me)CHC(Me)NDipp]<sub>2</sub><sup>2−</sup>) were synthesized and structurally characterized. The divalent samarium complexes <strong>2</strong> and <strong>3</strong> exhibited efficient catalytic activity with 0.1 mol% loading in the guanylation reactions. A systematic study revealed that the reactivity of these complexes is influenced by both the central metal and the nature of the bridging ligands.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1030 ","pages":"Article 123568"},"PeriodicalIF":2.1,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143438215","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 : 2025-02-14DOI: 10.1016/j.jorganchem.2025.123573
Abolfazl Bezaatpour , Mandana Amiri , Heinrich Vocke , Anise Akhundi , Michael Wark
In this research work, α-Fe2O3/CeBi2O2CO3-Pd was prepared using hydrothermal method and characterized using different physical techniques. It was used as photocatalyst for the CC Suzuki-Miyaura coupling reactions between halobenzene and phenylboronic acid with electron-withdrawing and electro-donating groups on the reactants. The photocatalytic CC Suzuki-Miyaura coupling reaction was carried out in the mixed solvent (H2O/EtOH, 1:1) at room temperature under visible light irradiation. The results showed that, the presence of the electron-withdrawing groups (-CF3) on iodobenzene as well as those of electron-donating groups (-CH3) on the arylboronic acids leads to excellent conversion (100 %) in 10 min, whereas the opposite; i.e., electron-donating groups (-CH3) on iodobenzene and electron-withdrawing groups (-CF3) on the arylboronic acids lowers the conversion drastically to only 77 % in 4 h. The prepared catalyst has a good stability that does not make a significant change in the efficiency of the catalyst after 6th runs.
{"title":"α-Fe2O3/CeBi2O2CO3 decorated with Pd as an efficient photo-assisted catalyst for Suzuki-Miyaura coupling (SMC) under visible light irradiation","authors":"Abolfazl Bezaatpour , Mandana Amiri , Heinrich Vocke , Anise Akhundi , Michael Wark","doi":"10.1016/j.jorganchem.2025.123573","DOIUrl":"10.1016/j.jorganchem.2025.123573","url":null,"abstract":"<div><div>In this research work, α-Fe<sub>2</sub>O<sub>3</sub>/CeBi<sub>2</sub>O<sub>2</sub>CO<sub>3</sub>-Pd was prepared using hydrothermal method and characterized using different physical techniques. It was used as photocatalyst for the C<img>C Suzuki-Miyaura coupling reactions between halobenzene and phenylboronic acid with electron-withdrawing and electro-donating groups on the reactants. The photocatalytic C<img>C Suzuki-Miyaura coupling reaction was carried out in the mixed solvent (H<sub>2</sub>O/EtOH, 1:1) at room temperature under visible light irradiation. The results showed that, the presence of the electron-withdrawing groups (-CF<sub>3</sub>) on iodobenzene as well as those of electron-donating groups (-CH<sub>3</sub>) on the arylboronic acids leads to excellent conversion (100 %) in 10 min, whereas the opposite; i.e., electron-donating groups (-CH<sub>3</sub>) on iodobenzene and electron-withdrawing groups (-CF<sub>3</sub>) on the arylboronic acids lowers the conversion drastically to only 77 % in 4 h. The prepared catalyst has a good stability that does not make a significant change in the efficiency of the catalyst after 6th runs.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1030 ","pages":"Article 123573"},"PeriodicalIF":2.1,"publicationDate":"2025-02-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143438214","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 : 2025-02-13DOI: 10.1016/j.jorganchem.2025.123569
Dana A. Kader , Mohammed Koksh Sidiq , Salam Ghafour Taher , Dara Muhammed Aziz
The Suzuki-Miyaura cross-coupling reaction is a landmark in synthetic chemistry for its effective ability to form carbon-carbon bonds. This palladium-catalyzed reaction, which couples boronic acids with halides or pseudohalides, has drastically simplified the synthesis of complex organic compounds. It is already playing a major role in the production of pharmaceutical products as well as agricultural chemicals and biomaterials, thus significantly changing modern industry by promoting cleaner, more sustainable ways to operate chemical plants. In this paper, we provide a comprehensive overview of recent developments in palladium-catalyzed systems from 2020 to 2024, focusing on reaction parameters, and ligand variants, shedding light on their impact on yield, selectivity, kinetics, and purity. Our findings about the manifold potential of the Suzuki-Miyaura reaction to enhance reaction conditions and catalyst design underscore its flexibility. That makes possible a wide variety of uses.
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