Journal of Organometallic Chemistry最新文献

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Facile green synthesis of MoO2/BiOCl nanocomposite using Hibiscus rosa-sinensis leaf extract and its application in visible-light-driven oxidative transformations

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-02-10 DOI: 10.1016/j.jorganchem.2025.123566

Jayalakshmi M, Aatika Nizam

This article describes a green approach for synthesizing MoO₂/BiOCl nanocomposite using a combustion procedure with Hibiscus rosa-sinensis leaf extract as a renewable fuel source, which also acts as a reducing and stabilizing agent. The synthesized material is characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and Fourier-transform infrared spectroscopy (FTIR), confirming the successful formation of the nanocomposite. The photocatalytic performance of MoO₂/BiOCl nanocomposite was evaluated for visible-light-driven oxidative transformations of different aromatic amines to nitroarenes. The unique structure of MoO₂/BiOCl provides better accessibility to the reactant molecules, facilitating faster and more efficient oxidation. The advantages of this oxidative process are high catalytic efficiency, mild reaction conditions, recyclability, environmental sustainability, and producing nitroarenes in good to exceptional yields (67–95 %). The conversion of the compounds was validated using gas chromatography-mass spectrometry (GC–MS), ¹H NMR, and ¹³C NMR. The results demonstrated that the MoO₂/BiOCl nanocomposite exhibited enhanced photocatalytic activity compared to its components, attributed to the synergistic effects between MoO₂ and BiOCl. The use of Hibiscus rosa-sinensis leaf extract in the synthesis is not only environmentally friendly and cost-effective but also contributes to the stability and efficiency of the nanocomposite.

{"title":"Facile green synthesis of MoO2/BiOCl nanocomposite using Hibiscus rosa-sinensis leaf extract and its application in visible-light-driven oxidative transformations","authors":"Jayalakshmi M, Aatika Nizam","doi":"10.1016/j.jorganchem.2025.123566","DOIUrl":"10.1016/j.jorganchem.2025.123566","url":null,"abstract":"<div><div>This article describes a green approach for synthesizing MoO2/BiOCl nanocomposite using a combustion procedure with Hibiscus rosa-sinensis leaf extract as a renewable fuel source, which also acts as a reducing and stabilizing agent. The synthesized material is characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and Fourier-transform infrared spectroscopy (FTIR), confirming the successful formation of the nanocomposite. The photocatalytic performance of MoO2/BiOCl nanocomposite was evaluated for visible-light-driven oxidative transformations of different aromatic amines to nitroarenes. The unique structure of MoO₂/BiOCl provides better accessibility to the reactant molecules, facilitating faster and more efficient oxidation. The advantages of this oxidative process are high catalytic efficiency, mild reaction conditions, recyclability, environmental sustainability, and producing nitroarenes in good to exceptional yields (67–95 %). The conversion of the compounds was validated using gas chromatography-mass spectrometry (GC–MS), 1H NMR, and 13C NMR. The results demonstrated that the MoO2/BiOCl nanocomposite exhibited enhanced photocatalytic activity compared to its components, attributed to the synergistic effects between MoO2 and BiOCl. The use of Hibiscus rosa-sinensis leaf extract in the synthesis is not only environmentally friendly and cost-effective but also contributes to the stability and efficiency of the nanocomposite.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1029 ","pages":"Article 123566"},"PeriodicalIF":2.1,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143421533","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}

引用次数: 0

Green approach to Ullmann and Sonogashira cross-coupling reactions in water: Co-MOF as a robust and recyclable nanostructure 在水中进行乌尔曼和索诺伽希拉交叉偶联反应的绿色方法：作为一种坚固且可回收的纳米结构的 Co-MOF

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-02-07 DOI: 10.1016/j.jorganchem.2025.123563

Norah Algethami , Marwea Al-hedrewy , Dharmesh Sur , Suhas Ballal , Manal Morad Karim , Abhayveer Singh , S. Sunitha , Rajashree Panigrahi

This work focuses on developing a novel metal-organic framework (MOF) and its application as a catalyst for carbon-oxygen and carbon-carbon bond formation. The catalytic transformation of aromatic halides is particularly challenging and holds significant importance in modern organic synthesis. Cross-coupling reactions that create carbon-heteroatom linkages are highly valued due to their widespread use in synthesizing of bioactive compounds and natural products. Consequently, the search for improved heterogeneous catalytic systems remains a key research priority. In this study, a cobalt-based MOF was synthesized using 4-amino-3-hydroxybenzoic acid, terephthalaldehyde, and cobalt acetate. This stable, efficient metal organic framework was characterized via FT-IR, TGA, CHNO, TEM, ICP, FE-SEM and BET techniques. Comprehensive characterization confirmed its structure and catalytic potential for cross-coupling reactions. The developed protocol offers an efficient and straightforward approach for C–O and CC bond formation, delivering excellent product yields. This method was specifically applied to Ullmann and Sonogashira reactions, marking the first reported use of Co-MOF as nanostructure in such applications. The use of cobalt as a replacement for expensive palladium not only reduces costs but also significantly enhances the sustainability and accessibility of this process. Compared to existing methods, this strategy offers several advantages, including high efficiency, short reactions, catalyst stability, and minimal environmental impact. Additionally, the cobalt-MOF catalyst is easily recovered from reaction mixtures and retains its activity over multiple cycles, making it economical and environmentally friendly.

{"title":"Green approach to Ullmann and Sonogashira cross-coupling reactions in water: Co-MOF as a robust and recyclable nanostructure","authors":"Norah Algethami , Marwea Al-hedrewy , Dharmesh Sur , Suhas Ballal , Manal Morad Karim , Abhayveer Singh , S. Sunitha , Rajashree Panigrahi","doi":"10.1016/j.jorganchem.2025.123563","DOIUrl":"10.1016/j.jorganchem.2025.123563","url":null,"abstract":"<div><div>This work focuses on developing a novel metal-organic framework (MOF) and its application as a catalyst for carbon-oxygen and carbon-carbon bond formation. The catalytic transformation of aromatic halides is particularly challenging and holds significant importance in modern organic synthesis. Cross-coupling reactions that create carbon-heteroatom linkages are highly valued due to their widespread use in synthesizing of bioactive compounds and natural products. Consequently, the search for improved heterogeneous catalytic systems remains a key research priority. In this study, a cobalt-based MOF was synthesized using 4-amino-3-hydroxybenzoic acid, terephthalaldehyde, and cobalt acetate. This stable, efficient metal organic framework was characterized via FT-IR, TGA, CHNO, TEM, ICP, FE-SEM and BET techniques. Comprehensive characterization confirmed its structure and catalytic potential for cross-coupling reactions. The developed protocol offers an efficient and straightforward approach for C–O and C<img>C bond formation, delivering excellent product yields. This method was specifically applied to Ullmann and Sonogashira reactions, marking the first reported use of Co-MOF as nanostructure in such applications. The use of cobalt as a replacement for expensive palladium not only reduces costs but also significantly enhances the sustainability and accessibility of this process. Compared to existing methods, this strategy offers several advantages, including high efficiency, short reactions, catalyst stability, and minimal environmental impact. Additionally, the cobalt-MOF catalyst is easily recovered from reaction mixtures and retains its activity over multiple cycles, making it economical and environmentally friendly.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1029 ","pages":"Article 123563"},"PeriodicalIF":2.1,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143394555","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}

引用次数: 0

Synthesis and properties of diphenylphosphanyl and di-isopropylphosphanyl triphenylsilanes and pentaphenyldisilanes

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-02-06 DOI: 10.1016/j.jorganchem.2025.123555

Mike Friebel , Uwe Böhme , Edwin Kroke

A new, less hazardous synthetic pathway to chloropentaphenyldisilane, ClSi₂Ph₅, has been developed. Starting from this compound and lithium diorganophosphides, the two previously unknown diorganophosphanyldisilanes (diphenylphosphanyl)pentaphenyldisilane, Ph₂PSi₂Ph₅, and (di-isopropylphosphanyl)pentaphenyldisilane, (i-Pr)₂PSi₂Ph₅, were prepared. To compare these compounds with the corresponding monosilanes, the known (diphenylphosphanyl)triphenylsilane, Ph₂PSiPh₃, and the unknown (di-isopropylphosphanyl)triphenylsilane, (i-Pr)₂PSiPh₃, were prepared, too. The former was prepared via new synthetic routes. The compounds were characterized with IR-, Raman-, ³¹P-, ²⁹Si-, and ¹H NMR spectroscopy and melting point determination. Single crystal structure analyses of ClSi₂Ph₅ and (i-Pr)₂PSiPh₃ were carried out and confirm the results presented.

{"title":"Synthesis and properties of diphenylphosphanyl and di-isopropylphosphanyl triphenylsilanes and pentaphenyldisilanes","authors":"Mike Friebel , Uwe Böhme , Edwin Kroke","doi":"10.1016/j.jorganchem.2025.123555","DOIUrl":"10.1016/j.jorganchem.2025.123555","url":null,"abstract":"<div><div>A new, less hazardous synthetic pathway to chloropentaphenyldisilane, ClSi2Ph5, has been developed. Starting from this compound and lithium diorganophosphides, the two previously unknown diorganophosphanyldisilanes (diphenylphosphanyl)pentaphenyldisilane, Ph2PSi2Ph5, and (di-isopropylphosphanyl)pentaphenyldisilane, (i-Pr)2PSi2Ph5, were prepared. To compare these compounds with the corresponding monosilanes, the known (diphenylphosphanyl)triphenylsilane, Ph2PSiPh3, and the unknown (di-isopropylphosphanyl)triphenylsilane, (i-Pr)2PSiPh3, were prepared, too. The former was prepared via new synthetic routes. The compounds were characterized with IR-, Raman-, 31P-, 29Si-, and 1H NMR spectroscopy and melting point determination. Single crystal structure analyses of ClSi2Ph5 and (i-Pr)2PSiPh3 were carried out and confirm the results presented.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1029 ","pages":"Article 123555"},"PeriodicalIF":2.1,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143388049","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}

引用次数: 0

Investigations into the reactivity of a molybdenocene formamidinate complex

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-02-05 DOI: 10.1016/j.jorganchem.2025.123556

Joscha Nellesen, Christian Ganter

A cationic molybdenocene amidinate complex was investigated in view of its suitability to serve as a precursor for a metalla-N-heterocyclic carbene. Upon deprotonation, an amidinate complex with a cyclopenatdiene substituent at the amidinate C atom was identified. This points to the intermediate formation of the sought-after carbene which nucleophilicly attacks a Cp ring of the remaining cationic molybdenocene precursor and subsequent fragmentation. In contrast, the nucleophilic attack of standard imidazolylidenes to the cationic molybdenocene amidinate yields stable adducts with a η⁴-cyclopentadiene ligand. The rotational dynamics of this structure has been studied by variable temperature NMR studies. The experimental findings are supported by DFT calculations.

引用次数: 0

Synthesis of rhodium complexes with chiral diene ligands based on R-carvone

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-02-03 DOI: 10.1016/j.jorganchem.2025.123554

Tatiana N. Petrushina, Alexey N. Rodionov, Yulia V. Nelyubina, Dmitry S. Perekalin

Allylic chlorination of R-carvone and subsequent nucleophilic substitution produced chiral diene ligands with additional pyrazole, phthalimide, or diethyl phosphonate coordinating groups. Reactions of these ligands with [(C₂H₄)₂RhCl]₂ produced the corresponding 16-electron rhodium complexes (carvone-L)RhCl. The pyrazole-based ligand formed the most stable complex, which was characterized by the X-ray diffraction. This complex catalyzed the insertion of aryldiazoacetates into B−H bond and cyclopropanation of 2,3-dihydrofurane but gave only racemic products.

引用次数: 0

A convenient synthesis of Os3(CO)12 from OsO4 and formic acid

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-02-01 DOI: 10.1016/j.jorganchem.2024.123480

Elumalai Kumaran, Weng Kee Leong

A convenient synthesis of the osmium carbonyl cluster Os₃(CO)₁₂ starting from osmium tetroxide and the in-situ generation of gaseous carbon monoxide via the decomposition of formic acid, is reported.

引用次数: 0

Transesterification of glycerol with dimethyl carbonate for the synthesis of glycerol carbonate and glycidol by Iron (III) salen complex

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-02-01 DOI: 10.1016/j.jorganchem.2024.123467

Long-Yat Lai, Pak-Chung Lau, Tsz-Lung Kwong, Ka-Fu Yung

The transesterification of glycerol and dimethyl carbonate (DMC) was investigated in the presence of

μ

-oxo-Fe(salen)₂ under the optimal reaction condition. Several transition metal(salen) were tested, and only Fe (salen) shows an excellent results towards transesterification of glycerol. Therefore, Fe (salen) was characterized by IR, elemental analysis, MS, XPS and Surface Basicity test, and it can be confirmed that the as-synthesized Fe(salen) was existed in the form of

μ

-oxo-Fe(salen)₂. It was proposed that the

μ

-oxo-Fe(salen)₂ can provide two different reaction pathway based on its molecular structures and the electronic configuration of iron itself.

μ

-oxo-Fe(salen)₂ was reacted with the mixture of glycerol and DMC under microwave-heating in 60 min at 100 °C and at the molar ratio of glycerol:DMC:

μ

-oxo-Fe(salen)₂ of 1:2:0.01 and obtaining the highest glycerol carbonate yield of 93.8 %.

{"title":"Transesterification of glycerol with dimethyl carbonate for the synthesis of glycerol carbonate and glycidol by Iron (III) salen complex","authors":"Long-Yat Lai, Pak-Chung Lau, Tsz-Lung Kwong, Ka-Fu Yung","doi":"10.1016/j.jorganchem.2024.123467","DOIUrl":"10.1016/j.jorganchem.2024.123467","url":null,"abstract":"<div><div>The transesterification of glycerol and dimethyl carbonate (DMC) was investigated in the presence of <math><mi>μ</mi></math>-oxo-Fe(salen)2 under the optimal reaction condition. Several transition metal(salen) were tested, and only Fe (salen) shows an excellent results towards transesterification of glycerol. Therefore, Fe (salen) was characterized by IR, elemental analysis, MS, XPS and Surface Basicity test, and it can be confirmed that the as-synthesized Fe(salen) was existed in the form of <math><mi>μ</mi></math>-oxo-Fe(salen)2. It was proposed that the <math><mi>μ</mi></math>-oxo-Fe(salen)2 can provide two different reaction pathway based on its molecular structures and the electronic configuration of iron itself. <math><mi>μ</mi></math>-oxo-Fe(salen)2 was reacted with the mixture of glycerol and DMC under microwave-heating in 60 min at 100 °C and at the molar ratio of glycerol:DMC:<math><mi>μ</mi></math>-oxo-Fe(salen)2 of 1:2:0.01 and obtaining the highest glycerol carbonate yield of 93.8 %.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1025 ","pages":"Article 123467"},"PeriodicalIF":2.1,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143138864","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}

引用次数: 0

Sequential phase transfer catalysis–hydrosilylation as an efficient method for the synthesis of polyfluorinated triethoxysilanes

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-02-01 DOI: 10.1016/j.jorganchem.2024.123483

M.A. Stepanov, Yu.I. Bolgova, O.M. Trofimova, E.F. Belogolova, A.I. Emel'yanov, A.I. Albanov, A.S. Pozdnyakov

An efficient approach to obtain of polyfluorinated triethoxysilanes H(CF₂)_nCH₂O(CH₂)₃Si(OEt)₃ with high yields, is presented using a sequential reactions of phase transfer catalysis and hydrosilylation. Tetrabutylammonium bromide and Speier's catalyst (200 ppm) were used as catalysts. The hydrosilylation reaction proceeds rather quickly within 1–3 h under mild conditions at room temperature. ¹H NMR monitoring indicates a selective process with the formation of only the main γ-addition product. The individuality of the synthesized triethoxy(polyfluoroalkoxy)propyl silanes have been confirmed by FTIR, ¹H, ¹³C, ¹⁹F, and ²⁹Si NMR spectroscopy and elemental analysis. Quantum chemical calculations have shown that with a decrease in the number of electronegative fragments CF₂ in the molecule, an increase in the energetic favorability of the hydrosilylation reaction is observed. The prospects for using the obtained fluorosilanes in polymer systems are discussed.

{"title":"Sequential phase transfer catalysis–hydrosilylation as an efficient method for the synthesis of polyfluorinated triethoxysilanes","authors":"M.A. Stepanov, Yu.I. Bolgova, O.M. Trofimova, E.F. Belogolova, A.I. Emel'yanov, A.I. Albanov, A.S. Pozdnyakov","doi":"10.1016/j.jorganchem.2024.123483","DOIUrl":"10.1016/j.jorganchem.2024.123483","url":null,"abstract":"<div><div>An efficient approach to obtain of polyfluorinated triethoxysilanes H(CF2)nCH2O(CH2)3Si(OEt)3 with high yields, is presented using a sequential reactions of phase transfer catalysis and hydrosilylation. Tetrabutylammonium bromide and Speier's catalyst (200 ppm) were used as catalysts. The hydrosilylation reaction proceeds rather quickly within 1–3 h under mild conditions at room temperature. 1H NMR monitoring indicates a selective process with the formation of only the main γ-addition product. The individuality of the synthesized triethoxy(polyfluoroalkoxy)propyl silanes have been confirmed by FTIR, 1H, 13C, 19F, and 29Si NMR spectroscopy and elemental analysis. Quantum chemical calculations have shown that with a decrease in the number of electronegative fragments CF2 in the molecule, an increase in the energetic favorability of the hydrosilylation reaction is observed. The prospects for using the obtained fluorosilanes in polymer systems are discussed.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1025 ","pages":"Article 123483"},"PeriodicalIF":2.1,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143138992","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}

引用次数: 0

A comparative study of CH and mCH mechanisms in hydrosilylation reactions

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-02-01 DOI: 10.1016/j.jorganchem.2024.123451

Manxin Hong , Zhengjian Qi , Yu Sun

The cyclic process of Si-H oxidation addition, olefin insertion, and reductive elimination was discussed by density functional theory (DFT) and high-precision quantum chemical calculations. All the calculations were performed at the B3LYP-D3/def2-TZVP level. Two fundamental mechanisms of Chalk-Harrod (CH) and modified Chalk-Harrod (mCH) were explored, in the perspective of computational chemistry. Pt(PH₃)₂ was used as model for the renowned Speier's catalyst, while HSiR (R=(CH₃)₃ and CH₃(OSi(CH₃)₃)₂ and CH₂=CHR’ (R’=H, CH₂OH and CH₂OCH₂CH₂OH) were used as the reactant models. Significant findings include the identification of the olefin insertion as the rate-determining step in both mechanisms.The energy barrier of rate-determining step was 27.6 kcal/mol and 41.0 kcal/mol, respectively, according to the CH mechanism and the mCH mechanism, when HSi(CH₃)₃ and CH₂=CH₂ were used as the reactant models. But the barrier of rate-determining step become to 27.2 kcal/mol and 28.4 kcal/mol, when HSiCH₃(OSi(CH₃)₃)₂ and CH₂=CHCH₂OCH₂CH₂OH were used as the reactant models. The difference in energy barriers betweeen the CH and mCH mechanisms become closer as the reactant models increase. The reaction between polyhydrosiloxane and allyl polyether may very potentially follow the mCH mechanism rather than CH mechanism.

{"title":"A comparative study of CH and mCH mechanisms in hydrosilylation reactions","authors":"Manxin Hong , Zhengjian Qi , Yu Sun","doi":"10.1016/j.jorganchem.2024.123451","DOIUrl":"10.1016/j.jorganchem.2024.123451","url":null,"abstract":"<div><div>The cyclic process of Si-H oxidation addition, olefin insertion, and reductive elimination was discussed by density functional theory (DFT) and high-precision quantum chemical calculations. All the calculations were performed at the B3LYP-D3/def2-TZVP level. Two fundamental mechanisms of Chalk-Harrod (CH) and modified Chalk-Harrod (mCH) were explored, in the perspective of computational chemistry. Pt(PH3)2 was used as model for the renowned Speier's catalyst, while HSiR (R=(CH3)3 and CH3(OSi(CH3)3)2 and CH2=CHR’ (R’=H, CH2OH and CH2OCH2CH2OH) were used as the reactant models. Significant findings include the identification of the olefin insertion as the rate-determining step in both mechanisms.The energy barrier of rate-determining step was 27.6 kcal/mol and 41.0 kcal/mol, respectively, according to the CH mechanism and the mCH mechanism, when HSi(CH3)3 and CH2=CH2 were used as the reactant models. But the barrier of rate-determining step become to 27.2 kcal/mol and 28.4 kcal/mol, when HSiCH3(OSi(CH3)3)2 and CH2=CHCH2OCH2CH2OH were used as the reactant models. The difference in energy barriers betweeen the CH and mCH mechanisms become closer as the reactant models increase. The reaction between polyhydrosiloxane and allyl polyether may very potentially follow the mCH mechanism rather than CH mechanism.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1025 ","pages":"Article 123451"},"PeriodicalIF":2.1,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143139469","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}

引用次数: 0

Application of supported palladium nanoparticles over chitosan-agarose encapsulated Fe3O4 microspheres as efficient catalyst in the Sonogashira cross-coupling reactions

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-02-01 DOI: 10.1016/j.jorganchem.2025.123553

Ali Kakanejadifard , Parisa Safarimehr , Bikash Karmakar , Mozhgan Pirhayati , Hojat Veisi

In this work, a simple and modified method for immobilizing Pd(0) NPs on the surface of dual functionalized magnetic Fe₃O₄ microspheres with chitosan-agarose (CS-Agar) has been used. The high area surface showed a dispersion of the minuscule Pd NPs. The key role of the CS-Agar hydrogel is to reduce Pd ions via a green pathway, stabilizing them via capping in the process. In order to determine the morphological aspects of the synthesized material, it was subjected to a variety of physicochemical techniques, including FE-SEM (Field Emission Scanning Electron Microscopy) and TEM (Transmission Electron Microscopy). The new material was studied catalytically as a reusable heterogeneous nanocatalyst that is effective in phosphine-free production of a variety of stilbene derivatives using the Sonogashira coupling method. Excellent results were obtained in every reaction, with the exception of chloroarenes and sterically hindered substrates. Without seeing a discernible decline in activity, the catalyst was reused seven times in a row.

{"title":"Application of supported palladium nanoparticles over chitosan-agarose encapsulated Fe3O4 microspheres as efficient catalyst in the Sonogashira cross-coupling reactions","authors":"Ali Kakanejadifard , Parisa Safarimehr , Bikash Karmakar , Mozhgan Pirhayati , Hojat Veisi","doi":"10.1016/j.jorganchem.2025.123553","DOIUrl":"10.1016/j.jorganchem.2025.123553","url":null,"abstract":"<div><div>In this work, a simple and modified method for immobilizing Pd(0) NPs on the surface of dual functionalized magnetic Fe3O4 microspheres with chitosan-agarose (CS-Agar) has been used. The high area surface showed a dispersion of the minuscule Pd NPs. The key role of the CS-Agar hydrogel is to reduce Pd ions via a green pathway, stabilizing them via capping in the process. In order to determine the morphological aspects of the synthesized material, it was subjected to a variety of physicochemical techniques, including FE-SEM (Field Emission Scanning Electron Microscopy) and TEM (Transmission Electron Microscopy). The new material was studied catalytically as a reusable heterogeneous nanocatalyst that is effective in phosphine-free production of a variety of stilbene derivatives using the Sonogashira coupling method. Excellent results were obtained in every reaction, with the exception of chloroarenes and sterically hindered substrates. Without seeing a discernible decline in activity, the catalyst was reused seven times in a row.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1029 ","pages":"Article 123553"},"PeriodicalIF":2.1,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143268005","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}

引用次数: 0

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Journal of Organometallic Chemistry

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