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A simple, highly selective ferrocene-based chalcone fluorescent probe for the detection of CrO42− and Cr2O72− ions
IF 2.1 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-12-26 DOI: 10.1016/j.jorganchem.2024.123489
Yuting Liu , Zixu Zhang , Dawei Yin , Yukai Huang , Ruilin Zheng , Yi Zhou , Jiabao Chen , Chi Dang
Cr (VI) is the most common water contaminant and is used in aluminum plating, paint production, leather tanning, etc. Cr (VI) is a kind of inhaled and swallowed poison, can enter the body through the digestive tract, respiratory tract, skin mucous membranes, may occur after skin contact dermatitis, or allergic phenomenon, in view of the harm of Cr (VI) to the human body, the development of a probe that can detect two kinds of Cr (VI) in the environment is an urgent problem. In this paper, 1-ferrocenyl-3-(2-hydroxyphenyl) allyl ketone (Probe A) was synthesized by solid phase grinding using acetyl ferrocene and o-hydroxybenzaldehyde as raw materials and I2 as catalyst by green synthesis method. It was found that 1-ferrocenyl-3-(2-hydroxyphenyl) allyl ketone had specific recognition ability to Cr2O72− and CrO42− by UV spectroscopy and fluorescence spectroscopy. It has better anti-interference performance under complex conditions. In addition, it was found that the binding ratio, binding constant and detection limit of 1-ferrocenyl-3-(2-hydroxyphenyl) allyl ketone for Cr2O72− and CrO42− were 1:1 and 3:2, respectively. 5.1330×106 M−1and 5.7048×104 M−1, 1.6714×10−4 M, 1.7246×10−4 M by UV titration experiment. The effect of pH and time on the recognition ions of 1-ferrocenyl-3-(2‑hydroxy-phenyl) allyl ketone was studied. In 80 min, the probe structure is stable, CrO42− and Cr2O72− can be identified stably. when the pH of the solution is 7∼8, the identification effect of probe A on Cr2O72− and CrO42− ions is the best. The sensing mechanism of 1-ferrocenyl-3-(2-hydroxyphenyl) allyl ketone with Cr2O72− and CrO42− was obtained by infrared and nuclear magnetic titration. And we carried out the test strip experiment, observed that with the increase of concentration, the color of the test strip changes significantly, which can be used for "naked eye" identification, this method can be more convenient and rapid detection of Cr (VI) solution.
{"title":"A simple, highly selective ferrocene-based chalcone fluorescent probe for the detection of CrO42− and Cr2O72− ions","authors":"Yuting Liu ,&nbsp;Zixu Zhang ,&nbsp;Dawei Yin ,&nbsp;Yukai Huang ,&nbsp;Ruilin Zheng ,&nbsp;Yi Zhou ,&nbsp;Jiabao Chen ,&nbsp;Chi Dang","doi":"10.1016/j.jorganchem.2024.123489","DOIUrl":"10.1016/j.jorganchem.2024.123489","url":null,"abstract":"<div><div>Cr (VI) is the most common water contaminant and is used in aluminum plating, paint production, leather tanning, etc. Cr (VI) is a kind of inhaled and swallowed poison, can enter the body through the digestive tract, respiratory tract, skin mucous membranes, may occur after skin contact dermatitis, or allergic phenomenon, in view of the harm of Cr (VI) to the human body, the development of a probe that can detect two kinds of Cr (VI) in the environment is an urgent problem. In this paper, 1-ferrocenyl-3-(2-hydroxyphenyl) allyl ketone (Probe A) was synthesized by solid phase grinding using acetyl ferrocene and o-hydroxybenzaldehyde as raw materials and I<sub>2</sub> as catalyst by green synthesis method. It was found that 1-ferrocenyl-3-(2-hydroxyphenyl) allyl ketone had specific recognition ability to Cr<sub>2</sub>O<sub>7</sub><sup>2−</sup> and CrO<sub>4</sub><sup>2−</sup> by UV spectroscopy and fluorescence spectroscopy. It has better anti-interference performance under complex conditions. In addition, it was found that the binding ratio, binding constant and detection limit of 1-ferrocenyl-3-(2-hydroxyphenyl) allyl ketone for Cr<sub>2</sub>O<sub>7</sub><sup>2−</sup> and CrO<sub>4</sub><sup>2−</sup> were 1:1 and 3:2, respectively. 5.1330×10<sup>6</sup> M<sup>−1</sup>and 5.7048×10<sup>4</sup> M<sup>−1</sup>, 1.6714×10<sup>−4</sup> M, 1.7246×10<sup>−4</sup> M by UV titration experiment. The effect of pH and time on the recognition ions of 1-ferrocenyl-3-(2‑hydroxy-phenyl) allyl ketone was studied. In 80 min, the probe structure is stable, CrO<sub>4</sub><sup>2−</sup> and Cr<sub>2</sub>O<sub>7</sub><sup>2−</sup> can be identified stably. when the pH of the solution is 7∼8, the identification effect of probe A on Cr<sub>2</sub>O<sub>7</sub><sup>2−</sup> and CrO<sub>4</sub><sup>2−</sup> ions is the best. The sensing mechanism of 1-ferrocenyl-3-(2-hydroxyphenyl) allyl ketone with Cr<sub>2</sub>O<sub>7</sub><sup>2−</sup> and CrO<sub>4</sub><sup>2−</sup> was obtained by infrared and nuclear magnetic titration. And we carried out the test strip experiment, observed that with the increase of concentration, the color of the test strip changes significantly, which can be used for \"naked eye\" identification, this method can be more convenient and rapid detection of Cr (VI) solution.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1026 ","pages":"Article 123489"},"PeriodicalIF":2.1,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143309545","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
Development of magnetically retrievable nanostructure Pd catalyst system supported on keratin-Schiff base and its application in catalytic and antioxidant activities
IF 2.1 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-12-26 DOI: 10.1016/j.jorganchem.2024.123492
Nuray Yılmaz Baran , Emel Çakmak , Yavuz Selim Çakmak , Talat Baran
<div><div>Recently, the production of biomaterial supported metal nanoparticles has gained significant importance as an emerging field with numerous applications ranging from healthcare to sustainable environment due to their unique chemical, catalytic, physical, and biological properties. In this paper, we fabricated magnetically retrievable Schiff base modified-keratin supported nano-sized Pd catalyst (Pd@keratin/Fe<sub>3</sub>O<sub>4</sub>/Sch) to investigate its catalytic and antioxidant characteristics. The design procedure for Pd@keratin/Fe<sub>3</sub>O<sub>4</sub>/Sch is as follows: (1) extraction of keratin from goose feathers, (2) loading of Fe<sub>3</sub>O<sub>4</sub> onto keratin (keratin/Fe<sub>3</sub>O<sub>4</sub>), (3) amino-functionalization of keratin/Fe<sub>3</sub>O<sub>4</sub> (keratin/Fe<sub>3</sub>O<sub>4</sub>/APT), (4) Schiff base modification of keratin/Fe<sub>3</sub>O<sub>4</sub>/APT (keratin/Fe<sub>3</sub>O<sub>4</sub>/Sch), and (5) preparation of the nano-structured Pd catalyst. Diverse analytical methods, bearing FT-IR, TEM, EDS, XRD, TGA, XPS, BET and FE-SEM were utilized to substantiate production of Pd nanoparticles. TEM results indicated that the formed Pd nanoparticles had an average particle size of 20 nm. The catalytic behavior of Pd@keratin/Fe<sub>3</sub>O<sub>4</sub>/Sch was then studied in the catalytic reduction of nitroaromatics (<em>p</em>-nitrophenol (<em>p</em>-NP), <em>p</em>-nitro-<em>o</em>-phenylenediamine (<em>p</em>-NPDA), <em>o</em>-nitroaniline (<em>o</em>-NA), <em>p</em>-nitroaniline (<em>p</em>-NA)) and organic dyes (rhodamine B (RhB), methyl orange (MO) and methylene blue (MB)). The Pd@keratin/Fe<sub>3</sub>O<sub>4</sub>/Sch successfully reduced <em>p</em>-NP, <em>p</em>-NPDA, <em>p</em>-NA, and <em>o</em>-NA rapidly with rate constants of 0.018 s<sup>−1</sup>, 0.013 s<sup>−1</sup>, 0.039 s<sup>−1</sup>, and 0.034 s<sup>−1</sup>, respectively. In addition, it promptly reduced MB, while it reduced MO and RhB with rate constants of 0.023 s<sup>−1</sup> and 0.054 s<sup>−1</sup>, respectively. The Pd@keratin/Fe<sub>3</sub>O<sub>4</sub>/Sch was readily recovered due to its magnetic nature and was reused up to six cycles. The stability of Pd@keratin/Fe<sub>3</sub>O<sub>4</sub>/Sch was confirmed through EDS and ICP analyses conducted after the reusability tests. The samples obtained after each step in the Pd@keratin/Fe<sub>3</sub>O<sub>4</sub>/Sch production were also investigated for their antioxidant activities. The order of antioxidant activity was found to decrease in the following sequence: keratin/Fe<sub>3</sub>O<sub>4</sub>, Pd@keratin/Fe<sub>3</sub>O<sub>4</sub>/Sch, keratin/Fe<sub>3</sub>O<sub>4</sub>/APT, keratin/Fe<sub>3</sub>O<sub>4</sub>/Sch and keratin, respectively. The fabricated Pd@keratin/Fe<sub>3</sub>O<sub>4</sub>/Sch is an ideal catalyst system for remediating wastewater contaminants and biological applications with excellent catalytic and antioxidant capacity, easy recovery, and
{"title":"Development of magnetically retrievable nanostructure Pd catalyst system supported on keratin-Schiff base and its application in catalytic and antioxidant activities","authors":"Nuray Yılmaz Baran ,&nbsp;Emel Çakmak ,&nbsp;Yavuz Selim Çakmak ,&nbsp;Talat Baran","doi":"10.1016/j.jorganchem.2024.123492","DOIUrl":"10.1016/j.jorganchem.2024.123492","url":null,"abstract":"&lt;div&gt;&lt;div&gt;Recently, the production of biomaterial supported metal nanoparticles has gained significant importance as an emerging field with numerous applications ranging from healthcare to sustainable environment due to their unique chemical, catalytic, physical, and biological properties. In this paper, we fabricated magnetically retrievable Schiff base modified-keratin supported nano-sized Pd catalyst (Pd@keratin/Fe&lt;sub&gt;3&lt;/sub&gt;O&lt;sub&gt;4&lt;/sub&gt;/Sch) to investigate its catalytic and antioxidant characteristics. The design procedure for Pd@keratin/Fe&lt;sub&gt;3&lt;/sub&gt;O&lt;sub&gt;4&lt;/sub&gt;/Sch is as follows: (1) extraction of keratin from goose feathers, (2) loading of Fe&lt;sub&gt;3&lt;/sub&gt;O&lt;sub&gt;4&lt;/sub&gt; onto keratin (keratin/Fe&lt;sub&gt;3&lt;/sub&gt;O&lt;sub&gt;4&lt;/sub&gt;), (3) amino-functionalization of keratin/Fe&lt;sub&gt;3&lt;/sub&gt;O&lt;sub&gt;4&lt;/sub&gt; (keratin/Fe&lt;sub&gt;3&lt;/sub&gt;O&lt;sub&gt;4&lt;/sub&gt;/APT), (4) Schiff base modification of keratin/Fe&lt;sub&gt;3&lt;/sub&gt;O&lt;sub&gt;4&lt;/sub&gt;/APT (keratin/Fe&lt;sub&gt;3&lt;/sub&gt;O&lt;sub&gt;4&lt;/sub&gt;/Sch), and (5) preparation of the nano-structured Pd catalyst. Diverse analytical methods, bearing FT-IR, TEM, EDS, XRD, TGA, XPS, BET and FE-SEM were utilized to substantiate production of Pd nanoparticles. TEM results indicated that the formed Pd nanoparticles had an average particle size of 20 nm. The catalytic behavior of Pd@keratin/Fe&lt;sub&gt;3&lt;/sub&gt;O&lt;sub&gt;4&lt;/sub&gt;/Sch was then studied in the catalytic reduction of nitroaromatics (&lt;em&gt;p&lt;/em&gt;-nitrophenol (&lt;em&gt;p&lt;/em&gt;-NP), &lt;em&gt;p&lt;/em&gt;-nitro-&lt;em&gt;o&lt;/em&gt;-phenylenediamine (&lt;em&gt;p&lt;/em&gt;-NPDA), &lt;em&gt;o&lt;/em&gt;-nitroaniline (&lt;em&gt;o&lt;/em&gt;-NA), &lt;em&gt;p&lt;/em&gt;-nitroaniline (&lt;em&gt;p&lt;/em&gt;-NA)) and organic dyes (rhodamine B (RhB), methyl orange (MO) and methylene blue (MB)). The Pd@keratin/Fe&lt;sub&gt;3&lt;/sub&gt;O&lt;sub&gt;4&lt;/sub&gt;/Sch successfully reduced &lt;em&gt;p&lt;/em&gt;-NP, &lt;em&gt;p&lt;/em&gt;-NPDA, &lt;em&gt;p&lt;/em&gt;-NA, and &lt;em&gt;o&lt;/em&gt;-NA rapidly with rate constants of 0.018 s&lt;sup&gt;−1&lt;/sup&gt;, 0.013 s&lt;sup&gt;−1&lt;/sup&gt;, 0.039 s&lt;sup&gt;−1&lt;/sup&gt;, and 0.034 s&lt;sup&gt;−1&lt;/sup&gt;, respectively. In addition, it promptly reduced MB, while it reduced MO and RhB with rate constants of 0.023 s&lt;sup&gt;−1&lt;/sup&gt; and 0.054 s&lt;sup&gt;−1&lt;/sup&gt;, respectively. The Pd@keratin/Fe&lt;sub&gt;3&lt;/sub&gt;O&lt;sub&gt;4&lt;/sub&gt;/Sch was readily recovered due to its magnetic nature and was reused up to six cycles. The stability of Pd@keratin/Fe&lt;sub&gt;3&lt;/sub&gt;O&lt;sub&gt;4&lt;/sub&gt;/Sch was confirmed through EDS and ICP analyses conducted after the reusability tests. The samples obtained after each step in the Pd@keratin/Fe&lt;sub&gt;3&lt;/sub&gt;O&lt;sub&gt;4&lt;/sub&gt;/Sch production were also investigated for their antioxidant activities. The order of antioxidant activity was found to decrease in the following sequence: keratin/Fe&lt;sub&gt;3&lt;/sub&gt;O&lt;sub&gt;4&lt;/sub&gt;, Pd@keratin/Fe&lt;sub&gt;3&lt;/sub&gt;O&lt;sub&gt;4&lt;/sub&gt;/Sch, keratin/Fe&lt;sub&gt;3&lt;/sub&gt;O&lt;sub&gt;4&lt;/sub&gt;/APT, keratin/Fe&lt;sub&gt;3&lt;/sub&gt;O&lt;sub&gt;4&lt;/sub&gt;/Sch and keratin, respectively. The fabricated Pd@keratin/Fe&lt;sub&gt;3&lt;/sub&gt;O&lt;sub&gt;4&lt;/sub&gt;/Sch is an ideal catalyst system for remediating wastewater contaminants and biological applications with excellent catalytic and antioxidant capacity, easy recovery, and ","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1026 ","pages":"Article 123492"},"PeriodicalIF":2.1,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143309521","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
Direct synthesis of hyperbranched oligoethylene using o-phenylene-bridged binuclear pyridine-imine Ni(II) catalysts
IF 2.1 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-12-25 DOI: 10.1016/j.jorganchem.2024.123491
Hua Wang , Yusheng Han , Yan Wang , Weiqing Lu , Hui Wang
Recently, nickel and palladium complexes based on pyridine-imine platform have found extensive application in olefin polymerization and copolymerization. In this study, we created two o-phenylene-bridged dinuclear nickel pyridine-imine catalysts for the oligomerization of ethylene. The dinuclear catalyst with an H atom at the 6-position of pyridine exhibited exceptionally high polymerization activity, which is an order of magnitude higher (2.82–4.65 vs 0.57–0.66 × 106 g.mol−1h−1) than that of its corresponding brominated analog. On the other hand, the oligoethylenes produced by this catalyst had a molecular weight that is also an order of magnitude higher (1582–2213 vs 315–382 g/mol) and possesses a lower branching density (88–101 vs. 133–161/1000C) compared to the oligoethylenes generated by the brominated analog. When further compared to the corresponding mononuclear nickel catalyst, the dinuclear catalyst demonstrated a stronger ability to inhibit chain transfer and chain walking, resulting in the production of oligoethylenes with higher molecular weight and lower branching density. This may be attributed to a bimetallic synergistic effect or merely a steric hindrance superposition effect. Additionally, nuclear magnetic resonance (NMR) analysis further confirmed the hyperbranched structure of the oligoethylenes.
{"title":"Direct synthesis of hyperbranched oligoethylene using o-phenylene-bridged binuclear pyridine-imine Ni(II) catalysts","authors":"Hua Wang ,&nbsp;Yusheng Han ,&nbsp;Yan Wang ,&nbsp;Weiqing Lu ,&nbsp;Hui Wang","doi":"10.1016/j.jorganchem.2024.123491","DOIUrl":"10.1016/j.jorganchem.2024.123491","url":null,"abstract":"<div><div>Recently, nickel and palladium complexes based on pyridine-imine platform have found extensive application in olefin polymerization and copolymerization. In this study, we created two <em>o</em>-phenylene-bridged dinuclear nickel pyridine-imine catalysts for the oligomerization of ethylene. The dinuclear catalyst with an H atom at the 6-position of pyridine exhibited exceptionally high polymerization activity, which is an order of magnitude higher (2.82–4.65 vs 0.57–0.66 × 10<sup>6</sup> g.mol<sup>−1</sup>h<sup>−1</sup>) than that of its corresponding brominated analog. On the other hand, the oligoethylenes produced by this catalyst had a molecular weight that is also an order of magnitude higher (1582–2213 vs 315–382 g/mol) and possesses a lower branching density (88–101 vs. 133–161/1000C) compared to the oligoethylenes generated by the brominated analog. When further compared to the corresponding mononuclear nickel catalyst, the dinuclear catalyst demonstrated a stronger ability to inhibit chain transfer and chain walking, resulting in the production of oligoethylenes with higher molecular weight and lower branching density. This may be attributed to a bimetallic synergistic effect or merely a steric hindrance superposition effect. Additionally, nuclear magnetic resonance (NMR) analysis further confirmed the hyperbranched structure of the oligoethylenes.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1026 ","pages":"Article 123491"},"PeriodicalIF":2.1,"publicationDate":"2024-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143309543","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
Deprotonative approach to poly(1,3-phenylene) synthesis by palladium-catalyzed cross-coupling polymerization
IF 2.1 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-12-20 DOI: 10.1016/j.jorganchem.2024.123488
Farid Fithrie bin Zainal Annuar , Shuichi Ikeda , Kentaro Okano , Atsunori Mori
The directing effect of oxygen atom in 4-halo-alkoxybenzene allowed ortho-lithiation at the carbon atom adjacent to the oxygen atom using lithium 2,2,6,6-tetramethylpiperidide (LiTMP). The obtained organolithium intermediate was trapped by a boron reagent to afford 2-borylated 4-halo-alkoxybenzene. The arylboronate underwent palladiumcatalyzed cross-coupling polymerization to give regioregular poly(1,3-phenylene) with the average degree of polymerization (DPn) close to the theoretical one based on the ratio of monomer feed vs. catalyst loading. The overall borylation-polymerization sequence was also found to proceed in a one-pot manner to afford poly(1,3-phenylene).
{"title":"Deprotonative approach to poly(1,3-phenylene) synthesis by palladium-catalyzed cross-coupling polymerization","authors":"Farid Fithrie bin Zainal Annuar ,&nbsp;Shuichi Ikeda ,&nbsp;Kentaro Okano ,&nbsp;Atsunori Mori","doi":"10.1016/j.jorganchem.2024.123488","DOIUrl":"10.1016/j.jorganchem.2024.123488","url":null,"abstract":"<div><div>The directing effect of oxygen atom in 4-halo-alkoxybenzene allowed ortho-lithiation at the carbon atom adjacent to the oxygen atom using lithium 2,2,6,6-tetramethylpiperidide (LiTMP). The obtained organolithium intermediate was trapped by a boron reagent to afford 2-borylated 4-halo-alkoxybenzene. The arylboronate underwent palladiumcatalyzed cross-coupling polymerization to give regioregular poly(1,3-phenylene) with the average degree of polymerization (<em>DP</em>n) close to the theoretical one based on the ratio of monomer feed vs. catalyst loading. The overall borylation-polymerization sequence was also found to proceed in a one-pot manner to afford poly(1,3-phenylene).</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1026 ","pages":"Article 123488"},"PeriodicalIF":2.1,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143309539","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
Study on the effect of auxiliary ligands in CoIII-NHC Complexes towards alkylation of amines using alcohols
IF 2.1 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-12-20 DOI: 10.1016/j.jorganchem.2024.123479
Misba Siddique, Biswaranjan Boity, Arnab Rit
Here, we have presented a systematic study on the cobalt-mediated alkylation of amines using aromatic primary alcohols with sterically demanding substrates. In this context, we have employed two newly synthesized cobalt-NHC complexes Co1 and Co2, and pyridine appended (Co3-Co6) complexes to evaluate their catalytic efficiency. Among them, the pyridine-based benzimidazolin-2-ylidene Co-NHC complexes Co4 and Co6 showed high efficiency. However, the complex Co4, featuring a Cp*, exhibited lesser reactivity with sterically demanding ortho-substituted anilines, whereas complex Co6, with an acetylacetonate (acac) ligand, outperformed the rest. This outcome aligns with the steric mapping results of the employed catalysts. Furthermore, complex Co6 proved to be effective for the cyclization of 2-nitroaniline via coupling with various substituted benzyl alcohols.
{"title":"Study on the effect of auxiliary ligands in CoIII-NHC Complexes towards alkylation of amines using alcohols","authors":"Misba Siddique,&nbsp;Biswaranjan Boity,&nbsp;Arnab Rit","doi":"10.1016/j.jorganchem.2024.123479","DOIUrl":"10.1016/j.jorganchem.2024.123479","url":null,"abstract":"<div><div>Here, we have presented a systematic study on the cobalt-mediated alkylation of amines using aromatic primary alcohols with sterically demanding substrates. In this context, we have employed two newly synthesized cobalt-NHC complexes <strong>Co1</strong> and <strong>Co2</strong>, and pyridine appended (<strong>Co3</strong>-<strong>Co6</strong>) complexes to evaluate their catalytic efficiency. Among them, the pyridine-based benzimidazolin-2-ylidene Co-NHC complexes <strong>Co4</strong> and <strong>Co6</strong> showed high efficiency. However, the complex <strong>Co4</strong>, featuring a <strong>Cp*</strong>, exhibited lesser reactivity with sterically demanding <em>ortho</em>-substituted anilines, whereas complex <strong>Co6</strong>, with an acetylacetonate (acac) ligand, outperformed the rest. This outcome aligns with the steric mapping results of the employed catalysts. Furthermore, complex <strong>Co6</strong> proved to be effective for the cyclization of 2-nitroaniline <em>via</em> coupling with various substituted benzyl alcohols.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1027 ","pages":"Article 123479"},"PeriodicalIF":2.1,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143358348","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
Theoretical studies on the mechanism of Rh−catalyzed [3+2+1] cycloaddition reaction of vinylidene cyclopropane with carbon monoxide
IF 2.1 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-12-19 DOI: 10.1016/j.jorganchem.2024.123487
Huimin Xu, Tao Wang, Wanjun Zhao, Ying Ren, Jianfeng Jia, Hai-Shun Wu
DFT calculations have been carried out to study the mechanism of the Rh-catalyzed Pauson-Khand [3+2+1] cycloaddition reaction of vinylidene cyclopropane with carbon monoxide, as well as the diastereoselectivity of the products. It is found that reaction initializes by oxidative addition involves the distal C−C bond cleavage of cyclopropane groups, which is promoted by Rh(I) complex, to give η4-TMM Rh(III) intermediate, followed by CO insertion. Continuing with the next process, olefin insertion, determines the formation of the cis-product or trans-product, depending on the orientation of coordinated olefin moiety to the Rh center. The calculations provide a successful interpretation of the experimental observersed diastereoselectivity.
{"title":"Theoretical studies on the mechanism of Rh−catalyzed [3+2+1] cycloaddition reaction of vinylidene cyclopropane with carbon monoxide","authors":"Huimin Xu,&nbsp;Tao Wang,&nbsp;Wanjun Zhao,&nbsp;Ying Ren,&nbsp;Jianfeng Jia,&nbsp;Hai-Shun Wu","doi":"10.1016/j.jorganchem.2024.123487","DOIUrl":"10.1016/j.jorganchem.2024.123487","url":null,"abstract":"<div><div>DFT calculations have been carried out to study the mechanism of the Rh-catalyzed Pauson-Khand [3+2+1] cycloaddition reaction of vinylidene cyclopropane with carbon monoxide, as well as the diastereoselectivity of the products. It is found that reaction initializes by oxidative addition involves the distal C−C bond cleavage of cyclopropane groups, which is promoted by Rh(I) complex, to give <em>η</em><sup>4</sup>-TMM Rh(III) intermediate, followed by CO insertion. Continuing with the next process, olefin insertion, determines the formation of the <em>cis</em>-product or <em>trans</em>-product, depending on the orientation of coordinated olefin moiety to the Rh center. The calculations provide a successful interpretation of the experimental observersed diastereoselectivity.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1026 ","pages":"Article 123487"},"PeriodicalIF":2.1,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143309524","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 structural characterization of 2,2’-bipyridine zinc formate: Analysis of formate bonding and hydrosilylation of CO2 and carbonyl compounds
IF 2.1 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-12-05 DOI: 10.1016/j.jorganchem.2024.123471
Gonzalo Fernandez de la Mora, Aaron Loo, Ran Yan, Eshe Hummingbird, Gerard Parkin
The zinc formate compound (bipy)Zn(O2CH)2 is obtained via the reaction of Zn(O2CH)2 with 2,2’-bipyridine (bipy). In addition, (bipy)Zn(O2CH)2 may be formed from zinc hydride via addition of bipy followed by addition of (i) HCO2H and (ii) CO2. The molecular structure of (bipy)Zn(O2CH)2 has been determined by X-ray diffraction, thereby demonstrating that it exists as a monomeric species with a distorted tetrahedral zinc center and κ1-monodentate formate ligands. As such, the coordination environment of the zinc provides a contrast to the octahedral sites in the isomeric 4,4’-bipyridine counterpart, (bipy4,4’)Zn(O2CH)2, and the aqua derivative, (bipy)Zn(O2CH)2(OH2)·H2O, both of which feature bridging formate ligands. Analysis of the bonding within the formate ligand indicates that the zinc–formate moiety is not best represented by a Zn–O–C(=O)H resonance structure, but instead possesses a significant ionic component that reduces the C=O bond order and increases the C–O bond order. The formate compound (bipy)Zn(O2CH)2 participates in hydrosilylation transformations involving CO2 and carbonyl compounds, including (i) the reaction of CO2 with (MeO)3SiH to afford HCO2Si(OMe)3 and (ii) insertion of Ph2CO, PhC(O)Me, Me2CO and PhCHO into the Si–H bonds of PhSiH3 to afford PhSi[OCH(R)R’]3 via PhSiH2[OCH(R)R’] and PhSiH[OCH(R)R’]2.
{"title":"Synthesis and structural characterization of 2,2’-bipyridine zinc formate: Analysis of formate bonding and hydrosilylation of CO2 and carbonyl compounds","authors":"Gonzalo Fernandez de la Mora,&nbsp;Aaron Loo,&nbsp;Ran Yan,&nbsp;Eshe Hummingbird,&nbsp;Gerard Parkin","doi":"10.1016/j.jorganchem.2024.123471","DOIUrl":"10.1016/j.jorganchem.2024.123471","url":null,"abstract":"<div><div>The zinc formate compound (bipy)Zn(O<sub>2</sub>CH)<sub>2</sub> is obtained <em>via</em> the reaction of Zn(O<sub>2</sub>CH)<sub>2</sub> with 2,2’-bipyridine (bipy). In addition, (bipy)Zn(O<sub>2</sub>CH)<sub>2</sub> may be formed from zinc hydride <em>via</em> addition of bipy followed by addition of (i) HCO<sub>2</sub>H and (ii) CO<sub>2</sub>. The molecular structure of (bipy)Zn(O<sub>2</sub>CH)<sub>2</sub> has been determined by X-ray diffraction, thereby demonstrating that it exists as a monomeric species with a distorted tetrahedral zinc center and κ<sup>1</sup>-monodentate formate ligands. As such, the coordination environment of the zinc provides a contrast to the octahedral sites in the isomeric 4,4’-bipyridine counterpart, (bipy<sup>4,4’</sup>)Zn(O<sub>2</sub>CH)<sub>2</sub>, and the aqua derivative, (bipy)Zn(O<sub>2</sub>CH)<sub>2</sub>(OH<sub>2</sub>)·H<sub>2</sub>O, both of which feature bridging formate ligands. Analysis of the bonding within the formate ligand indicates that the zinc–formate moiety is not best represented by a Zn–O–C(=O)H resonance structure, but instead possesses a significant ionic component that reduces the C=O bond order and increases the C–O bond order. The formate compound (bipy)Zn(O<sub>2</sub>CH)<sub>2</sub> participates in hydrosilylation transformations involving CO<sub>2</sub> and carbonyl compounds, including (i) the reaction of CO<sub>2</sub> with (MeO)<sub>3</sub>SiH to afford HCO<sub>2</sub>Si(OMe)<sub>3</sub> and (ii) insertion of Ph<sub>2</sub>CO, PhC(O)Me, Me<sub>2</sub>CO and PhCHO into the Si–H bonds of PhSiH<sub>3</sub> to afford PhSi[OCH(R)R’]<sub>3</sub> <em>via</em> PhSiH<sub>2</sub>[OCH(R)R’] and PhSiH[OCH(R)R’]<sub>2</sub>.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1030 ","pages":"Article 123471"},"PeriodicalIF":2.1,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143444591","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
One-pot sustainable synthesis of novel pyrido[2,3-d]pyrimidinones and their evaluation for antitubercular and anticancer activity 新型吡啶[2,3-d]嘧啶类化合物的一锅可持续合成及其抗结核和抗癌活性评价
IF 2.1 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-26 DOI: 10.1016/j.jorganchem.2024.123450
Sumaiya Tabassum , Sankar Ganesh Ramaraj , J. Rajprasad , Vivekananthan Sadaiyandi , Niraj Kumar , Santhosh Govindaraju
A novel green protocol for the construction of diversified pyrido[2,3-d]pyrimidinones was accomplished by a single-pot reaction of aryl aldehydes, Meldrum's acid, thiobarbituric acid, and ammonium acetate/aniline in H2O using ʟ-proline as an expeditious reusable catalyst at room temperature (26 °C). Our strategy provides an innovative synthetic avenue for the construction of pyrido[2,3-d]pyrimidinones, as well as several advantages over traditional methods, including a simple procedure, shorter reaction duration, excellent yields, safe handling, easy workup, catalyst recovery, and environmental compatibility. Furthermore, the synthesised compounds were tested for their impact on different cell lines and microorganisms. Compounds 5d and 5e were particularly effective against Mycobacterium tuberculosis (antitubercular), human breast cancer cells (MCF-7), lung cancer cells (A549 and NCI-H460), and both Gram-positive (S. pyogenes) and Gram-negative (E. coli) bacteria. The derivatives with hydroxyl and nitro substitutions [5e, 5f] showed the highest potency against MCF-7, A549, and NCI-H460 cell lines, with IC50 values of 3.68–4.36, 3.82–3.41, and 11.34–12.28 µg/mL, respectively.
在室温(26°C)下,以脯氨酸作为快速可重复使用的催化剂,芳基醛、梅尔德鲁姆酸、硫代巴比妥酸和乙酸铵/苯胺在水中进行单锅反应,完成了构建多种吡啶[2,3-d]嘧啶酮的新型绿色方案。我们的策略为构建吡啶多[2,3-d]嘧啶酮提供了一种创新的合成途径,并且与传统方法相比具有几个优点,包括程序简单,反应时间短,收率高,处理安全,易于处理,催化剂回收,环境相容性好。此外,还测试了合成的化合物对不同细胞系和微生物的影响。化合物5d和5e对结核分枝杆菌(抗结核)、人乳腺癌细胞(MCF-7)、肺癌细胞(A549和NCI-H460)以及革兰氏阳性(化脓性葡萄球菌)和革兰氏阴性(大肠杆菌)都特别有效。羟基和硝基取代的衍生物[5e, 5f]对MCF-7、A549和NCI-H460细胞株的IC50值分别为3.68 ~ 4.36、3.82 ~ 3.41和11.34 ~ 12.28µg/mL。
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引用次数: 0
Catalytic epoxidation of olefin over metal-organic framework solids: A mini-review 烯烃在金属-有机骨架固体上的催化环氧化反应:综述
IF 2.1 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-26 DOI: 10.1016/j.jorganchem.2024.123449
Subratanath Koner
By the turn of new millennium, especially last two decades witnessed an explosive growth of metal-organic framework (MOF) chemistry and studies on their functional properties. In the last few years, in particular, usage of metal-organic framework in heterogeneous catalysis have attracted a lot of attention. Catalytic research is mainly focused on the transition metal MOFs, however, of late, non-transition metal-based MOFs are also used. Here, epoxidation/oxidation reaction catalyzed by MOF under heterogeneous condition will be summarized. We have designed quite a few lanthanide metal-based MOFs that showed spectacular catalytic activity in oxidation/epoxidation. This mini-review will give a brief description of catalytic epoxidation over metal-organic frameworks along with research activity in our laboratory on this particular area.
进入新世纪以来,特别是近二十年来,金属有机骨架(MOF)化学及其功能性质的研究得到了迅猛发展。近年来,金属-有机骨架在多相催化中的应用引起了广泛的关注。催化研究主要集中在过渡金属MOFs上,但近年来非过渡金属MOFs也得到了应用。本文综述了在非均相条件下MOF催化的环氧化/氧化反应。我们已经设计了相当多的镧系金属基mof,它们在氧化/环氧化反应中表现出惊人的催化活性。这篇小综述将简要介绍金属有机框架的催化环氧化反应以及我们实验室在这一特定领域的研究活动。
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引用次数: 0
Recent progress in synthesis, reactivity, and biological activities of selenopheno[2,3-c/3,2-c] pyrazole heterocycles 硒吩并[2,3-c/3,2-c] 吡唑杂环的合成、反应性和生物活性研究的最新进展
IF 2.1 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2024-11-24 DOI: 10.1016/j.jorganchem.2024.123447
Moustafa A. Gouda , Osama Alharbi , Nahlah A. Al-Hadhrami , Reem A.K. Alharbi , Rasha Jame
Pyrazole and selenophene are valuable heterocyclic compounds that play a crucial role in the development of new drug molecules. Combining the selenophene and pyrazole moieties to hybrid structures has opened exciting possibilities for various pharmacological activities, leading to the discovery of selenophenopyrazoles, including selenopheno[2,3-c]pyrazole and selenopheno[3,2-c]pyrazole. All of which exhibit intriguing properties. The synthesis of selenophenopyrazoles can be accomplished through several chemical reactions: Vilsmeier–Haack reaction, Thorpe–Ziegler cyclization, and Suzuki cross-coupling.
吡唑和硒吩是有价值的杂环化合物,在新药物分子的开发中起着至关重要的作用。将硒吩和吡唑分子结合成杂交结构,为各种药理活性提供了令人兴奋的可能性,从而发现了硒吩并吡唑,包括硒吩并[2,3-c]吡唑和硒吩并[3,2-c]吡唑。所有这些都表现出令人感兴趣的特性。硒吩并吡唑可通过几种化学反应合成:Vilsmeier-Haack 反应、Thorpe-Ziegler 环化反应和铃木交叉偶联反应。
{"title":"Recent progress in synthesis, reactivity, and biological activities of selenopheno[2,3-c/3,2-c] pyrazole heterocycles","authors":"Moustafa A. Gouda ,&nbsp;Osama Alharbi ,&nbsp;Nahlah A. Al-Hadhrami ,&nbsp;Reem A.K. Alharbi ,&nbsp;Rasha Jame","doi":"10.1016/j.jorganchem.2024.123447","DOIUrl":"10.1016/j.jorganchem.2024.123447","url":null,"abstract":"<div><div>Pyrazole and selenophene are valuable heterocyclic compounds that play a crucial role in the development of new drug molecules. Combining the selenophene and pyrazole moieties to hybrid structures has opened exciting possibilities for various pharmacological activities, leading to the discovery of selenophenopyrazoles, including selenopheno[2,3-<em>c</em>]pyrazole and selenopheno[3,2-<em>c</em>]pyrazole. All of which exhibit intriguing properties. The synthesis of selenophenopyrazoles can be accomplished through several chemical reactions: Vilsmeier–Haack reaction, Thorpe–Ziegler cyclization, and Suzuki cross-coupling.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1024 ","pages":"Article 123447"},"PeriodicalIF":2.1,"publicationDate":"2024-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142721819","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
期刊
Journal of Organometallic Chemistry
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