This work describes the synthesis and characterisation of six novel Schiff base complexes, Cu(II), Pd(II), and Fe(II), which, under the right circumstances, function as very efficient catalysts for the production of cyclic carbonates from CO2 and epoxides. FT-IR spectroscopy, elemental analysis, UV–Vis spectroscopy, molar conductivity, melting point, and magnetic susceptibility measurements are among the spectroscopic methods used to characterize newly synthesized complexes. The molar conductivity values, ranging from 2.58 to 4.03 µS/cm, suggest that the complexes exhibit no molar conductivity. Co-catalysts, such as 4-(dimethylamino)pyridine, pyridine, triethylamine, and triphenyl phosphine, were used in these processes, both with and without one. 4-(Dimethylamino)pyridine was used as the co-catalyst in the catalytic studies. Additionally, a number of variables that affect the cycloaddition process were examined, including the temperature, CO2 pressure, reaction time, and co-catalyst. All novel catalysts exhibited exceptional catalytic activity and selectivity in the catalytic assays. Regarding the coupling of CO2 and epichlorohydrin as epoxides, the L2-Cu catalyst outperformed other catalysts in terms of catalytic activity (90.7%) and selectivity (98.9%).
{"title":"Synthesis and catalytic application to form cyclic carbonates of novel Pd(II) Cu(II), and Fe(II) benzoate-based Schiff base metal complexes","authors":"Hatice Gamze Sogukomerogullari , Emine Aytar , Reşit Çakmak , Eyüp Başaran","doi":"10.1016/j.jorganchem.2024.123424","DOIUrl":"10.1016/j.jorganchem.2024.123424","url":null,"abstract":"<div><div>This work describes the synthesis and characterisation of six novel Schiff base complexes, Cu(II), Pd(II), and Fe(II), which, under the right circumstances, function as very efficient catalysts for the production of cyclic carbonates from CO<sub>2</sub> and epoxides. FT-IR spectroscopy, elemental analysis, UV–Vis spectroscopy, molar conductivity, melting point, and magnetic susceptibility measurements are among the spectroscopic methods used to characterize newly synthesized complexes. The molar conductivity values, ranging from 2.58 to 4.03 µS/cm, suggest that the complexes exhibit no molar conductivity. Co-catalysts, such as 4-(dimethylamino)pyridine, pyridine, triethylamine, and triphenyl phosphine, were used in these processes, both with and without one. 4-(Dimethylamino)pyridine was used as the co-catalyst in the catalytic studies. Additionally, a number of variables that affect the cycloaddition process were examined, including the temperature, CO<sub>2</sub> pressure, reaction time, and co-catalyst. All novel catalysts exhibited exceptional catalytic activity and selectivity in the catalytic assays. Regarding the coupling of CO<sub>2</sub> and epichlorohydrin as epoxides, the L2-Cu catalyst outperformed other catalysts in terms of catalytic activity (90.7%) and selectivity (98.9%).</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1023 ","pages":"Article 123424"},"PeriodicalIF":2.1,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142571513","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 : 2024-10-28DOI: 10.1016/j.jorganchem.2024.123432
Anqun Su , Dabo Jiang , Wenwei Hu , Shuting Liang , Kai Yu , Weijie Zhou , Jing Wang , Zaihui Fu , Yachun Liu , Jianxin Liu
The selective oxidation of hydrocarbons (RH) by dioxygen (O2) is a very important method for industrial production of bulk oxygen-containing compounds, However, due to the high chemical inertness of RH and O2, achieving this reaction under mild conditions still faces significant challenges. This paper discloses an efficient hybridizing engineering (HE) strategy of decatungstate (DT) with 3d transition metal ions (Mn+=Ni2+, Co2+ or Cu2+)-modified carbon quantum dots (Mn+/CQD) as the dopants. Compared to pure CQD, The Mn+/CQD can more efficiently combine with DT anion to fabricate a high-quality hybrid via electrostatic interactions, thereby bestowing the hybrid with an enhanced visible light response especially the separation efficiency of photo-generated charge pairs. Furthermore, the above hybridization effects of Mn+/CQD on DT anion can be fine-tuned and gradually improved with a change of the metal ion from Cu2+, Co2+ to Ni2+, along with a continuous enhancement of the hybrid's photo-catalytic efficiency in the visible light- triggered selective oxidation of ethylbenzene with O2 in acetonitrile. The best Ni2+/CQD-doped TBADT can achieve ca. 48% ethylbenzene conversion and 87.6% acetophenone selectivity in the presence of 2 M HCl, and it also shows a much higher photo-catalytic activity for the photo-oxidation of toluene, cyclohexane and benzyl alcohol compared to pure TBADT. The HE strategy with Mn+/CQD as the cationized hybridizers is much superior to that with pure CQD or Ni2+ as the hybridizer in hoisting the photo-catalytic performance of DT.
{"title":"Hybridizing engineering strategy of decatungstate III: Transition metal modified carbon quantum dot-regulated photo-catalytic oxidation performance of decatungstate","authors":"Anqun Su , Dabo Jiang , Wenwei Hu , Shuting Liang , Kai Yu , Weijie Zhou , Jing Wang , Zaihui Fu , Yachun Liu , Jianxin Liu","doi":"10.1016/j.jorganchem.2024.123432","DOIUrl":"10.1016/j.jorganchem.2024.123432","url":null,"abstract":"<div><div>The selective oxidation of hydrocarbons (RH) by dioxygen (O<sub>2</sub>) is a very important method for industrial production of bulk oxygen-containing compounds, However, due to the high chemical inertness of RH and O<sub>2</sub>, achieving this reaction under mild conditions still faces significant challenges. This paper discloses an efficient hybridizing engineering (HE) strategy of decatungstate (DT) with 3d transition metal ions (M<sup>n+</sup>=Ni<sup>2+</sup>, Co<sup>2+</sup> or Cu<sup>2+</sup>)-modified carbon quantum dots (M<sup>n+</sup>/CQD) as the dopants. Compared to pure CQD, The M<sup>n+</sup>/CQD can more efficiently combine with DT anion to fabricate a high-quality hybrid <em>via</em> electrostatic interactions, thereby bestowing the hybrid with an enhanced visible light response especially the separation efficiency of photo-generated charge pairs. Furthermore, the above hybridization effects of M<sup>n+</sup>/CQD on DT anion can be fine-tuned and gradually improved with a change of the metal ion from Cu<sup>2+</sup>, Co<sup>2+</sup> to Ni<sup>2+</sup>, along with a continuous enhancement of the hybrid's photo-catalytic efficiency in the visible light- triggered selective oxidation of ethylbenzene with O<sub>2</sub> in acetonitrile. The best Ni<sup>2+</sup>/CQD-doped TBADT can achieve ca. 48% ethylbenzene conversion and 87.6% acetophenone selectivity in the presence of 2 M HCl, and it also shows a much higher photo-catalytic activity for the photo-oxidation of toluene, cyclohexane and benzyl alcohol compared to pure TBADT. The HE strategy with M<sup>n+</sup>/CQD as the cationized hybridizers is much superior to that with pure CQD or Ni<sup>2+</sup> as the hybridizer in hoisting the photo-catalytic performance of DT.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1023 ","pages":"Article 123432"},"PeriodicalIF":2.1,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142593978","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 : 2024-10-24DOI: 10.1016/j.jorganchem.2024.123412
Vishal Singh, Ramaswamy Murugavel
Synthesis of C3-symmetric triarylboranes, tris(4-bromo-2,6-dimethylphenyl)-borane (1), N,N',N''-(boranetriyltris(3,5-diisopropyl-3′,5′-dimethyl-[1,1′-biphenyl]-4′,4-diyl))tris(1,1-diphenylmethanimine) (2), N,N',N''-(boranetriyltris(3′,5′-dimethyl-[1,1′-biphenyl]-4′,4-diyl))tris-(1,1-diphenylmethanimine) (3), 4′,4′'',4′''''-boranetriyltris(3′,5′-dimethyl-[1,1′-biphenyl]-4-carbaldehyde) (4), 4,4′,4′'-boranetriyltris(3,5-dimethylaniline) (5), 4′,4′'',4′''''-borane-triyltris(3′,5′-dimethyl-[1,1′-biphenyl]-4-carbonitrile) (6), 4′,4′'',4′''''-boranetriyltris(3′,5′-dimethyl-[1,1′-biphenyl]-4-amine) (7), and 4,4′,4′'-boranetriyltris(3,5-dimethylbenzaldehyde) (8) has been accomplished using well-known synthetic methodologies. These new potential building blocks have been characterized by various spectroscopic and analytical techniques and their photophysical properties have been examined. It is observed that photophysical properties of these compounds are enhanced with π conjugation expansions along the branches when donor moieties such as -NH2 groups are present at the para-position of the aryl rings. The highest quantum yield of 0.293 is observed for 4′,4′'',4′''''-boranetriyltris(3′,5′-dimethyl-[1,1′-biphenyl]-4-amine) (7). Interestingly, red-shifted fluorescence spectra follow the same trend as absorption spectra. The fluorescence lifetime increases with the number of donor moieties. The present findings demonstrate the possible use of these C3-symmetric boron-containing building blocks in developing new polymeric materials with improved photophysical properties for various applications.
{"title":"C3-symmetric triarylboron building blocks: Synthesis, structures, and photophysical properties","authors":"Vishal Singh, Ramaswamy Murugavel","doi":"10.1016/j.jorganchem.2024.123412","DOIUrl":"10.1016/j.jorganchem.2024.123412","url":null,"abstract":"<div><div>Synthesis of C<sub>3</sub>-symmetric triarylboranes, tris(4-bromo-2,6-dimethylphenyl)-borane <strong>(1)</strong>, N,N',N''-(boranetriyltris(3,5-diisopropyl-3′,5′-dimethyl-[1,1′-biphenyl]-4′,4-diyl))tris(1,1-diphenylmethanimine) (<strong>2</strong>), N,N',N''-(boranetriyltris(3′,5′-dimethyl-[1,1′-biphenyl]-4′,4-diyl))tris-(1,1-diphenylmethanimine) (<strong>3</strong>), 4′,4′'',4′''''-boranetriyltris(3′,5′-dimethyl-[1,1′-biphenyl]-4-carbaldehyde) (<strong>4),</strong> 4,4′,4′'-boranetriyltris(3,5-dimethylaniline) (<strong>5</strong>), 4′,4′'',4′''''-borane-triyltris(3′,5′-dimethyl-[1,1′-biphenyl]-4-carbonitrile) (<strong>6</strong>), 4′,4′'',4′''''-boranetriyltris(3′,5′-dimethyl-[1,1′-biphenyl]-4-amine) (<strong>7</strong>), and 4,4′,4′'-boranetriyltris(3,5-dimethylbenzaldehyde) (<strong>8</strong>) has been accomplished using well-known synthetic methodologies. These new potential building blocks have been characterized by various spectroscopic and analytical techniques and their photophysical properties have been examined. It is observed that photophysical properties of these compounds are enhanced with π conjugation expansions along the branches when donor moieties such as -NH<sub>2</sub> groups are present at the para-position of the aryl rings. The highest quantum yield of 0.293 is observed for 4′,4′'',4′''''-boranetriyltris(3′,5′-dimethyl-[1,1′-biphenyl]-4-amine) (<strong>7</strong>). Interestingly, red-shifted fluorescence spectra follow the same trend as absorption spectra. The fluorescence lifetime increases with the number of donor moieties. The present findings demonstrate the possible use of these C<sub>3</sub>-symmetric boron-containing building blocks in developing new polymeric materials with improved photophysical properties for various applications.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1022 ","pages":"Article 123412"},"PeriodicalIF":2.1,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142538524","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 : 2024-10-24DOI: 10.1016/j.jorganchem.2024.123414
Yumeng Cao, Dean J. Tantillo
Three-center, two-electron bonding arrays in σ-complexes between CC bonds and transition metals were examined using density functional theory computations. Variations in ligands and metals were connected to variations in strengths of bonding interactions in these arrays.
利用密度泛函理论计算研究了 CC 键与过渡金属之间的 σ 复合物中的三中心双电子键阵列。配体和金属的变化与这些阵列中成键相互作用强度的变化有关。
{"title":"Substituent and metal effects on CC σ-complex stabilization","authors":"Yumeng Cao, Dean J. Tantillo","doi":"10.1016/j.jorganchem.2024.123414","DOIUrl":"10.1016/j.jorganchem.2024.123414","url":null,"abstract":"<div><div>Three-center, two-electron bonding arrays in σ-complexes between C<img>C bonds and transition metals were examined using density functional theory computations. Variations in ligands and metals were connected to variations in strengths of bonding interactions in these arrays.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1023 ","pages":"Article 123414"},"PeriodicalIF":2.1,"publicationDate":"2024-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142560664","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 : 2024-10-23DOI: 10.1016/j.jorganchem.2024.123423
Qian Qiu , JianRong Song , Hui Zheng , Marjan Shahriari , Attalla F. El-kott , Ali G. Alkhathami , Kareem Morsy
This paper reports the synthesis of a novel class of Fe3O4@CS-Gl/Au core-shell pattern nanoparticles by employing Au NPs and chitosan-gelatin composite. The biogenic synthesis was mediated by dual composite hydrogel of chitosan and gelatin as a green reducing as well as stabilizing agent under ambient conditions. Physicochemical features the so obtained nanomaterial was assessed by using FT-IR, TEM, FE-SEM, EDX, elemental mapping, VSM and XRD. Click synthesis of 5-substituted-1H-tetrazoles utilizing aryl halides was our aim in catalytic investigation. The Fe3O4@CS-Gl/Au catalyst, which is highly effective and reusable, was used to catalyze the [3 + 2]-cycloaddition of benzonitriles with NaN3, leading to the solvent-free synthesis of corresponding tetrazole derivatives at 120 °C. This method was carried out using K4[Fe(CN)6] as a non-hazardous cyanide precursor. Following a 12-hour process, the different substrates produced yields ranging from 70 to 96 %. Hot filtration, leaching and reusability studies were conducted 12 times in a succession, all of which confirmed the catalyst's resilience. Furthermore, in the biological studies % cell viability of Fe3O4@CS-Gl/Au NPs was found very low against common human uterine cell lines i.e. AN3-CA and HEC-1-A, devoid of any cytotoxicity on normal cell lines like HUVEC. The best anti-uterine effect was observed against the AN3-CA cell line. For investigating the antioxidant properties of nanobio-composite, the DPPH assay was used. Fe3O4@CS-Gl/Au NPs inhibited half of the DPPH molecules in the concentration of 139 µg/mL. The antioxidant activity of the NPs is significantly related to its anti-uterine cancer potentials. Based on the above findings, the Fe3O4@CS-Gl/Au NPs could be administered in restricting diverse human cancers.
{"title":"Supported Au NPs over magnetic chitosan-gelatin nanocomposite: Investigation of its catalytic activity for one-pot synthesis of tetrazoles, study of antioxidant activity and anti-uterine cancer performances","authors":"Qian Qiu , JianRong Song , Hui Zheng , Marjan Shahriari , Attalla F. El-kott , Ali G. Alkhathami , Kareem Morsy","doi":"10.1016/j.jorganchem.2024.123423","DOIUrl":"10.1016/j.jorganchem.2024.123423","url":null,"abstract":"<div><div>This paper reports the synthesis of a novel class of Fe<sub>3</sub>O<sub>4</sub>@CS-Gl/Au core-shell pattern nanoparticles by employing Au NPs and chitosan-gelatin composite. The biogenic synthesis was mediated by dual composite hydrogel of chitosan and gelatin as a green reducing as well as stabilizing agent under ambient conditions. Physicochemical features the so obtained nanomaterial was assessed by using FT-IR, TEM, FE-SEM, EDX, elemental mapping, VSM and XRD. Click synthesis of 5-substituted-1H-tetrazoles utilizing aryl halides was our aim in catalytic investigation. The Fe<sub>3</sub>O<sub>4</sub>@CS-Gl/Au catalyst, which is highly effective and reusable, was used to catalyze the [3 + 2]-cycloaddition of benzonitriles with NaN<sub>3</sub>, leading to the solvent-free synthesis of corresponding tetrazole derivatives at 120 °C. This method was carried out using K<sub>4</sub>[Fe(CN)<sub>6</sub>] as a non-hazardous cyanide precursor. Following a 12-hour process, the different substrates produced yields ranging from 70 to 96 %. Hot filtration, leaching and reusability studies were conducted 12 times in a succession, all of which confirmed the catalyst's resilience. Furthermore, in the biological studies % cell viability of Fe<sub>3</sub>O<sub>4</sub>@CS-Gl/Au NPs was found very low against common human uterine cell lines i.e. AN3-CA and HEC-1-A, devoid of any cytotoxicity on normal cell lines like HUVEC. The best anti-uterine effect was observed against the AN3-CA cell line. For investigating the antioxidant properties of nanobio-composite, the DPPH assay was used. Fe<sub>3</sub>O<sub>4</sub>@CS-Gl/Au NPs inhibited half of the DPPH molecules in the concentration of 139 µg/mL. The antioxidant activity of the NPs is significantly related to its anti-uterine cancer potentials. Based on the above findings, the Fe<sub>3</sub>O<sub>4</sub>@CS-Gl/Au NPs could be administered in restricting diverse human cancers.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1023 ","pages":"Article 123423"},"PeriodicalIF":2.1,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142554767","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 : 2024-10-22DOI: 10.1016/j.jorganchem.2024.123420
Jiaxin Zhang , Miao Wang , Jun Zhang , Qingyi Zhang , Lin Sun , Taiping Gao , Weili Wang , Tomás Guerrero , Xiuwei Gao
Imidazoles and benzimidazoles are privileged heterocyclic compounds that can be extensively found in medicinal and materials chemistry, however, the experimental procedures for their synthesis are limited to multicomponent condensation reactions and normally are strongly dependent upon the desired substitution pattern, consequently several procedures with different conditions and catalysts are available in literature. Accordingly, the development of synthetic methodologies to afford these compounds remains a very attractive research problem. In this regard, dioxomolybdenum based catalysts are emerging as versatile and non-expensive reagents for a myriad of chemically relevant transformations. Within this context, an expedient and efficient synthesis of 2,4,5-trialkyl-1H-imidazoles and benzimidazoles from a multicomponent one-pot condensation has been developed with a tridentate Schiff base dioxomolybdenum(VI) complex, resulting in an efficient, simple and readily available catalyst to promote the aforementioned reaction. This reaction offers advantages such as good to excellent yields, good selectivity of products, low catalyst loadings and simple reaction work-up.
{"title":"Expeditious and selective synthesis of 2,4,5-trialkyl-1H-imdazoles and benzimidazoles via multicomponent one-pot reaction catalyzed by Schiff base dioxomolybdenum(VI) complex","authors":"Jiaxin Zhang , Miao Wang , Jun Zhang , Qingyi Zhang , Lin Sun , Taiping Gao , Weili Wang , Tomás Guerrero , Xiuwei Gao","doi":"10.1016/j.jorganchem.2024.123420","DOIUrl":"10.1016/j.jorganchem.2024.123420","url":null,"abstract":"<div><div>Imidazoles and benzimidazoles are privileged heterocyclic compounds that can be extensively found in medicinal and materials chemistry, however, the experimental procedures for their synthesis are limited to multicomponent condensation reactions and normally are strongly dependent upon the desired substitution pattern, consequently several procedures with different conditions and catalysts are available in literature. Accordingly, the development of synthetic methodologies to afford these compounds remains a very attractive research problem. In this regard, dioxomolybdenum based catalysts are emerging as versatile and non-expensive reagents for a myriad of chemically relevant transformations. Within this context, an expedient and efficient synthesis of 2,4,5-trialkyl-1<em>H</em>-imidazoles and benzimidazoles from a multicomponent one-pot condensation has been developed with a tridentate Schiff base dioxomolybdenum(VI) complex, resulting in an efficient, simple and readily available catalyst to promote the aforementioned reaction. This reaction offers advantages such as good to excellent yields, good selectivity of products, low catalyst loadings and simple reaction work-up.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1023 ","pages":"Article 123420"},"PeriodicalIF":2.1,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142593980","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 : 2024-10-21DOI: 10.1016/j.jorganchem.2024.123410
Nermin Meriç , Uğur Işık , Anuar Dauletbakov , Darya Zolotareva , Alexey Zazybin , Mehmet Şerif Sever , Veysi Okumuş , Nil Ertekin Binbay , Veysel Binbay , Cezmi Kayan , Remziye Güzel , Murat Aydemir
We report two phosphinite ligands derived from chiral amino alcohols, and their complexes with ruthenium(II). These compounds were characterized by spectroscopic methods. Then, antimicrobial, antioxidant, and DNA binding activities of the chiral Ru(II)-phosphinite complexes were tested. Complex (1R)-2-{benzyl[(1S)-1-(naphthalen-1-yl)ethyl]amino}-1-phenylethyl diphenylphos- phinito[dichloro(η6-p-cymene)ruthenium(II)], 7 showed both the highest radical scavenging activity (90.93 ± 0.98 %) and the highest metal chelating activity (65.45 ± 1.46 %) at 200.0 mg l-1 concentration. In addition, all of complexes had different rates of binding activity to calf thymus DNA (CT-DNA). Moreover, extensive theoretical and experimental investigations were conducted to gain a more profound understanding of the chemical descriptors and the diverse electronic transitions taking place within the ruthenium complexes, as well as their electrochemical characteristics.
{"title":"Advanced-designed Ru(II) complexes containing phosphinite ligands derived from chiral amino alcohols: Electrochemical behavior, DFT calculations, and biological activity","authors":"Nermin Meriç , Uğur Işık , Anuar Dauletbakov , Darya Zolotareva , Alexey Zazybin , Mehmet Şerif Sever , Veysi Okumuş , Nil Ertekin Binbay , Veysel Binbay , Cezmi Kayan , Remziye Güzel , Murat Aydemir","doi":"10.1016/j.jorganchem.2024.123410","DOIUrl":"10.1016/j.jorganchem.2024.123410","url":null,"abstract":"<div><div>We report two phosphinite ligands derived from chiral amino alcohols, and their complexes with ruthenium(II). These compounds were characterized by spectroscopic methods. Then, antimicrobial, antioxidant, and DNA binding activities of the chiral Ru(II)-phosphinite complexes were tested. Complex (1<em>R</em>)-2-{benzyl[(1<em>S</em>)-1-(naphthalen-1-yl)ethyl]amino}-1-phenylethyl diphenylphos- phinito[dichloro(η<sup>6</sup>-<em>p</em>-cymene)ruthenium(II)], 7 showed both the highest radical scavenging activity (90.93 ± 0.98 %) and the highest metal chelating activity (65.45 ± 1.46 %) at 200.0 mg l<sup>-1</sup> concentration. In addition, all of complexes had different rates of binding activity to calf thymus DNA (CT-DNA). Moreover, extensive theoretical and experimental investigations were conducted to gain a more profound understanding of the chemical descriptors and the diverse electronic transitions taking place within the ruthenium complexes, as well as their electrochemical characteristics.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1023 ","pages":"Article 123410"},"PeriodicalIF":2.1,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142525789","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 : 2024-10-20DOI: 10.1016/j.jorganchem.2024.123416
Tian-Tian Sun, Yang Gao, Song Pan, Zhong Li, Ai-Quan Jia, Qian-Feng Zhang
Treatment of [(Me3tacn)RuIII(κ2-S2CNR2)Cl]PF6 (Me3tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane) with methanol in the presence of zinc powder in air afforded four ruthenium methoxy complexes [(Me3tacn)RuIII(κ2-S2CNR2)(OCH3)]PF6 (R = Me 1, Et 2, nPr 3, iPr 4). Further reactions of complexes 1–4 and phenylacetylene gave four ruthenium vinylidene complexes [(Me3tacn)(κ2-S2CNR2)Ru=C=CHPh]PF6 (R = Me 5, Et 6, nPr 7, iPr 8). Molecular structures of complexes 1, 2, 3, 6, 7 and 8 were established by single crystal X-ray diffraction analysis. Moreover, all complexes were characterized by infrared, UV–vis, fluorescence and mass spectrometry, and their electrochemical properties were also investigated. The visible-light-induced catalytic properties of complexes 5–8 for H2 evolution by water splitting were explored.
在空气中，在锌粉存在下，用甲醇处理[(Me3tacn)RuIII(κ2-S2CNR2)Cl]PF6（Me3tacn = 1,4,7-三甲基-1,4,7-三氮杂环壬烷），得到四个甲氧基钌络合物[(Me3tacn)RuIII(κ2-S2CNR2)(OCH3)]PF6（R = Me 1, Et 2, nPr 3, iPr 4）。络合物 1-4 与苯乙炔进一步反应，得到四个亚乙烯基钌络合物 [(Me3tacn)(κ2-S2CNR2)Ru=C=CHPh]PF6（R = Me 5、Et 6、nPr 7、iPr 8）。通过单晶 X 射线衍射分析，确定了复合物 1、2、3、6、7 和 8 的分子结构。此外，还利用红外光谱、紫外-可见光谱、荧光光谱和质谱对所有配合物进行了表征，并研究了它们的电化学性质。研究还探讨了 5-8 复合物在可见光诱导下通过水分裂进化 H2 的催化特性。
{"title":"Ruthenium methoxy and ruthenium vinylidene complexes featuring dithiocarbamate ligands","authors":"Tian-Tian Sun, Yang Gao, Song Pan, Zhong Li, Ai-Quan Jia, Qian-Feng Zhang","doi":"10.1016/j.jorganchem.2024.123416","DOIUrl":"10.1016/j.jorganchem.2024.123416","url":null,"abstract":"<div><div>Treatment of [(Me<sub>3</sub>tacn)Ru<sup>III</sup>(κ<sup>2</sup>-S<sub>2</sub>CNR<sub>2</sub>)Cl]PF<sub>6</sub> (Me<sub>3</sub>tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane) with methanol in the presence of zinc powder in air afforded four ruthenium methoxy complexes [(Me<sub>3</sub>tacn)Ru<sup>III</sup>(<em>κ</em><sup>2</sup>-S<sub>2</sub>CNR<sub>2</sub>)(OCH<sub>3</sub>)]PF<sub>6</sub> (<em>R</em> = Me <strong>1</strong>, Et <strong>2</strong>, <sup>n</sup>Pr <strong>3</strong>, <sup>i</sup>Pr <strong>4</strong>). Further reactions of complexes <strong>1–4</strong> and phenylacetylene gave four ruthenium vinylidene complexes [(Me<sub>3</sub>tacn)(κ<sup>2</sup>-S<sub>2</sub>CNR<sub>2</sub>)Ru=C=CHPh]PF<sub>6</sub> (<em>R</em> = Me <strong>5</strong>, Et <strong>6</strong>, <sup>n</sup>Pr <strong>7</strong>, <sup>i</sup>Pr <strong>8</strong>). Molecular structures of complexes <strong>1, 2, 3, 6, 7</strong> and <strong>8</strong> were established by single crystal X-ray diffraction analysis. Moreover, all complexes were characterized by infrared, UV–vis, fluorescence and mass spectrometry, and their electrochemical properties were also investigated. The visible-light-induced catalytic properties of complexes <strong>5–8</strong> for H<sub>2</sub> evolution by water splitting were explored.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1022 ","pages":"Article 123416"},"PeriodicalIF":2.1,"publicationDate":"2024-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142538525","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 : 2024-10-19DOI: 10.1016/j.jorganchem.2024.123422
Saswati Ray , Sanajit Kumar Mandal , Joyanta Choudhury
In electrochemical CO2-conversion strategies, various transition metal-based molecular electrocatalysts are employed to reduce CO2 into products like CO and HCO2H, with H2 as a competitive side product. However, achieving selectivity towards HCO2H remains challenging, and suitable catalysts for the same are limited. Herein we report a normal and an abnormal protic-NHC-based Cp*Ir(III)-half sandwich complexes for catalytic CO2 electroreduction in an aqueous acetonitrile solvent. Both the catalysts predominantly produced HCO2H as the CO2-reduced product at an applied potential of –2.66 V vs Fc+/Fc with 5 % H2O as the proton source; however, the normal protic-NHC-bound complex achieved a Faradic efficiency (FE) of 86±4 %, while the complex with the abnormal protic-NHC ligand furnished FE up to 72±4 %. The protic proton of the protic NHC ligand in these complexes was proposed to participate in a proton relay process, facilitating generation of the crucial Ir–H intermediate, which reacts with CO2 to produce HCO2H through stabilization of the Ir–OCHO intermediate.
在电化学二氧化碳转化策略中，采用了各种基于过渡金属的分子电催化剂，将二氧化碳还原成 CO 和 HCO2H 等产物，并将 H2 作为竞争性副产品。然而，实现对 HCO2H 的选择性仍然具有挑战性，而且适用的催化剂也很有限。在此，我们报告了一种基于正常和异常原生 NHC 的 Cp*Ir(III)-half sandwich 复合物，用于在乙腈水溶液中催化 CO2 电还原。在以 5% H2O 为质子源、对 Fc+/Fc 的施加电位为 -2.66 V 时，这两种催化剂都主要产生 HCO2H 作为 CO2 还原产物；然而，正常的原核-NHC 结合络合物的法拉第效率 (FE) 为 86±4%，而带有异常原核-NHC 配体的络合物的法拉第效率 (FE) 则高达 72±4%。据推测，这些复合物中原生 NHC 配体的原生质子参与了质子中继过程，促进了关键的 Ir-H 中间体的生成，通过稳定 Ir-OCHO 中间体，Ir-H 中间体与 CO2 反应生成 HCO2H。
{"title":"Electrocatalytic CO2 reduction to HCO2H by protic NHC-Ir complexes","authors":"Saswati Ray , Sanajit Kumar Mandal , Joyanta Choudhury","doi":"10.1016/j.jorganchem.2024.123422","DOIUrl":"10.1016/j.jorganchem.2024.123422","url":null,"abstract":"<div><div>In electrochemical CO<sub>2</sub>-conversion strategies, various transition metal-based molecular electrocatalysts are employed to reduce CO<sub>2</sub> into products like CO and HCO<sub>2</sub>H, with H<sub>2</sub> as a competitive side product. However, achieving selectivity towards HCO<sub>2</sub>H remains challenging, and suitable catalysts for the same are limited. Herein we report a normal and an abnormal protic-NHC-based Cp*Ir(III)-half sandwich complexes for catalytic CO<sub>2</sub> electroreduction in an aqueous acetonitrile solvent. Both the catalysts predominantly produced HCO<sub>2</sub>H as the CO<sub>2</sub>-reduced product at an applied potential of –2.66 V vs Fc<sup>+</sup>/Fc with 5 % H<sub>2</sub>O as the proton source; however, the normal protic-NHC-bound complex achieved a Faradic efficiency (FE) of 86±4 %, while the complex with the abnormal protic-NHC ligand furnished FE up to 72±4 %. The protic proton of the protic NHC ligand in these complexes was proposed to participate in a proton relay process, facilitating generation of the crucial Ir–H intermediate, which reacts with CO<sub>2</sub> to produce HCO<sub>2</sub>H through stabilization of the Ir–OCHO intermediate.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1022 ","pages":"Article 123422"},"PeriodicalIF":2.1,"publicationDate":"2024-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142538522","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 : 2024-10-18DOI: 10.1016/j.jorganchem.2024.123419
Jason A. Denny , Georgette M. Lang , Shane Autry , Vivek Dixit , Tyler L. Woodby , Annie McClellan , Jaclyn M. Trate , Nathan I. Hammer , Charles Edwin Webster , T. Keith Hollis
A series of CCCNHC pincer Pd(II)X complexes, where X = Cl, Br, or I, were synthesized by a metalation/transmetalation reaction sequence and characterized by NMR and Raman spectroscopy, photophysical studies, X-ray crystallography, and DFT computational studies. This is the first detailed report of the CCCNHC pincer Pd complexes analogous to the previously reported Pt analogs. Photophysical measurements show that by varying the X ligand, the emission wavelength can be tuned. The chloride complex is a water and air stable blue emitter with a quantum yield of 46 % and all three complexes have photostabilities >90 %. A combined DFT and TD-DFT study has been carried out to investigate ground state and excited state geometries as well as absorption and emission processes of CCCNHC Pd complexes. Theoretical results were compared with the corresponding experimental results and showed good agreement. Raman spectroscopy (computational and experimental) was used to examine Pd-X vibrations which have been rarely reported in the literature. Several by-products of the metalation/transmetalation procedure were identified. A rare mixed normal/abnormal carbene pincer Pd(II)Cl complex was isolated and crystallographically characterized.
{"title":"Air-stable palladium NHeterocyclic carbene based CCCNHC pincer complexes: Synthesis, characterization, photophysical and Raman vibrational studies, and DFT studies, plus observation of an abnormal carbene pincer","authors":"Jason A. Denny , Georgette M. Lang , Shane Autry , Vivek Dixit , Tyler L. Woodby , Annie McClellan , Jaclyn M. Trate , Nathan I. Hammer , Charles Edwin Webster , T. Keith Hollis","doi":"10.1016/j.jorganchem.2024.123419","DOIUrl":"10.1016/j.jorganchem.2024.123419","url":null,"abstract":"<div><div>A series of CCC<img>NHC pincer Pd(II)X complexes, where X = Cl, Br, or I, were synthesized by a metalation/transmetalation reaction sequence and characterized by NMR and Raman spectroscopy, photophysical studies, X-ray crystallography, and DFT computational studies. This is the first detailed report of the CCC<img>NHC pincer Pd complexes analogous to the previously reported Pt analogs. Photophysical measurements show that by varying the X ligand, the emission wavelength can be tuned. The chloride complex is a water and air stable blue emitter with a quantum yield of 46 % and all three complexes have photostabilities >90 %. A combined DFT and TD-DFT study has been carried out to investigate ground state and excited state geometries as well as absorption and emission processes of CCC<img>NHC Pd complexes. Theoretical results were compared with the corresponding experimental results and showed good agreement. Raman spectroscopy (computational and experimental) was used to examine Pd-X vibrations which have been rarely reported in the literature. Several by-products of the metalation/transmetalation procedure were identified. A rare mixed normal/abnormal carbene pincer Pd(II)Cl complex was isolated and crystallographically characterized.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1023 ","pages":"Article 123419"},"PeriodicalIF":2.1,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142652649","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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