Exploring novel efficient electrochemiluminescent (ECL) dyes derived from transition metal complexes with new skeletons is always one of the hot and important topics of ECL-related studies. Herein, three bis-tridentate iridium(III) complexes (BisLT-Ir-NHC-R, where R represents H, CH3 and CF3) with N-heterocyclic carbenes (NHC) ligands have been prepared in this work. Beside photophysics (PL), theoretical calculations and cyclic voltammetry (CV), ECL properties have been comparatively investigated in this work. Notably, not only did the BisLT-Ir-NHC- CF3 have the highest photoluminescence efficiency value of 13.26 %, but most importantly, the ECL efficiency of bis-tridentate iridium(III) complexes in this work was up to 3.4 times than the benchmark of Ru(bpy)32+ under the same experimental conditions. These results demonstrates that bis-tridentate iridium(III) complexes with NHC ligands have great potential applications in ECL-based analysis technology and could open a new avenue to develop highly efficient ECL dyes derived from bis-tridentate iridium complexes in the future.
{"title":"Comparative electrochemiluminescence studies about bis-tridentate iridium(III) complexes comprising Nheterocyclic carbene","authors":"Yaoyao Xu , Chenji Dai , Ziwang Mao, Libing Ke, Rongxiu Deng, Fangming Zhu, Yuyang Zhou","doi":"10.1016/j.jorganchem.2025.123595","DOIUrl":"10.1016/j.jorganchem.2025.123595","url":null,"abstract":"<div><div>Exploring novel efficient electrochemiluminescent (ECL) dyes derived from transition metal complexes with new skeletons is always one of the hot and important topics of ECL-related studies. Herein, three bis-tridentate iridium(III) complexes (BisL<sub>T</sub>-Ir-NHC-R, where R represents H, CH<sub>3</sub> and CF<sub>3</sub>) with N-heterocyclic carbenes (NHC) ligands have been prepared in this work. Beside photophysics (PL), theoretical calculations and cyclic voltammetry (CV), ECL properties have been comparatively investigated in this work. Notably, not only did the BisL<sub>T</sub>-Ir-NHC- CF<sub>3</sub> have the highest photoluminescence efficiency value of 13.26 %, but most importantly, the ECL efficiency of bis-tridentate iridium(III) complexes in this work was up to 3.4 times than the benchmark of Ru(bpy)<sub>3</sub><sup>2+</sup> under the same experimental conditions. These results demonstrates that bis-tridentate iridium(III) complexes with NHC ligands have great potential applications in ECL-based analysis technology and could open a new avenue to develop highly efficient ECL dyes derived from bis-tridentate iridium complexes in the future.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1031 ","pages":"Article 123595"},"PeriodicalIF":2.1,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143548191","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-01DOI: 10.1016/j.jorganchem.2025.123578
Enock D. Amoateng, Bruno Donnadieu, Evans Fosu, T. Keith Hollis
Selective dehydrogenative silylation of vinylarenes with tertiary silanes catalyzed by well-defined CCC–NHC pincer Rh complexes has been developed. The CCC–NHC pincer Rh precatalysts [(BuCiCiCBu)RhCl(µ-Cl)2Rh(COD)] (7), [(BuCiCiCBu)RhCl(µ-Cl)]2 (8), [(BuCiCiCBu)RhCl2(NHMe2)] (9), and [(BuCiCiCBu)RhCl2Py] (10), (BuCiCiCBu = 2-((1,3-bis(N-butylimidazol-2-ylidene)phenylene) that were evaluated were all found to promote the dehydrogenative silylation of vinylarenes with Et3SiH to selectively form the corresponding (E)-alkenylsilane under solvent-free conditions. The most active precatalyst was the novel mixed valent Rh(III)/Rh(I) complex, [(BuCiCiCBu)RhCl(µ-Cl)2Rh(COD)] (7). The catalytic system displays wide substrate scope. Electron rich and electron deficient vinylarenes were well tolerated affording the corresponding alkenylsilanes in good yields (65–86 %). Preliminary mechanistic investigations indicated that the Rh(III) center was responsible for the catalytic performance.
{"title":"Dehydrogenative silylation of vinylarenes with Et3SiH catalyzed by mixed valent CCC-NHC Rh(III)/Rh(I) pincer complex","authors":"Enock D. Amoateng, Bruno Donnadieu, Evans Fosu, T. Keith Hollis","doi":"10.1016/j.jorganchem.2025.123578","DOIUrl":"10.1016/j.jorganchem.2025.123578","url":null,"abstract":"<div><div>Selective dehydrogenative silylation of vinylarenes with tertiary silanes catalyzed by well-defined CCC–NHC pincer Rh complexes has been developed. The CCC–NHC pincer Rh precatalysts [(<sup>Bu</sup>C<sup>i</sup>C<sup>i</sup>C<sup>Bu</sup>)RhCl(µ-Cl)<sub>2</sub>Rh(COD)] (<strong>7</strong>), [(<sup>Bu</sup>C<sup>i</sup>C<sup>i</sup>C<sup>Bu</sup>)RhCl(µ-Cl)]<sub>2</sub> (<strong>8</strong>), [(<sup>Bu</sup>C<sup>i</sup>C<sup>i</sup>C<sup>Bu</sup>)RhCl<sub>2</sub>(NHMe<sub>2</sub>)] (<strong>9</strong>), and [(<sup>Bu</sup>C<sup>i</sup>C<sup>i</sup>C<sup>Bu</sup>)RhCl<sub>2</sub>Py] (<strong>10</strong>), (<sup>Bu</sup>C<sup>i</sup>C<sup>i</sup>C<sup>Bu</sup> = 2-((1,3-bis(N-butylimidazol-2-ylidene)phenylene) that were evaluated were all found to promote the dehydrogenative silylation of vinylarenes with Et<sub>3</sub>SiH to selectively form the corresponding (<em>E</em>)-alkenylsilane under solvent-free conditions. The most active precatalyst was the novel mixed valent Rh(III)/Rh(I) complex, [(<sup>Bu</sup>C<sup>i</sup>C<sup>i</sup>C<sup>Bu</sup>)RhCl(µ-Cl)<sub>2</sub>Rh(COD)] (<strong>7</strong>). The catalytic system displays wide substrate scope. Electron rich and electron deficient vinylarenes were well tolerated affording the corresponding alkenylsilanes in good yields (65–86 %). Preliminary mechanistic investigations indicated that the Rh(III) center was responsible for the catalytic performance.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1031 ","pages":"Article 123578"},"PeriodicalIF":2.1,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143578414","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-01DOI: 10.1016/j.jorganchem.2025.123596
Jerry Chun-Kit Yau , Franco King-Chi Leung
Supramolecular assemblies, composed of molecular building blocks held together by reversible noncovalent interactions, offer a versatile toolbox to create well-defined architectures. Among these interactions, metal-ligand coordination is of particular interest for its directionality and controllability, enabling the construction of stimuli-responsive materials to external stimulations such as light, pH, chemicals and mechanical force. However, dual stimuli-controlled supramolecular assembly of silver(I) with pyridiyl ligand remain largely unexplored. Herein, we present the synthesis and behavior of a novel dipyridine-functionalized stiff-stilbene StPy in coordination with silver(I) ions, forming stimuli-responsive supramolecular assemblies. StPy exhibits good photochemical properties under UV-light in common organic solvents including DMSO, ACN, and THF. Upon mixing with AgBF4, StPy coordinates with Ag(I) in a 1:1 ratio and assembles into metallosupramolecular architectures, confirmed by UV–vis spectroscopy and Job's plot analysis. Under UV-light irradiation, the StPy undergoes isomerization, modulating its metal-ligand interactions and transforming the StPy-Ag assemblies from vesicles to micelles. Additionally, the addition of TBACl induces disassembly, forming silver chloride nanoparticles. This dual photo- and chemical-modulated system provides a simple strategy to create advanced supramolecular coordination complexes and smart materials.
{"title":"Dual-controlled metallosupramolecular assemblies of pyridyl stiff-stilbene with silver(I) ions","authors":"Jerry Chun-Kit Yau , Franco King-Chi Leung","doi":"10.1016/j.jorganchem.2025.123596","DOIUrl":"10.1016/j.jorganchem.2025.123596","url":null,"abstract":"<div><div>Supramolecular assemblies, composed of molecular building blocks held together by reversible noncovalent interactions, offer a versatile toolbox to create well-defined architectures. Among these interactions, metal-ligand coordination is of particular interest for its directionality and controllability, enabling the construction of stimuli-responsive materials to external stimulations such as light, pH, chemicals and mechanical force. However, dual stimuli-controlled supramolecular assembly of silver(I) with pyridiyl ligand remain largely unexplored. Herein, we present the synthesis and behavior of a novel dipyridine-functionalized stiff-stilbene <strong>StPy</strong> in coordination with silver(I) ions, forming stimuli-responsive supramolecular assemblies. <strong>StPy</strong> exhibits good photochemical properties under UV-light in common organic solvents including DMSO, ACN, and THF. Upon mixing with AgBF<sub>4</sub>, <strong>StPy</strong> coordinates with Ag(I) in a 1:1 ratio and assembles into metallosupramolecular architectures, confirmed by UV–vis spectroscopy and Job's plot analysis. Under UV-light irradiation, the <strong>StPy</strong> undergoes isomerization, modulating its metal-ligand interactions and transforming the <strong>StPy-Ag</strong> assemblies from vesicles to micelles. Additionally, the addition of TBACl induces disassembly, forming silver chloride nanoparticles. This dual photo- and chemical-modulated system provides a simple strategy to create advanced supramolecular coordination complexes and smart materials.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1031 ","pages":"Article 123596"},"PeriodicalIF":2.1,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143563070","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-01DOI: 10.1016/j.jorganchem.2025.123597
Jie Liu , Liqing Guo
Recently, coupled bio-nanomaterials containing gold nanoparticles have attracted attention as a potentially useful platform for biological composites of the future. Accordingly, we reported a new anticancer agent (Au NPs@GG) supported by Au NPs under sonication energy. Many physicochemical techniques, including UV–Vis spectroscopy, FESEM, TEM, EDX, XRD, and ICP-OES, were used to thoroughly analyze the prepared desired nanocomposite. The material was catalytically explored in the Suzuki-Miyaura coupling for synthesis of different biaryl compounds under aqueous conditions. The catalyst, Au NPs@GG, resulted the related products in good yields at short reaction times. Furthermore, one of the widely utilized antioxidant techniques, DPPH, was employed to study the antioxidant potential of Au NPs@GG. The DPPH test findings demonstrated that Au NPs@GG had superior antioxidant qualities when compared to the controls. The antioxidant test revealed that Au NPs@GG had an IC50 of 135 µg/mL. The Au NPs@GG nanocomposite showed no cytotoxicity on the normal cell line, while its cell viability against bladder cancer (5637 and TCCSUP) cell lines was extremely low. The TCCSUP cell line exhibited the best anti-human bladder cancer characteristics of the nanocomposite when compared to the aforementioned cell lines. The nanocomposite may be used to treat various forms of bladder cancer in people, based on the results given above.
{"title":"Suzuki coupling reaction catalyzed by biosynthesized of gold nanoparticles in water under ultrasonic conditions and its application for treatment of bladder cancer","authors":"Jie Liu , Liqing Guo","doi":"10.1016/j.jorganchem.2025.123597","DOIUrl":"10.1016/j.jorganchem.2025.123597","url":null,"abstract":"<div><div>Recently, coupled bio-nanomaterials containing gold nanoparticles have attracted attention as a potentially useful platform for biological composites of the future. Accordingly, we reported a new anticancer agent (Au NPs@GG) supported by Au NPs under sonication energy. Many physicochemical techniques, including UV–Vis spectroscopy, FESEM, TEM, EDX, XRD, and ICP-OES, were used to thoroughly analyze the prepared desired nanocomposite. The material was catalytically explored in the Suzuki-Miyaura coupling for synthesis of different biaryl compounds under aqueous conditions. The catalyst, Au NPs@GG, resulted the related products in good yields at short reaction times. Furthermore, one of the widely utilized antioxidant techniques, DPPH, was employed to study the antioxidant potential of Au NPs@GG. The DPPH test findings demonstrated that Au NPs@GG had superior antioxidant qualities when compared to the controls. The antioxidant test revealed that Au NPs@GG had an IC<sub>50</sub> of 135 µg/mL. The Au NPs@GG nanocomposite showed no cytotoxicity on the normal cell line, while its cell viability against bladder cancer (5637 and TCCSUP) cell lines was extremely low. The TCCSUP cell line exhibited the best anti-human bladder cancer characteristics of the nanocomposite when compared to the aforementioned cell lines. The nanocomposite may be used to treat various forms of bladder cancer in people, based on the results given above.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1031 ","pages":"Article 123597"},"PeriodicalIF":2.1,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143578406","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-01DOI: 10.1016/j.jorganchem.2025.123591
Ke Yang , Sisi Cheng , Shijia Li, Kun Zhu, Ziqin Yao
The influencing factors of ZIF-8 synthesis were systematically investigated by the green synthesis method and the samples were also compared with ZIF-8 synthesized in other ways, and an optimal synthesis route was found by exploring the synthesis conditions. On this basis, the synthesis mechanism of ZIF-8 was analyzed. The research results show that the key influencing factors in the reaction process are the amount of NaOH and the pH value of the system. Different amounts of NaOH will produce different intermediates, and these intermediates further affect the pH value of the entire reaction system. The pH value of the system plays a decisive role in the deprotonation process of the ligand in the reaction, and this process is the key to whether the ZIF-8 structure can be formed. It is worth mentioning that the ZIF - 8 synthesized in this study demonstrates varying removal performances for different dyes under different conditions. Under specific conditions, it exhibits the maximum removal rate for Rhodamine B (RhB), reaching 99.97 %. This excellent removal performance is closely associated with the pore - structure characteristics of the synthesized material, which fully indicates that the ZIF - 8 synthesized through the green route has certain application potential and promising application prospects in related fields.
{"title":"Exploration of a green synthesis route of ZIF-8 and testing of its dye adsorption performance","authors":"Ke Yang , Sisi Cheng , Shijia Li, Kun Zhu, Ziqin Yao","doi":"10.1016/j.jorganchem.2025.123591","DOIUrl":"10.1016/j.jorganchem.2025.123591","url":null,"abstract":"<div><div>The influencing factors of ZIF-8 synthesis were systematically investigated by the green synthesis method and the samples were also compared with ZIF-8 synthesized in other ways, and an optimal synthesis route was found by exploring the synthesis conditions. On this basis, the synthesis mechanism of ZIF-8 was analyzed. The research results show that the key influencing factors in the reaction process are the amount of NaOH and the pH value of the system. Different amounts of NaOH will produce different intermediates, and these intermediates further affect the pH value of the entire reaction system. The pH value of the system plays a decisive role in the deprotonation process of the ligand in the reaction, and this process is the key to whether the ZIF-8 structure can be formed. It is worth mentioning that the ZIF - 8 synthesized in this study demonstrates varying removal performances for different dyes under different conditions. Under specific conditions, it exhibits the maximum removal rate for Rhodamine B (RhB), reaching 99.97 %. This excellent removal performance is closely associated with the pore - structure characteristics of the synthesized material, which fully indicates that the ZIF - 8 synthesized through the green route has certain application potential and promising application prospects in related fields.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1031 ","pages":"Article 123591"},"PeriodicalIF":2.1,"publicationDate":"2025-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143578416","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-27DOI: 10.1016/j.jorganchem.2025.123590
Mohamed H. Helal , Hanan I. Althagbi , Nourah A. Al Zahrani , Rasha Jame , Moustafa A. Gouda
The fusion of benzene with 4H-selenopyran motifs yields three distinct structures: condensed 2H-selenochromene, 4H-selenochromene, and 1H-isoselenochromene. Notably, isoselenochromene features a selenium atom in the second position rather than the first, a configuration that, as far as current knowledge indicates, lacks specific published reports and has predominantly served as a foundational building block. The synthesis of 1H-isoselenochromenes and their analogues can be achieved through various chemical pathways, such as the Sonogashira coupling reaction, nucleophilic addition, organometallic reactions, metal substitution, and other established methods in organic synthesis.
{"title":"2-Selenochromenes and their salts: Structure and reactivity","authors":"Mohamed H. Helal , Hanan I. Althagbi , Nourah A. Al Zahrani , Rasha Jame , Moustafa A. Gouda","doi":"10.1016/j.jorganchem.2025.123590","DOIUrl":"10.1016/j.jorganchem.2025.123590","url":null,"abstract":"<div><div>The fusion of benzene with 4<em>H</em>-selenopyran motifs yields three distinct structures: condensed 2<em>H</em>-selenochromene, 4<em>H</em>-selenochromene, and 1<em>H</em>-isoselenochromene. Notably, isoselenochromene features a selenium atom in the second position rather than the first, a configuration that, as far as current knowledge indicates, lacks specific published reports and has predominantly served as a foundational building block. The synthesis of 1<em>H</em>-isoselenochromenes and their analogues can be achieved through various chemical pathways, such as the Sonogashira coupling reaction, nucleophilic addition, organometallic reactions, metal substitution, and other established methods in organic synthesis.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1031 ","pages":"Article 123590"},"PeriodicalIF":2.1,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143578316","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-25DOI: 10.1016/j.jorganchem.2025.123592
Sara Payamifar , Majid Abdouss , Ahmad Poursattar Marjani
β-Cyclodextrins are the most considerable type of supramolecular, which are being vastly investigated for diverse uses owing to their outstanding features such as biodegradability, abundant, nontoxic, cheap, and excellent performance in organic conversions. Sonogashira cross-coupling reaction is the most well-known in the area of chemistry. Sonogashira reaction is a precious strategy for creating C–C bonds. They have been broadly employed in the preparation of multiple carbon molecules. The Sonogashira reaction is a well-known, efficient, and useful reaction widely employed in organic chemistry. They are used in multiple fields like organic synthesis, synthesis of heterocycles, pharmaceuticals, natural products, and nanomaterials. This coupling reaction is a renowned procedure for sp2-carbon-sp-carbon bond construction in organic synthesis. This review intends to summarize the usage of β-cyclodextrin-based catalyst systems in carbon-carbon coupling Sonogashira reactions and overview articles up to 2025. We hope the chemistry of β-cyclodextrin and its uses for green organic conversions debated in the current review will inspire new thinking and open new doors in this area.
{"title":"A review of using β-cyclodextrin-based catalysts for Sonogashira reactions","authors":"Sara Payamifar , Majid Abdouss , Ahmad Poursattar Marjani","doi":"10.1016/j.jorganchem.2025.123592","DOIUrl":"10.1016/j.jorganchem.2025.123592","url":null,"abstract":"<div><div>β-Cyclodextrins are the most considerable type of supramolecular, which are being vastly investigated for diverse uses owing to their outstanding features such as biodegradability, abundant, nontoxic, cheap, and excellent performance in organic conversions. Sonogashira cross-coupling reaction is the most well-known in the area of chemistry. Sonogashira reaction is a precious strategy for creating C–C bonds. They have been broadly employed in the preparation of multiple carbon molecules. The Sonogashira reaction is a well-known, efficient, and useful reaction widely employed in organic chemistry. They are used in multiple fields like organic synthesis, synthesis of heterocycles, pharmaceuticals, natural products, and nanomaterials. This coupling reaction is a renowned procedure for sp<sup>2</sup>-carbon-sp-carbon bond construction in organic synthesis. This review intends to summarize the usage of β-cyclodextrin-based catalyst systems in carbon-carbon coupling Sonogashira reactions and overview articles up to 2025. We hope the chemistry of β-cyclodextrin and its uses for green organic conversions debated in the current review will inspire new thinking and open new doors in this area.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1031 ","pages":"Article 123592"},"PeriodicalIF":2.1,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143519923","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-24DOI: 10.1016/j.jorganchem.2025.123589
Eva M. Gulotty , Gregory D. Kortman , Nicole E. Proctor , Richard J. Staples , Shannon M. Biros , Matthias Bremer , William R. Winchester
The delocalization of electrons across a vinylbis(trimethylsilyl)silyl anion has been studied with both lithium and potassium as counterions. The reaction of vinyl tris(trimethylsilyl)silane with potassium tert-butoxide forms the potassium salt while reaction with methyllithium produces the lithium salt, both by nucleophilic displacement of a trimethylsilyl group. The anion formed has been studied by 1H, 13C and 29Si NMR spectroscopy. A crystal structure of the 12-crown-4 complex of the lithium salt of the vinylbis(trimethylsilyl)silyl anion has been obtained. Reactions of the anion with acetic acid, Ph3SiCl, Ph2MeSiCl, PhCH2Cl and BrCH2CH2Br have been studied and the crystal structure of the product from reaction with Ph3SiCl is reported. Finally, we have studied the anion delocalization for these species using density functional theory and report the calculated rotational barrier for the vinyl silicon bond.
{"title":"Synthesis, characterization and reactions of the Vinylbis(trimethylsilyl)silyl anion","authors":"Eva M. Gulotty , Gregory D. Kortman , Nicole E. Proctor , Richard J. Staples , Shannon M. Biros , Matthias Bremer , William R. Winchester","doi":"10.1016/j.jorganchem.2025.123589","DOIUrl":"10.1016/j.jorganchem.2025.123589","url":null,"abstract":"<div><div>The delocalization of electrons across a vinylbis(trimethylsilyl)silyl anion has been studied with both lithium and potassium as counterions. The reaction of vinyl tris(trimethylsilyl)silane with potassium <em>tert</em>-butoxide forms the potassium salt while reaction with methyllithium produces the lithium salt, both by nucleophilic displacement of a trimethylsilyl group. The anion formed has been studied by <sup>1</sup>H, <sup>13</sup>C and <sup>29</sup>Si NMR spectroscopy. A crystal structure of the 12-crown-4 complex of the lithium salt of the vinylbis(trimethylsilyl)silyl anion has been obtained. Reactions of the anion with acetic acid, Ph<sub>3</sub>SiCl, Ph<sub>2</sub>MeSiCl, PhCH<sub>2</sub>Cl and BrCH<sub>2</sub>CH<sub>2</sub>Br have been studied and the crystal structure of the product from reaction with Ph<sub>3</sub>SiCl is reported. Finally, we have studied the anion delocalization for these species using density functional theory and report the calculated rotational barrier for the vinyl silicon bond.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1031 ","pages":"Article 123589"},"PeriodicalIF":2.1,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143548192","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-23DOI: 10.1016/j.jorganchem.2025.123576
Satyanarayana Battula , Mahesh K. Zilla , Jigar Y. Soni
Here, we report an efficient and simple application of hyper valent iodine-based benzyne precursor, phenyl(mesityl)iodonium tosylate salt in the facile and metal free synthesis of 9-aryldihydrophenanthrenes, wherein the base induced ortho CH deprotonation of the iodonium salt followed by elimination of leaving group (LG) generates benzyne intermediate, and that react with diverse styrenes at ambient temperatures in situ by a tandem protocol to achieve substituted 9,10-dihydrophenanthrines with moderate to appreciable yields.
{"title":"Hypervalent iodine salt as an aryne synthon: An easy access to a tandem synthesis of 9-aryldihydrophenanthrenes with styrenes","authors":"Satyanarayana Battula , Mahesh K. Zilla , Jigar Y. Soni","doi":"10.1016/j.jorganchem.2025.123576","DOIUrl":"10.1016/j.jorganchem.2025.123576","url":null,"abstract":"<div><div>Here, we report an efficient and simple application of hyper valent iodine-based benzyne precursor, phenyl(mesityl)iodonium tosylate salt in the facile and metal free synthesis of 9-aryldihydrophenanthrenes, wherein the base induced ortho C<img>H deprotonation of the iodonium salt followed by elimination of leaving group (LG) generates benzyne intermediate, and that react with diverse styrenes at ambient temperatures in situ by a tandem protocol to achieve substituted 9,10-dihydrophenanthrines with moderate to appreciable yields.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1031 ","pages":"Article 123576"},"PeriodicalIF":2.1,"publicationDate":"2025-02-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143509455","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-21DOI: 10.1016/j.jorganchem.2025.123579
Enock D. Amoateng, Evans Fosu, T. Keith Hollis
A highly selective hydrosilylation of alkenes at room temperature, catalyzed by well-defined CCC–NHC pincer Rh complexes, [(BuCiCiCBu)RhCl2Py] (1), [(BuCiCiCBu)RhCl2(NHMe2)] (2), [(BuCiCiCBu)RhCl(µ-Cl)2Rh(COD)] (3), and [(BuCiCiCBu)RhCl(µ-Cl)]2 (4), (BuCiCiCBu = 2-(1,3-bis(N-butylimidazol-2-ylidene)phenylene) has been achieved. The catalytic system exhibits excellent regioselectivity, affording anti-Markovnikov products in moderate to excellent conversions (48–100 %). Precatalyst [(BuCiCiCBu)RhCl(µ-Cl)2Rh(COD)] (3) demonstrated the highest efficiency in promoting the anti-Markovnikov hydrosilylation of both aryl and alkyl alkenes with excellent selectivity (>99 %) when Et3SiH is used as silane source in acetonitrile. Notably, the system tolerates straight chain alkyl alkenes without inducing isomerization, a commonly encountered limitation with many hydrosilylation catalytic systems.
{"title":"Highly regioselective anti-Markovnikov hydrosilylation of alkenes under mild conditions: Application of CCC-NHC pincer Rh complexes","authors":"Enock D. Amoateng, Evans Fosu, T. Keith Hollis","doi":"10.1016/j.jorganchem.2025.123579","DOIUrl":"10.1016/j.jorganchem.2025.123579","url":null,"abstract":"<div><div>A highly selective hydrosilylation of alkenes at room temperature, catalyzed by well-defined CCC–NHC pincer Rh complexes, [(<sup>Bu</sup>C<sup>i</sup>C<sup>i</sup>C<sup>Bu</sup>)RhCl<sub>2</sub>Py] (<strong>1</strong>), [(<sup>Bu</sup>C<sup>i</sup>C<sup>i</sup>C<sup>Bu</sup>)RhCl<sub>2</sub>(NHMe<sub>2</sub>)] (<strong>2</strong>), [(<sup>Bu</sup>C<sup>i</sup>C<sup>i</sup>C<sup>Bu</sup>)RhCl(µ-Cl)<sub>2</sub>Rh(COD)] (<strong>3</strong>), and [(<sup>Bu</sup>C<sup>i</sup>C<sup>i</sup>C<sup>Bu</sup>)RhCl(µ-Cl)]<sub>2</sub> (<strong>4</strong>), (<sup>Bu</sup>C<sup>i</sup>C<sup>i</sup>C<sup>Bu</sup> = 2-(1,3-bis(N-butylimidazol-2-ylidene)phenylene) has been achieved. The catalytic system exhibits excellent regioselectivity, affording anti-Markovnikov products in moderate to excellent conversions (48–100 %). Precatalyst [(<sup>Bu</sup>C<sup>i</sup>C<sup>i</sup>C<sup>Bu</sup>)RhCl(µ-Cl)<sub>2</sub>Rh(COD)] (<strong>3</strong>) demonstrated the highest efficiency in promoting the anti-Markovnikov hydrosilylation of both aryl and alkyl alkenes with excellent selectivity (>99 %) when Et<sub>3</sub>SiH is used as silane source in acetonitrile. Notably, the system tolerates straight chain alkyl alkenes without inducing isomerization, a commonly encountered limitation with many hydrosilylation catalytic systems.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1031 ","pages":"Article 123579"},"PeriodicalIF":2.1,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143519921","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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