Journal of Organometallic Chemistry最新文献

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Regioselective domino C–C/C–O arylation of 1,2,3-triiodobenzenes and 1,3-diketones: Synthesis and in silico evaluation of 7-iodobenzo[b]furan as potential ALK inhibitors

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-01-21 DOI: 10.1016/j.jorganchem.2025.123526

Raed M. Al-Zoubi , Walid K. Al-Jammal , Mohanad Shkoor , Abdulilah D. Bani-Yaseen , Abbas Khan , Abdelali Agouni , Robert McDonald

We report a simple, direct, and regioselective protocol for the synthesis of 2,3-disubstituted 7-iodobenzo[b]furans via domino double CC/CO arylations of 1,2,3-triiodobenzene and 1,3-dicarbonyl compounds. Remarkably, the C-arylation occurred exclusively at the terminal positions, which are the most reactive and least sterically hindered. The O-arylation reactions were selectively performed with the more reactive carbonyl group. This domino process demonstrated excellent substrate tolerance. Under optimized conditions, the reaction of electron-deficient 1,2,3-triiodoarenes with dicarbonyl compounds afforded the highest isolated yields. Furthermore, the designed novel compounds were screened against ALK, revealing that among the 17 tested, ALK-9p, ALK-9b, ALK-9n, and ALK-9m exhibited the best docking scores using the extra-precision docking method. Molecular simulations of these compounds with ALK confirmed their stable binding behavior, compact topology, and minimal residue flexibility. Finally, binding free energy calculations using MM/PBSA and MM/GBSA methods further validated the pharmacological potential of these shortlisted hits as ALK inhibitors. These results demand prompt experimental validation to determine the promising clinical applications of these compounds in the management of cancer

{"title":"Regioselective domino C–C/C–O arylation of 1,2,3-triiodobenzenes and 1,3-diketones: Synthesis and in silico evaluation of 7-iodobenzo[b]furan as potential ALK inhibitors","authors":"Raed M. Al-Zoubi , Walid K. Al-Jammal , Mohanad Shkoor , Abdulilah D. Bani-Yaseen , Abbas Khan , Abdelali Agouni , Robert McDonald","doi":"10.1016/j.jorganchem.2025.123526","DOIUrl":"10.1016/j.jorganchem.2025.123526","url":null,"abstract":"<div><div>We report a simple, direct, and regioselective protocol for the synthesis of 2,3-disubstituted 7-iodobenzo[b]furans via domino double C<img>C/C<img>O arylations of 1,2,3-triiodobenzene and 1,3-dicarbonyl compounds. Remarkably, the C-arylation occurred exclusively at the terminal positions, which are the most reactive and least sterically hindered. The O-arylation reactions were selectively performed with the more reactive carbonyl group. This domino process demonstrated excellent substrate tolerance. Under optimized conditions, the reaction of electron-deficient 1,2,3-triiodoarenes with dicarbonyl compounds afforded the highest isolated yields. Furthermore, the designed novel compounds were screened against ALK, revealing that among the 17 tested, ALK-9p, ALK-9b, ALK-9n, and ALK-9m exhibited the best docking scores using the extra-precision docking method. Molecular simulations of these compounds with ALK confirmed their stable binding behavior, compact topology, and minimal residue flexibility. Finally, binding free energy calculations using MM/PBSA and MM/GBSA methods further validated the pharmacological potential of these shortlisted hits as ALK inhibitors. These results demand prompt experimental validation to determine the promising clinical applications of these compounds in the management of cancer</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1028 ","pages":"Article 123526"},"PeriodicalIF":2.1,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143357118","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Cutting-edge research on mixed-metal MOFs: fabrication, characterization, properties, and uses

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-01-20 DOI: 10.1016/j.jorganchem.2025.123531

Philips C. Tagbo , Islam Ibrahim , Gehad G. Mohamed , Ngutor Simon Akiiga

Significant strides have been made in recent years to tackle the challenges associated with metal-organic frameworks (MOFs) through the incorporation of heterometallic ions into their secondary building units (SBUs) using various synthesis techniques. The design of mixed- metal–organic frameworks (MM-MOFs) presents a promising strategy to enhance the physicochemical properties of conventional MOFs, thereby improving their performance in diverse applications such as gas storage and separation, catalysis, energy storage and conversion, theranostics, and sensing technologies. Although this field is still in its early stages, there is a growing demand for regular insights into the latest advancements, trends, and innovations associated with the design, synthesis, fabrication, and applications of MM-MOFs. As a result, this review seeks to underscore recent synthesis strategies, advanced characterization techniques, and novel applications of MM-MOFs. Special emphasis is placed on the latest methods utilized in the development of this unique class of materials, with the aim of informing a broader audience about recent breakthroughs in the synthesis of MM-MOFs.

{"title":"Cutting-edge research on mixed-metal MOFs: fabrication, characterization, properties, and uses","authors":"Philips C. Tagbo , Islam Ibrahim , Gehad G. Mohamed , Ngutor Simon Akiiga","doi":"10.1016/j.jorganchem.2025.123531","DOIUrl":"10.1016/j.jorganchem.2025.123531","url":null,"abstract":"<div><div>Significant strides have been made in recent years to tackle the challenges associated with metal-organic frameworks (MOFs) through the incorporation of heterometallic ions into their secondary building units (SBUs) using various synthesis techniques. The design of mixed- metal–organic frameworks (MM-MOFs) presents a promising strategy to enhance the physicochemical properties of conventional MOFs, thereby improving their performance in diverse applications such as gas storage and separation, catalysis, energy storage and conversion, theranostics, and sensing technologies. Although this field is still in its early stages, there is a growing demand for regular insights into the latest advancements, trends, and innovations associated with the design, synthesis, fabrication, and applications of MM-MOFs. As a result, this review seeks to underscore recent synthesis strategies, advanced characterization techniques, and novel applications of MM-MOFs. Special emphasis is placed on the latest methods utilized in the development of this unique class of materials, with the aim of informing a broader audience about recent breakthroughs in the synthesis of MM-MOFs.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1028 ","pages":"Article 123531"},"PeriodicalIF":2.1,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143322264","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

Advancements in ferrocene-based burning rate catalysts: Preparations, properties, catalytic and anti-migration mechanism

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-01-19 DOI: 10.1016/j.jorganchem.2025.123524

Muhammad Owais Malik, Li Wang, Haojie Yu, Jinyi Liu, Basem E. Keshta, Md Alim Uddin, Abdul Basit, Khan Manqoosh Awan

Competent composite solid propellants (CSPs) demand high burning rates (BRs) for optimal performance. Adding burning rate catalysts (BRCs) in a propellant system is one of the key strategies to achieve the desired characteristics, as the BRCs show a settling character in enhancing the working efficiency of CSPs. Among various types of BRCs, ferrocene (Fc)-based compounds are notable for their superior catalytic performance in the burning process. This review explores the preparation of Fc derivatives, Fc-based polymers, Fc-terminated dendrimers, Fc-based MOFs, and Fc-based carbon-rich materials. Also explores the electrochemical, thermal, catalytic, and anti- migration properties of Fc-BRCs in detail. Furthermore, this review highlights the catalytic mechanism of Fc-BRCs as ammonium perchlorate (AP) decomposers as well as the anti-migration mechanism in CSPs. Additionally, a summary has been created to contrast the anti-migration and catalytic activities of different Fc-BRCs. Fc-BRCs are expected to significantly improve the combustion performance of propellants by facilitating more uniform and efficient burning. Their unique structural properties allow for improved oxidation processes, which can lead to higher energy yields and reduced soot formation. This development not only improves the reliability and effectiveness of numerous propulsion systems but also opens up new avenues for designing innovative propellant formulations and applications in the aerospace and defense sectors.

{"title":"Advancements in ferrocene-based burning rate catalysts: Preparations, properties, catalytic and anti-migration mechanism","authors":"Muhammad Owais Malik, Li Wang, Haojie Yu, Jinyi Liu, Basem E. Keshta, Md Alim Uddin, Abdul Basit, Khan Manqoosh Awan","doi":"10.1016/j.jorganchem.2025.123524","DOIUrl":"10.1016/j.jorganchem.2025.123524","url":null,"abstract":"<div><div>Competent composite solid propellants (CSPs) demand high burning rates (BRs) for optimal performance. Adding burning rate catalysts (BRCs) in a propellant system is one of the key strategies to achieve the desired characteristics, as the BRCs show a settling character in enhancing the working efficiency of CSPs. Among various types of BRCs, ferrocene (Fc)-based compounds are notable for their superior catalytic performance in the burning process. This review explores the preparation of Fc derivatives, Fc-based polymers, Fc-terminated dendrimers, Fc-based MOFs, and Fc-based carbon-rich materials. Also explores the electrochemical, thermal, catalytic, and anti- migration properties of Fc-BRCs in detail. Furthermore, this review highlights the catalytic mechanism of Fc-BRCs as ammonium perchlorate (AP) decomposers as well as the anti-migration mechanism in CSPs. Additionally, a summary has been created to contrast the anti-migration and catalytic activities of different Fc-BRCs. Fc-BRCs are expected to significantly improve the combustion performance of propellants by facilitating more uniform and efficient burning. Their unique structural properties allow for improved oxidation processes, which can lead to higher energy yields and reduced soot formation. This development not only improves the reliability and effectiveness of numerous propulsion systems but also opens up new avenues for designing innovative propellant formulations and applications in the aerospace and defense sectors.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1028 ","pages":"Article 123524"},"PeriodicalIF":2.1,"publicationDate":"2025-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143322267","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

Exploration of photophysical, electrochemical and electronic properties of rhenium(I) complexes incorporating acridine moiety: Role of coligands in tuning the spectral and electronic properties

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-01-18 DOI: 10.1016/j.jorganchem.2025.123529

Sneha Ray, Kajal Krishna Rajak

Dinuclear rhenium complex possesing fac-[Re(CO)₃]⁺ core having the formula [Re₂(CO)₆(L)₂] (1) and bearing acridine moiety has been synthesized in excellent yields by the reaction of acridin-4-ol with [Re(CO)₅Cl] in 1:1 ratio in toluene under argon atmosphere. Here, L is the deprotonated form of acridin-4-ol. The reaction of the synthesized dinuclear complex with imidazole (Im), N-methylimidazole (N-MeIm), quinoline (Quin), and 2-methylquinoline (Me-Quin) in dry dichloromethane furnished the mononuclear complexes with the formula, [Re(CO)₃L(Im)] (1a), [Re(CO)₃L(N-MeIm)] (1b), [Re(CO)₃L(Quin)] (1c), and [Re(CO)₃L(Me-Quin)] (1d) in good yields. Molecular structure of fac-[Re₂(CO)₆(L)₂] was confirmed by single crystal X-ray diffraction. Elemental analysis, ESI mass spectroscopy and ¹H NMR spectroscopy were utilised to confirm the formation of the desired complexes. The as-synthesized complexes were further utilised to explore the photophysical, electrochemical, and electronic properties. Photophysical measurements reveal a bathochromic shift upon incorporation of different coligands into the fac-[Re(CO)₃]⁺ core. The emission behaviour of the molecules is consistent with an admixture of ³MLCT and ³ILCT character. To gain insight into the charge transfer-associated conducting nature of the molecules, Electrochemical Impedance Spectra analysis was carried out. Herein, the coligands played a crucial role in tuning the opto-electronic properties of the designed complexes. The ground and excited state geometries of the molecules were explored by theoretical calculations, employing DFT and TD-DFT measurements.

{"title":"Exploration of photophysical, electrochemical and electronic properties of rhenium(I) complexes incorporating acridine moiety: Role of coligands in tuning the spectral and electronic properties","authors":"Sneha Ray, Kajal Krishna Rajak","doi":"10.1016/j.jorganchem.2025.123529","DOIUrl":"10.1016/j.jorganchem.2025.123529","url":null,"abstract":"<div><div>Dinuclear rhenium complex possesing <em>fac</em>-<em>[Re(CO)</em><sub><em>3</em></sub><em>]</em><sup>+</sup> core having the formula [Re<sub>2</sub>(CO)<sub>6</sub>(L)<sub>2</sub>] (<strong>1</strong>) and bearing acridine moiety has been synthesized in excellent yields by the reaction of acridin-4-ol with [Re(CO)<sub>5</sub>Cl] in 1:1 ratio in toluene under argon atmosphere. Here, L is the deprotonated form of acridin-4-ol. The reaction of the synthesized dinuclear complex with imidazole (Im), <em>N</em>-methylimidazole (<em>N</em>-MeIm), quinoline (Quin), and 2-methylquinoline (Me-Quin) in dry dichloromethane furnished the mononuclear complexes with the formula, [Re(CO)<sub>3</sub>L(Im)] (<strong>1a</strong>), [Re(CO)<sub>3</sub>L(<em>N</em>-MeIm)] (<strong>1b</strong>), [Re(CO)<sub>3</sub>L(Quin)] (<strong>1c</strong>), and [Re(CO)<sub>3</sub>L(Me-Quin)] (<strong>1d</strong>) in good yields. Molecular structure of <em>fac</em>-[Re<sub>2</sub>(CO)<sub>6</sub>(L)<sub>2</sub>] was confirmed by single crystal X-ray diffraction. Elemental analysis, ESI mass spectroscopy and <sup>1</sup>H NMR spectroscopy were utilised to confirm the formation of the desired complexes. The as-synthesized complexes were further utilised to explore the photophysical, electrochemical, and electronic properties. Photophysical measurements reveal a bathochromic shift upon incorporation of different coligands into the <em>fac</em>-<em>[Re(CO)</em><sub><em>3</em></sub><em>]</em><sup>+</sup> core. The emission behaviour of the molecules is consistent with an admixture of <sup>3</sup>MLCT and <sup>3</sup>ILCT character. To gain insight into the charge transfer-associated conducting nature of the molecules, Electrochemical Impedance Spectra analysis was carried out. Herein, the coligands played a crucial role in tuning the opto-electronic properties of the designed complexes. The ground and excited state geometries of the molecules were explored by theoretical calculations, employing DFT and TD-DFT measurements.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1028 ","pages":"Article 123529"},"PeriodicalIF":2.1,"publicationDate":"2025-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143322268","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

Mono- and dinuclear tin(IV) complexes with Schiff bases: Synthesis, structures, redox and optoelectronic properties

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-01-18 DOI: 10.1016/j.jorganchem.2025.123527

Irina V. Krylova , Varvara Yu. Proshutinskaya , Liliya D. Labutskaya , Victoriya A. Balycheva , Mikhail E. Minyaev , Mariya O. Markova , Valery M. Pechennikov , Elena N. Nikolaevskaya , Mikhail A. Syroeshkin , Mikhail P. Egorov , Pavel G. Shangin

A Schiff base (named after Hugo Schiff) is a sub-class of imines, being either secondary ketimines or secondary aldimines depending on their structure. Due to relatively simplicity to synthesize, a Schiff bases allow to tune structural and physico-chemical properties of metal complexes based on them. In the present work Schiff base complexes of tin(IV) are prepared. The interaction was carried out through the microwave-assisted treatment of Et₂SnO with symmetrical and unsymmetrical Schiff base ligands based on salicylaldehyde/naphthaldehyde and a series of hydrazides/thiosemicarbazide. ¹H, ¹³C, ¹¹⁹Sn NMR spectroscopy, high resolution mass spectroscopy, UV–Vis spectroscopy and X-ray analysis were employed to investigate the molecular structure of the produced ligands and its associated metal complexes The use of symmetric derivatives with unconjugated -(CH₂)₄ and conjugated pyridine bridges allows to show that the electrochemical reduction proceeds independently at both “ends” of the molecule in the case of the unconjugated bridge and differs significantly in the case of the bridge participating in the common conjugation. All new mono- and dinuclear Sn(IV) complexes demonstrated rather narrow HOMO-LUMO gap, less than 3 eV.

{"title":"Mono- and dinuclear tin(IV) complexes with Schiff bases: Synthesis, structures, redox and optoelectronic properties","authors":"Irina V. Krylova , Varvara Yu. Proshutinskaya , Liliya D. Labutskaya , Victoriya A. Balycheva , Mikhail E. Minyaev , Mariya O. Markova , Valery M. Pechennikov , Elena N. Nikolaevskaya , Mikhail A. Syroeshkin , Mikhail P. Egorov , Pavel G. Shangin","doi":"10.1016/j.jorganchem.2025.123527","DOIUrl":"10.1016/j.jorganchem.2025.123527","url":null,"abstract":"<div><div>A Schiff base (named after Hugo Schiff) is a sub-class of imines, being either secondary ketimines or secondary aldimines depending on their structure. Due to relatively simplicity to synthesize, a Schiff bases allow to tune structural and physico-chemical properties of metal complexes based on them. In the present work Schiff base complexes of tin(IV) are prepared. The interaction was carried out through the microwave-assisted treatment of Et<sub>2</sub>SnO with symmetrical and unsymmetrical Schiff base ligands based on salicylaldehyde/naphthaldehyde and a series of hydrazides/thiosemicarbazide. <sup>1</sup>H, <sup>13</sup>C, <sup>119</sup>Sn NMR spectroscopy, high resolution mass spectroscopy, UV–Vis spectroscopy and X-ray analysis were employed to investigate the molecular structure of the produced ligands and its associated metal complexes The use of symmetric derivatives with unconjugated -(CH<sub>2</sub>)<sub>4</sub> and conjugated pyridine bridges allows to show that the electrochemical reduction proceeds independently at both “ends” of the molecule in the case of the unconjugated bridge and differs significantly in the case of the bridge participating in the common conjugation. All new mono- and dinuclear Sn(IV) complexes demonstrated rather narrow HOMO-LUMO gap, less than 3 eV.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1028 ","pages":"Article 123527"},"PeriodicalIF":2.1,"publicationDate":"2025-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143322266","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

Visible to near-infrared light activated photoacids: Molecular architecture for chemical and biological applications

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-01-18 DOI: 10.1016/j.jorganchem.2025.123525

Jiayang Jiang , Zihan Xu , Tang Li , Zhuang Lv

Photoacids (PAs) are compounds capable of modulating proton concentration in response to light. PAs have evolved to address the limitations of UV light, which include phototoxicity and shallow tissue penetration. The shift towards PAs activated by visible to near-infrared wavelengths offers several advantages such as deeper tissue penetration, reduced phototoxic and enhanced environmental sustainability. These PAs allow for precise control over reaction conditions and are crucial for applications in biomedicine and materials science. The classification of these PAs includes photolytic, excited-state, and photoisomerized types, each with unique properties for light absorption and acid generation. Strategies for functional enhancement of these PAs are summarized, such as introduction of electron-donating and withdrawing substituents, enlargement of the conjugated system, incorporation of D-π-A structures, and enhancement of two-photon absorption cross-sections. These strategies are essential for improving photoacidic performance in applications like photocatalysis, drug delivery, and photoacid therapy. Besides, the impediments to the practical utilization of PAs across various domains are discussed as well.

{"title":"Visible to near-infrared light activated photoacids: Molecular architecture for chemical and biological applications","authors":"Jiayang Jiang , Zihan Xu , Tang Li , Zhuang Lv","doi":"10.1016/j.jorganchem.2025.123525","DOIUrl":"10.1016/j.jorganchem.2025.123525","url":null,"abstract":"<div><div>Photoacids (PAs) are compounds capable of modulating proton concentration in response to light. PAs have evolved to address the limitations of UV light, which include phototoxicity and shallow tissue penetration. The shift towards PAs activated by visible to near-infrared wavelengths offers several advantages such as deeper tissue penetration, reduced phototoxic and enhanced environmental sustainability. These PAs allow for precise control over reaction conditions and are crucial for applications in biomedicine and materials science. The classification of these PAs includes photolytic, excited-state, and photoisomerized types, each with unique properties for light absorption and acid generation. Strategies for functional enhancement of these PAs are summarized, such as introduction of electron-donating and withdrawing substituents, enlargement of the conjugated system, incorporation of D-π-A structures, and enhancement of two-photon absorption cross-sections. These strategies are essential for improving photoacidic performance in applications like photocatalysis, drug delivery, and photoacid therapy. Besides, the impediments to the practical utilization of PAs across various domains are discussed as well.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1027 ","pages":"Article 123525"},"PeriodicalIF":2.1,"publicationDate":"2025-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143332196","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

Copper catalysed construction of C-P bond: C-H functionalization

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-01-12 DOI: 10.1016/j.jorganchem.2025.123512

Rajnikant N. Ghoghari, Kishor H. Chikhalia

Over the past decades, transition metal catalysed synthesis of organophosphorus compounds appears with rapid advancements. Phosphorus annulated compounds achieved popularity because of their broad range of applications such as, ligands in catalysis, as bioactive natural products, medicines, agrochemicals and building blocks. It leads to further augmentation of relevant methodologies for the construction of bioactive scaffolds having C-P bond, which is new frontier in synthetic organic chemistry. Currently, organophosphorus compounds are being synthesised through transition metal catalyst. Metal catalysed pre-functionalization of heterocycles through phosphorus hydrogen (P- H) bond leads to the C-P linked heterocycles through C-H functionalization concept. The synthesis of several structurally varied complex compounds requires the use of copper catalysed reactions because of their strong bond forming abilities under moderate reaction conditions and broad functional group tolerance.

This review (2015–2024) focusses the advancement in copper catalysed C-P bond formation encompassing both intra and intermolecular transformations. Key aspects like reaction mechanism, substrate scope, catalyst design are discussed highlighting the versatility and applicability of synthetic approach. Furthermore, applications of the synthetic routes in the design of building blocks, agrochemicals and functional materials have been emphasized with respective mechanisms. Finally challenges and future directions in this field are outlined, aiming inspiration to researchers involved in construction of C-P bond.

{"title":"Copper catalysed construction of C-P bond: C-H functionalization","authors":"Rajnikant N. Ghoghari, Kishor H. Chikhalia","doi":"10.1016/j.jorganchem.2025.123512","DOIUrl":"10.1016/j.jorganchem.2025.123512","url":null,"abstract":"<div><div>Over the past decades, transition metal catalysed synthesis of organophosphorus compounds appears with rapid advancements. Phosphorus annulated compounds achieved popularity because of their broad range of applications such as, ligands in catalysis, as bioactive natural products, medicines, agrochemicals and building blocks. It leads to further augmentation of relevant methodologies for the construction of bioactive scaffolds having C-P bond, which is new frontier in synthetic organic chemistry. Currently, organophosphorus compounds are being synthesised through transition metal catalyst. Metal catalysed pre-functionalization of heterocycles through phosphorus hydrogen (P- H) bond leads to the C-P linked heterocycles through C<img>-H functionalization concept. The synthesis of several structurally varied complex compounds requires the use of copper catalysed reactions because of their strong bond forming abilities under moderate reaction conditions and broad functional group tolerance.</div><div>This review (2015–2024) focusses the advancement in copper catalysed C-P bond formation encompassing both intra and intermolecular transformations. Key aspects like reaction mechanism, substrate scope, catalyst design are discussed highlighting the versatility and applicability of synthetic approach. Furthermore, applications of the synthetic routes in the design of building blocks, agrochemicals and functional materials have been emphasized with respective mechanisms. Finally challenges and future directions in this field are outlined, aiming inspiration to researchers involved in construction of C-P bond.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1027 ","pages":"Article 123512"},"PeriodicalIF":2.1,"publicationDate":"2025-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143333167","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 characterization of gold(I) N-heterocyclic carbenes complexes bearing methacrylate moiety

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-01-11 DOI: 10.1016/j.jorganchem.2025.123514

Rim Hamdi , Ida Staccioni , Julie Gerber , Sandrine Rup-Jacques , Jasmine Hertzog , Vincent Carré , Michèle Sindt , Corentin Lefebvre , Taoufik Boubaker , Jean-François Longevial

The study focuses on gold(I) N-heterocyclic carbene (NHC) complexes. The research aims to synthesize a family of four mono- and four bis-gold(I) N-heterocyclic carbene complexes, each bearing a methacrylate motif, with yields ranging from 63% to 98%. Two model complexes from this series were tested toward sulfur-based nucleophilic attack to assess the possibility of a Michael addition to the acrylate motif, with a view to future bioconjugation. Experimental results reveal that thiolate addition occurs exclusively at the gold(I) center, regardless of whether the N-heterocyclic carbene is a mono- or a bis-carbene, leaving the acrylate motif untouched. This outcome is supported by theoretical calculations, which predict an activation energy of at least 4 kcal/mol favoring nucleophilic attack at the gold(I) center. These findings suggest that gold(I) NHC complexes could serve as effective "clickable" motifs in themselves, challenging the necessity of further functionalizing them with additional clickable groups for bioconjugation applications.

{"title":"Synthesis and characterization of gold(I) N-heterocyclic carbenes complexes bearing methacrylate moiety","authors":"Rim Hamdi , Ida Staccioni , Julie Gerber , Sandrine Rup-Jacques , Jasmine Hertzog , Vincent Carré , Michèle Sindt , Corentin Lefebvre , Taoufik Boubaker , Jean-François Longevial","doi":"10.1016/j.jorganchem.2025.123514","DOIUrl":"10.1016/j.jorganchem.2025.123514","url":null,"abstract":"<div><div>The study focuses on gold(I) N-heterocyclic carbene (NHC) complexes. The research aims to synthesize a family of four mono- and four bis-gold(I) N-heterocyclic carbene complexes, each bearing a methacrylate motif, with yields ranging from 63% to 98%. Two model complexes from this series were tested toward sulfur-based nucleophilic attack to assess the possibility of a Michael addition to the acrylate motif, with a view to future bioconjugation. Experimental results reveal that thiolate addition occurs exclusively at the gold(I) center, regardless of whether the N-heterocyclic carbene is a mono- or a bis-carbene, leaving the acrylate motif untouched. This outcome is supported by theoretical calculations, which predict an activation energy of at least 4 kcal/mol favoring nucleophilic attack at the gold(I) center. These findings suggest that gold(I) NHC complexes could serve as effective \"clickable\" motifs in themselves, challenging the necessity of further functionalizing them with additional clickable groups for bioconjugation applications.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1027 ","pages":"Article 123514"},"PeriodicalIF":2.1,"publicationDate":"2025-01-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143332195","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

Isolation and characterization of [n-Bu2Sn(OH2)(phen)(OSO2CF3)](O3SCF3) (phen = 1,10-phenanthroline): The missing link

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-01-10 DOI: 10.1016/j.jorganchem.2025.123511

Hélène Cattey, Marie-José Penouilh, Quentin Bonin, Laurent Plasseraud

Reaction of [n-Bu₂Sn(μ-OH)(H₂O)(OSO₂CF₃)]₂ (1) with 1,10-phenanthroline (phen) in acetonitrile at room temperature in a 1:0.75 molar ratio leads to the formation of a mixture of three species comprising [{n-Bu₂Sn(H₂O)}₂O·n-Bu₂Sn(OH)₂](O₃SCF₃)₂ (2) and [{n-Bu₂Sn(OH)(OSO₂CF₃)}(n-Bu₂SnO)]₂ (3) as well as the title compound [n-Bu₂Sn(OH₂)(phen)(OSO₂CF₃)](O₃SCF₃) (4). Compounds 1, 2 and 3 crystallize in dichloromethane at –20 °C, while 4 remains in solution under these conditions. After filtration and by repeating this procedure several times (four in total), it was possible to isolate only 4. Single-crystals of 4, suitable for an X-ray diffraction analysis, were grown from a mixture of dichloromethane/toluene. Compound 4 consists of a mononcationic di-n-butyltin(IV) complex, N,N-chelated by one phen ligand and coordinated by one water molecule and one trifluoromethanesulfonato ligand. In the crystal lattice, the individual molecule of 4 are associated in dimers resulting from intermolecular hydrogen-bonding interactions between aqua ligands and trifluoromethasulfonate counteranions. The isolation and characterization of compound 4 provides new insights into the reactivity of 1 with phen.

{"title":"Isolation and characterization of [n-Bu2Sn(OH2)(phen)(OSO2CF3)](O3SCF3) (phen = 1,10-phenanthroline): The missing link","authors":"Hélène Cattey, Marie-José Penouilh, Quentin Bonin, Laurent Plasseraud","doi":"10.1016/j.jorganchem.2025.123511","DOIUrl":"10.1016/j.jorganchem.2025.123511","url":null,"abstract":"<div><div>Reaction of [<em>n</em>-Bu<sub>2</sub>Sn(<em>μ</em>-OH)(H<sub>2</sub>O)(OSO<sub>2</sub>CF<sub>3</sub>)]<sub>2</sub> (<strong>1</strong>) with 1,10-phenanthroline (phen) in acetonitrile at room temperature in a 1:0.75 molar ratio leads to the formation of a mixture of three species comprising [{<em>n</em>-Bu<sub>2</sub>Sn(H<sub>2</sub>O)}<sub>2</sub>O·<em>n</em>-Bu<sub>2</sub>Sn(OH)<sub>2</sub>](O<sub>3</sub>SCF<sub>3</sub>)<sub>2</sub> (<strong>2</strong>) and [{<em>n</em>-Bu<sub>2</sub>Sn(OH)(OSO<sub>2</sub>CF<sub>3</sub>)}(<em>n</em>-Bu<sub>2</sub>SnO)]<sub>2</sub> (<strong>3</strong>) as well as the title compound [<em>n</em>-Bu<sub>2</sub>Sn(OH<sub>2</sub>)(phen)(OSO<sub>2</sub>CF<sub>3</sub>)](O<sub>3</sub>SCF<sub>3</sub>) (<strong>4</strong>). Compounds <strong>1, 2</strong> and <strong>3</strong> crystallize in dichloromethane at –20 °C, while <strong>4</strong> remains in solution under these conditions. After filtration and by repeating this procedure several times (four in total), it was possible to isolate only <strong>4</strong>. Single-crystals of <strong>4</strong>, suitable for an X-ray diffraction analysis, were grown from a mixture of dichloromethane/toluene. Compound <strong>4</strong> consists of a mononcationic di-<em>n</em>-butyltin(IV) complex, <em>N,N</em>-chelated by one phen ligand and coordinated by one water molecule and one trifluoromethanesulfonato ligand. In the crystal lattice, the individual molecule of <strong>4</strong> are associated in dimers resulting from intermolecular hydrogen-bonding interactions between aqua ligands and trifluoromethasulfonate counteranions. The isolation and characterization of compound <strong>4</strong> provides new insights into the reactivity of <strong>1</strong> with phen.</div></div>","PeriodicalId":374,"journal":{"name":"Journal of Organometallic Chemistry","volume":"1027 ","pages":"Article 123511"},"PeriodicalIF":2.1,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143332193","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Cu-catalyzed reductive Friedel-Crafts alkylation of indoles with ketones for one-pot synthesis of 3-substituted indoles

IF 2.1 3区化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR

Journal of Organometallic Chemistry

Pub Date : 2025-01-09 DOI: 10.1016/j.jorganchem.2025.123513

Wengang Wang, Zewei Mao

3-Substituted indoles have attracted more and more attention bearing good bioactivity. In this work, we have explored an effective method for Cu-catalyzed reductive Friedel-Crafts alkylation of indoles with ketones using Et₃SiH as reductant to give 3-substituted indoles in good yields, and it could be applicable for both substituted indoles and N-methylindoles.

引用次数: 0

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