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Enabling Nickel-Catalyzed Suzuki–Miyaura Cross-Coupling of Carbamoyl Fluorides: Mechanism and Scope 镍催化氟氨甲酰的Suzuki-Miyaura交叉偶联：机理和范围
ChemistryEurope Pub Date : 2025-08-30 DOI: 10.1002/ceur.202500213
Lulu Han, Viktor Boshevski, Yi Yang, Dan Louvel, Margherita Colombo, Gaël Tran, Emmanuel Lacôte, Abderrahmane Amgoune, Anis Tlili
{"title":"Enabling Nickel-Catalyzed Suzuki–Miyaura Cross-Coupling of Carbamoyl Fluorides: Mechanism and Scope","authors":"Lulu Han,&nbsp;Viktor Boshevski,&nbsp;Yi Yang,&nbsp;Dan Louvel,&nbsp;Margherita Colombo,&nbsp;Gaël Tran,&nbsp;Emmanuel Lacôte,&nbsp;Abderrahmane Amgoune,&nbsp;Anis Tlili","doi":"10.1002/ceur.202500213","DOIUrl":"https://doi.org/10.1002/ceur.202500213","url":null,"abstract":"<p>The first Ni-catalyzed Suzuki cross-coupling amide synthesis using stable carbamoyl fluoride starting materials under mild conditions is reported. Mechanistic studies are carried out to document the reactivity of nickel toward the C<span></span>F bond oxidative addition of carbamoyl fluorides and the transmetalation with arylboronic acids. Stoichiometric reactions and isolation of key organometallic intermediates allow us to identify the transmetalation as the most challenging step of the coupling reaction mechanism. The use of tris(4-methoxyphenyl) phosphine ligands enables the development of robust and practical catalytic approach for the synthesis of a broad range of amides.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500213","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129475","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Enabling Nickel-Catalyzed Suzuki–Miyaura Cross-Coupling of Carbamoyl Fluorides: Mechanism and Scope 镍催化氟氨甲酰的Suzuki-Miyaura交叉偶联：机理和范围
ChemistryEurope Pub Date : 2025-08-30 DOI: 10.1002/ceur.202500213
Lulu Han, Viktor Boshevski, Yi Yang, Dan Louvel, Margherita Colombo, Gaël Tran, Emmanuel Lacôte, Abderrahmane Amgoune, Anis Tlili
{"title":"Enabling Nickel-Catalyzed Suzuki–Miyaura Cross-Coupling of Carbamoyl Fluorides: Mechanism and Scope","authors":"Lulu Han,&nbsp;Viktor Boshevski,&nbsp;Yi Yang,&nbsp;Dan Louvel,&nbsp;Margherita Colombo,&nbsp;Gaël Tran,&nbsp;Emmanuel Lacôte,&nbsp;Abderrahmane Amgoune,&nbsp;Anis Tlili","doi":"10.1002/ceur.202500213","DOIUrl":"https://doi.org/10.1002/ceur.202500213","url":null,"abstract":"<p>The first Ni-catalyzed Suzuki cross-coupling amide synthesis using stable carbamoyl fluoride starting materials under mild conditions is reported. Mechanistic studies are carried out to document the reactivity of nickel toward the C<span></span>F bond oxidative addition of carbamoyl fluorides and the transmetalation with arylboronic acids. Stoichiometric reactions and isolation of key organometallic intermediates allow us to identify the transmetalation as the most challenging step of the coupling reaction mechanism. The use of tris(4-methoxyphenyl) phosphine ligands enables the development of robust and practical catalytic approach for the synthesis of a broad range of amides.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500213","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129476","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Room-Temperature Direct Spectroscopic Observation of High-Valent Terminal Iron-Oxo Species of a µ-Nitrido-Bridged Iron Phthalocyanine Dimer Deposited on a Highly Oriented Pyrolytic Graphite Surface 室温直接光谱观察微氮桥接酞菁铁二聚体在高取向热解石墨表面沉积的高价末端铁氧态
ChemistryEurope Pub Date : 2025-08-25 DOI: 10.1002/ceur.202500277
Yasuyuki Yamada, Yuka Toyoda, Masanari Nagasaka, Naoki Nakatani, Takanori Koitaya, Akiyoshi Kuzume, Kentaro Tanaka
{"title":"Room-Temperature Direct Spectroscopic Observation of High-Valent Terminal Iron-Oxo Species of a µ-Nitrido-Bridged Iron Phthalocyanine Dimer Deposited on a Highly Oriented Pyrolytic Graphite Surface","authors":"Yasuyuki Yamada,&nbsp;Yuka Toyoda,&nbsp;Masanari Nagasaka,&nbsp;Naoki Nakatani,&nbsp;Takanori Koitaya,&nbsp;Akiyoshi Kuzume,&nbsp;Kentaro Tanaka","doi":"10.1002/ceur.202500277","DOIUrl":"https://doi.org/10.1002/ceur.202500277","url":null,"abstract":"<p>High-valent metal-oxo species, such as iron(IV)-oxo porphyrin π-cation radical, are known to be involved in a variety of oxidative C<span></span>H bond activation by metal complexes in the presence of oxidants. Although spectroscopic observations of these high-valent metal-oxo species are important for understanding reaction mechanisms, their high reactivities sometimes hamper direct observations, especially at ambient temperature. Herein, a high-valent iron-oxo species, involved in catalytic CH<sub>4</sub> oxidation by a µ-nitrido-bridged iron phthalocyanine dimer in an aqueous solution in the presence of excess H<sub>2</sub>O<sub>2</sub>, was successfully investigated by X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), Raman, and matrix-assisted laser desorption and ionization-time-of-flight mass spectroscopy (MALDI-TOF MS) studies after deposition on a highly oriented pyrolytic graphite (HOPG) surface at room temperature. XPS study indicated the formation of a species with high oxidation states after treatment of the µ-nitrido-bridged iron phthalocyanine dimer attached on a HOPG with H<sub>2</sub>O<sub>2</sub>. Raman and O K-edge XAS studies, in combination with MALDI-TOF MS results, indicated the evidence for the formation of a species containing an oxygen atom with a double-bond character.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500277","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129381","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Room-Temperature Direct Spectroscopic Observation of High-Valent Terminal Iron-Oxo Species of a µ-Nitrido-Bridged Iron Phthalocyanine Dimer Deposited on a Highly Oriented Pyrolytic Graphite Surface 室温直接光谱观察微氮桥接酞菁铁二聚体在高取向热解石墨表面沉积的高价末端铁氧态
ChemistryEurope Pub Date : 2025-08-25 DOI: 10.1002/ceur.202500277
Yasuyuki Yamada, Yuka Toyoda, Masanari Nagasaka, Naoki Nakatani, Takanori Koitaya, Akiyoshi Kuzume, Kentaro Tanaka
{"title":"Room-Temperature Direct Spectroscopic Observation of High-Valent Terminal Iron-Oxo Species of a µ-Nitrido-Bridged Iron Phthalocyanine Dimer Deposited on a Highly Oriented Pyrolytic Graphite Surface","authors":"Yasuyuki Yamada,&nbsp;Yuka Toyoda,&nbsp;Masanari Nagasaka,&nbsp;Naoki Nakatani,&nbsp;Takanori Koitaya,&nbsp;Akiyoshi Kuzume,&nbsp;Kentaro Tanaka","doi":"10.1002/ceur.202500277","DOIUrl":"https://doi.org/10.1002/ceur.202500277","url":null,"abstract":"<p>High-valent metal-oxo species, such as iron(IV)-oxo porphyrin π-cation radical, are known to be involved in a variety of oxidative C<span></span>H bond activation by metal complexes in the presence of oxidants. Although spectroscopic observations of these high-valent metal-oxo species are important for understanding reaction mechanisms, their high reactivities sometimes hamper direct observations, especially at ambient temperature. Herein, a high-valent iron-oxo species, involved in catalytic CH<sub>4</sub> oxidation by a µ-nitrido-bridged iron phthalocyanine dimer in an aqueous solution in the presence of excess H<sub>2</sub>O<sub>2</sub>, was successfully investigated by X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), Raman, and matrix-assisted laser desorption and ionization-time-of-flight mass spectroscopy (MALDI-TOF MS) studies after deposition on a highly oriented pyrolytic graphite (HOPG) surface at room temperature. XPS study indicated the formation of a species with high oxidation states after treatment of the µ-nitrido-bridged iron phthalocyanine dimer attached on a HOPG with H<sub>2</sub>O<sub>2</sub>. Raman and O K-edge XAS studies, in combination with MALDI-TOF MS results, indicated the evidence for the formation of a species containing an oxygen atom with a double-bond character.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500277","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129398","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
The Parent GaH2SbH2 Monomer Stabilized by an N-Heterocyclic Carbene n -杂环卡宾稳定的GaH2SbH2母单体
ChemistryEurope Pub Date : 2025-08-25 DOI: 10.1002/ceur.202500301
Robert Szlosek, Kevin Dollberg, Gábor Balázs, Michael Seidl, Carsten von Hänisch, Manfred Scheer
{"title":"The Parent GaH2SbH2 Monomer Stabilized by an N-Heterocyclic Carbene","authors":"Robert Szlosek,&nbsp;Kevin Dollberg,&nbsp;Gábor Balázs,&nbsp;Michael Seidl,&nbsp;Carsten von Hänisch,&nbsp;Manfred Scheer","doi":"10.1002/ceur.202500301","DOIUrl":"https://doi.org/10.1002/ceur.202500301","url":null,"abstract":"<p>The synthesis and characterization of the stibanyltrielanes IDipp·GaH<sub>2</sub>Sb(SiMe<sub>3</sub>)<sub>2</sub> (<b>1a</b>) and IDipp·BH<sub>2</sub>Sb(SiMe<sub>3</sub>)<sub>2</sub> (<b>1b</b>) are presented. <b>1a</b> represents the first example for the isolation of a molecular stibanylgallane monomer stabilized only by a Lewis base (LB). While methanolytic cleavage of the {SiMe<sub>3</sub>} residues in <b>1a</b> cannot be achieved, the direct salt metathesis reactions of K(18c6)SbH<sub>2</sub> with LB·EH<sub>2</sub>X (LB = IDipp, NMe<sub>3</sub>; E = B, Ga; X = I, OTf) afford the isolation of the parent compounds IDipp·BH<sub>2</sub>SbH<sub>2</sub> (<b>2a</b>), Me<sub>3</sub>N·BH<sub>2</sub>SbH<sub>2</sub> (<b>2b</b>), and IDipp·GaH<sub>2</sub>SbH<sub>2</sub> (<b>3</b>) for the first time in moderate yields. Specifically, the synthesis of <b>3</b> not only represents the first stabilization of the {GaH<sub>2</sub>SbH<sub>2</sub>} motif as the so far heaviest known ethylene-like parent group 13/15 element combination but also validates its stabilization procedure by a LB to access a first sterically unhindered primary stibane. All compounds display drastic sensitivity toward air, light, and temperature. The products are characterized by NMR and infrared spectroscopy, as well as by single-crystal X-ray structure determination and mass spectrometry and the electronic structure is investigated by density functional theory calculations. Furthermore, the reaction of IDipp·GaCl<sub>3</sub> with K(18c6)SbH<sub>2</sub> yields a product mixture, in which <b>3</b> and the unprecedented IDipp·GaH(SbH<sub>2</sub>)<sub>2</sub> (<b>4</b>) can be identified.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500301","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129399","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
The Parent GaH2SbH2 Monomer Stabilized by an N-Heterocyclic Carbene n -杂环卡宾稳定的GaH2SbH2母单体
ChemistryEurope Pub Date : 2025-08-25 DOI: 10.1002/ceur.202500301
Robert Szlosek, Kevin Dollberg, Gábor Balázs, Michael Seidl, Carsten von Hänisch, Manfred Scheer
{"title":"The Parent GaH2SbH2 Monomer Stabilized by an N-Heterocyclic Carbene","authors":"Robert Szlosek,&nbsp;Kevin Dollberg,&nbsp;Gábor Balázs,&nbsp;Michael Seidl,&nbsp;Carsten von Hänisch,&nbsp;Manfred Scheer","doi":"10.1002/ceur.202500301","DOIUrl":"https://doi.org/10.1002/ceur.202500301","url":null,"abstract":"<p>The synthesis and characterization of the stibanyltrielanes IDipp·GaH<sub>2</sub>Sb(SiMe<sub>3</sub>)<sub>2</sub> (<b>1a</b>) and IDipp·BH<sub>2</sub>Sb(SiMe<sub>3</sub>)<sub>2</sub> (<b>1b</b>) are presented. <b>1a</b> represents the first example for the isolation of a molecular stibanylgallane monomer stabilized only by a Lewis base (LB). While methanolytic cleavage of the {SiMe<sub>3</sub>} residues in <b>1a</b> cannot be achieved, the direct salt metathesis reactions of K(18c6)SbH<sub>2</sub> with LB·EH<sub>2</sub>X (LB = IDipp, NMe<sub>3</sub>; E = B, Ga; X = I, OTf) afford the isolation of the parent compounds IDipp·BH<sub>2</sub>SbH<sub>2</sub> (<b>2a</b>), Me<sub>3</sub>N·BH<sub>2</sub>SbH<sub>2</sub> (<b>2b</b>), and IDipp·GaH<sub>2</sub>SbH<sub>2</sub> (<b>3</b>) for the first time in moderate yields. Specifically, the synthesis of <b>3</b> not only represents the first stabilization of the {GaH<sub>2</sub>SbH<sub>2</sub>} motif as the so far heaviest known ethylene-like parent group 13/15 element combination but also validates its stabilization procedure by a LB to access a first sterically unhindered primary stibane. All compounds display drastic sensitivity toward air, light, and temperature. The products are characterized by NMR and infrared spectroscopy, as well as by single-crystal X-ray structure determination and mass spectrometry and the electronic structure is investigated by density functional theory calculations. Furthermore, the reaction of IDipp·GaCl<sub>3</sub> with K(18c6)SbH<sub>2</sub> yields a product mixture, in which <b>3</b> and the unprecedented IDipp·GaH(SbH<sub>2</sub>)<sub>2</sub> (<b>4</b>) can be identified.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500301","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129397","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Phenothiazylpropylsulfonate: A High-Potential Posolyte for Redox-Flow Batteries: Study of the Instability in the Charged State 吩噻嗪基丙基磺酸盐：一种用于氧化还原液流电池的高电位电解质：带电状态下不稳定性的研究
ChemistryEurope Pub Date : 2025-08-15 DOI: 10.1002/ceur.202500226
Roman Ishchenko, Matthieu Becuwe, Lionel Dubois, Serge Gambarelli, Christine Cézard, Emmanuel Baudrin
{"title":"Phenothiazylpropylsulfonate: A High-Potential Posolyte for Redox-Flow Batteries: Study of the Instability in the Charged State","authors":"Roman Ishchenko,&nbsp;Matthieu Becuwe,&nbsp;Lionel Dubois,&nbsp;Serge Gambarelli,&nbsp;Christine Cézard,&nbsp;Emmanuel Baudrin","doi":"10.1002/ceur.202500226","DOIUrl":"https://doi.org/10.1002/ceur.202500226","url":null,"abstract":"<p>The development of aqueous organic redox-flow batteries (AORFB) requires finding new posolyte alternatives to the ferrocyanide salts used presently. Among the potential families, phenothiazine has been reported to be of interest if its solubility in aqueous medium is successfully increased. In this article, the phenothiazine propyl sulfonate (PTZPS) is evaluated as a promising high-potential posolyte for neutral-medium aqueous redox-flow battery. It is demonstrated that electrochemical reversibility is highly dependent on pH, with namely a fast capacity loss in neutral medium. Through the preparation of the oxidized form of this molecule, a kinetic study is performed, confirming the crucial role of the electron transfer step between two molecules at this redox state. Even if density functional theory (DFT) calculations of the electron transfer are not successful due to the significant multireference character of the oxidized form's dyad, using MD simulations, the behavior of the oxidized form in various media is qualitatively predicted, including the effect of addition of chaotropic additives.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500226","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129119","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Phenothiazylpropylsulfonate: A High-Potential Posolyte for Redox-Flow Batteries: Study of the Instability in the Charged State 吩噻嗪基丙基磺酸盐：一种用于氧化还原液流电池的高电位电解质：带电状态下不稳定性的研究
ChemistryEurope Pub Date : 2025-08-15 DOI: 10.1002/ceur.202500226
Roman Ishchenko, Matthieu Becuwe, Lionel Dubois, Serge Gambarelli, Christine Cézard, Emmanuel Baudrin
{"title":"Phenothiazylpropylsulfonate: A High-Potential Posolyte for Redox-Flow Batteries: Study of the Instability in the Charged State","authors":"Roman Ishchenko,&nbsp;Matthieu Becuwe,&nbsp;Lionel Dubois,&nbsp;Serge Gambarelli,&nbsp;Christine Cézard,&nbsp;Emmanuel Baudrin","doi":"10.1002/ceur.202500226","DOIUrl":"https://doi.org/10.1002/ceur.202500226","url":null,"abstract":"<p>The development of aqueous organic redox-flow batteries (AORFB) requires finding new posolyte alternatives to the ferrocyanide salts used presently. Among the potential families, phenothiazine has been reported to be of interest if its solubility in aqueous medium is successfully increased. In this article, the phenothiazine propyl sulfonate (PTZPS) is evaluated as a promising high-potential posolyte for neutral-medium aqueous redox-flow battery. It is demonstrated that electrochemical reversibility is highly dependent on pH, with namely a fast capacity loss in neutral medium. Through the preparation of the oxidized form of this molecule, a kinetic study is performed, confirming the crucial role of the electron transfer step between two molecules at this redox state. Even if density functional theory (DFT) calculations of the electron transfer are not successful due to the significant multireference character of the oxidized form's dyad, using MD simulations, the behavior of the oxidized form in various media is qualitatively predicted, including the effect of addition of chaotropic additives.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500226","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129118","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Lone Pair–π Interactions Modulated by Coordination Geometry in NDI-di-NHC Metal Chloride Complexes NDI-di-NHC金属氯化物配合物配位几何调制的孤对-π相互作用
ChemistryEurope Pub Date : 2025-08-10 DOI: 10.1002/ceur.202500161
Cristian L. Gutiérrez-Peña, Macarena Poyatos, Eduardo Peris
{"title":"Lone Pair–π Interactions Modulated by Coordination Geometry in NDI-di-NHC Metal Chloride Complexes","authors":"Cristian L. Gutiérrez-Peña,&nbsp;Macarena Poyatos,&nbsp;Eduardo Peris","doi":"10.1002/ceur.202500161","DOIUrl":"https://doi.org/10.1002/ceur.202500161","url":null,"abstract":"<p>Two dimetallic complexes of Au(I) and Ru(II), featuring a naphthalene-diimide (NDI)-linked bis-N-heterocyclic carbene (NHC) ligand, have been synthesized and fully characterized. Spectroscopic analyses, combined with structural data, reveal the presence of lone pair–<i>π</i> (lp–<i>π</i>) interactions between the chloride ligands coordinated to the metal centers and the central NDI unit. The nature of this interaction varies with the metal's coordination geometry: in the di-Au(I) complex, the lp–<i>π</i> interaction is intermolecular, whereas in the di-Ru(II) complex it is intramolecular, leading to the formation of two atropisomers that are distinguishable by conventional spectroscopic techniques. NMR studies of both complexes provided key insights into the lp–<i>π</i> interaction. For the di-Ru(II) complex in particular, these studies enabled the determination of the kinetic and thermodynamic parameters governing the equilibrium between the atropisomers, revealing a barrier to interconversion (Δ<i>H</i>≠) of 10.4 kcal mol<sup>–</sup><sup>1</sup>, indicative of a strong covalent character in the lp–<i>π</i> interaction.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500161","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129014","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Lone Pair–π Interactions Modulated by Coordination Geometry in NDI-di-NHC Metal Chloride Complexes NDI-di-NHC金属氯化物配合物配位几何调制的孤对-π相互作用
ChemistryEurope Pub Date : 2025-08-10 DOI: 10.1002/ceur.202500161
Cristian L. Gutiérrez-Peña, Macarena Poyatos, Eduardo Peris
{"title":"Lone Pair–π Interactions Modulated by Coordination Geometry in NDI-di-NHC Metal Chloride Complexes","authors":"Cristian L. Gutiérrez-Peña,&nbsp;Macarena Poyatos,&nbsp;Eduardo Peris","doi":"10.1002/ceur.202500161","DOIUrl":"https://doi.org/10.1002/ceur.202500161","url":null,"abstract":"<p>Two dimetallic complexes of Au(I) and Ru(II), featuring a naphthalene-diimide (NDI)-linked bis-N-heterocyclic carbene (NHC) ligand, have been synthesized and fully characterized. Spectroscopic analyses, combined with structural data, reveal the presence of lone pair–<i>π</i> (lp–<i>π</i>) interactions between the chloride ligands coordinated to the metal centers and the central NDI unit. The nature of this interaction varies with the metal's coordination geometry: in the di-Au(I) complex, the lp–<i>π</i> interaction is intermolecular, whereas in the di-Ru(II) complex it is intramolecular, leading to the formation of two atropisomers that are distinguishable by conventional spectroscopic techniques. NMR studies of both complexes provided key insights into the lp–<i>π</i> interaction. For the di-Ru(II) complex in particular, these studies enabled the determination of the kinetic and thermodynamic parameters governing the equilibrium between the atropisomers, revealing a barrier to interconversion (Δ<i>H</i>≠) of 10.4 kcal mol<sup>–</sup><sup>1</sup>, indicative of a strong covalent character in the lp–<i>π</i> interaction.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"3 5","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202500161","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145129013","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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