David Rezazgui, Jiří Schulz, Frank Uhlig, Petr Štěpnička
{"title":"A Simple Micellar Gold Catalyst Supported by a Hydrophilic Phosphinoferrocene Amidosulfonate Ligand","authors":"David Rezazgui, Jiří Schulz, Frank Uhlig, Petr Štěpnička","doi":"10.1002/ejic.202500338","DOIUrl":"https://doi.org/10.1002/ejic.202500338","url":null,"abstract":"<p>The design of micellar catalysts is instrumental in transferring metal-catalyzed organic reactions into aqueous reaction media and enabling catalyst reuse. Herein, it is reported that phosphinoferrocene amidosulfonate Ph<sub>2</sub>PfcC(O)NHCH<sub>2</sub>SO<sub>3</sub>(HNEt<sub>3</sub>) (<b>1</b>, fc = ferrocene-1,1′-diyl) and its chlorogold(I) complex [AuCl(<b>1</b>-κ<i>P</i>)] (<b>8</b>) form stable micelles in water. The latter compound is found to be an efficient, self-activating catalyst for the gold-catalyzed cyclization of <i>N</i>-propargyl benzamide into 4,5-dihydro-5-methylene-2-phenyloxazole in a water-ethyl acetate mixture. Structure determination of <b>8</b>·½CH<sub>2</sub>Cl<sub>2</sub> reveals extensive hydrogen bonding between the polar amidosulfonate pendants, in line with the compound's surfactant-like behavior. Density functional theory calculations of the plausible LAu<sup>+</sup> type catalyst suggest a possible in situ self-activation of complex <b>8</b> in water via chloride loss, possibly facilitated by the amidosulfonate group and the formation of Au(I)-aqua species.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 25","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500338","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145058046","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Meng Yang, Ralph Otmar Kusche, Sebastian Anhäuser, Jakob Möbs, Gregor Witte, Johanna Heine
{"title":"A Family of Luminescent Halido Cadmates with Bifunctional Diammonium Cations","authors":"Meng Yang, Ralph Otmar Kusche, Sebastian Anhäuser, Jakob Möbs, Gregor Witte, Johanna Heine","doi":"10.1002/ejic.202500264","DOIUrl":"https://doi.org/10.1002/ejic.202500264","url":null,"abstract":"<p>This study presents the synthesis, single crystal structures, and optical properties of a series of six halido cadmates featuring the diammonium cations 4-(ammoniomethyl)pyridinium (H<sub>2</sub>AMP<sup>2+</sup>) and 4-(ammonioethyl)pyridinium (H<sub>2</sub>AEP<sup>2+</sup>). The chlorido cadmates (H<sub>2</sub>AMP)<sub>2</sub>Cd<sub>3</sub>Cl<sub>10</sub>·4H<sub>2</sub>O (<b>1</b>) and (H<sub>2</sub>AEP)<sub>4</sub>Cd<sub>5</sub>Cl<sub>18</sub> (<b>2</b>) feature complex polymeric anion motifs, while the bromido and iodio cadmates (H<sub>2</sub>AMP)CdBr<sub>4</sub>·H<sub>2</sub>O (<b>3</b>), (H<sub>2</sub>AEP)CdBr<sub>4</sub> (<b>4</b>), (H<sub>2</sub>AMP)CdI<sub>4</sub> (<b>5</b>), and (H<sub>2</sub>AEP)CdI<sub>4</sub> · H<sub>2</sub>O (<b>6</b>) are composed of mononuclear {CdX<sub>4</sub>} units (X = halogen) packed in different arrangements. (H<sub>2</sub>AEP)<sub>4</sub>Cd<sub>5</sub>Cl<sub>18</sub> (<b>2</b>) displays a phase transition between 100 K and room temperature, which is studied in detail. All compounds show decomposition temperatures above 180 °C. Optical bandgaps of the compounds are estimated in the range from 3.4 to 4.4 eV, with all compounds showing significant sub-bandgap absorption. Compounds <b>1</b>–<b>6</b> also show broad low-temperature emission centred between 1.95 and 2.5 eV.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 23","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-07-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500264","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144905303","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Olga Impert, Alessandro Niorettini, Titas Kumar Mukhopadhyay, Debabrata Chatterjee
{"title":"RuIII(edta) Complex-Mediated Oxidation of Hydrazine to Nitrogen: Spectral, Electrochemical, and Kinetic Studies","authors":"Olga Impert, Alessandro Niorettini, Titas Kumar Mukhopadhyay, Debabrata Chatterjee","doi":"10.1002/ejic.202500269","DOIUrl":"https://doi.org/10.1002/ejic.202500269","url":null,"abstract":"<p>The [Ru<sup>III</sup>(edta)pz]<sup>−</sup> complex (edta<sup>4−</sup> = ethylenediaminetetraacetate; pz = pyrazine), despite being a substantially weak electron-accepting oxidant (E<sub>1/2</sub> = 0.24 V vs Normal Hydrogen Electrode for Ru<sup>III/II</sup> couple), can effect the oxidation of hydrazinium ion (NH<sub>2</sub>NH<sub>3</sub><sup>+</sup>) to nitrogen (N<sub>2</sub>) selectively with concomitant formation of the [Ru<sup>II</sup>(edta)pz]<sup>2−</sup> product complex. The time course of the reaction is followed spectrophotometrically at the characteristic band of [Ru<sup>II</sup>(edta)(pz)]<sup>2−</sup> (λ<sub>max</sub> = 462 nm) as a function of [NH<sub>2</sub>NH<sub>3</sub><sup>+</sup>]<sub><i>T</i></sub>, pH, and temperature. A mechanism involving hydrogen atom transfer from NH<sub>2</sub>NH<sub>3</sub><sup>+</sup> to the remote N-atom of the coordinated pyrazine in the [Ru<sup>III</sup>(edta)pz]<sup>−</sup> complex is proposed for the aforesaid oxidation reaction. Electrochemical and spectroelectrochemical studies reveal that Ru<sup>III</sup>(edta)pz]<sup>−</sup> can act as a “redox relay” for the electrochemical oxidation of NH<sub>2</sub>NH<sub>3</sub><sup>+</sup> to N<sub>2</sub> at 0.5 V (vs saturated calomel reference electrode) under argon atmosphere. Density functional theory (DFT) calculations are utilized to optimize the structures of the reactant and product complexes. Detailed mechanistic proposals in agreement with the spectral, electrochemical, kinetic, and DFT computation data are presented for the aforesaid oxidation reaction.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 24","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144914872","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Wiebke G. Rehfuß, Andreas Kalytta-Mewes, Maryana Kraft, Dirk Volkmer
{"title":"Electronic and Photophysical Properties of a Heterometallic Ru(II)–Cu(I) Kuratowski Complex: Insights from Spectroscopy and Density Functional Theory Calculations","authors":"Wiebke G. Rehfuß, Andreas Kalytta-Mewes, Maryana Kraft, Dirk Volkmer","doi":"10.1002/ejic.202500190","DOIUrl":"https://doi.org/10.1002/ejic.202500190","url":null,"abstract":"<p>Polynuclear metal complexes offer tunable electronic properties that are valuable for photocatalysis and molecular electronics. Herein, the synthesis and characterization of a poly-heteronuclear Kuratowski complex, [Ru<sup>II</sup>Cu<sup>I</sup><sub>4</sub>(Me<sub>2</sub>bta)<sub>6</sub>(PPh<sub>3</sub>)<sub>4</sub>] is presented. This complex is designed to investigate the electronic coupling between strongly reducing Cu(I) centers and a Ru(II) ion, mediated by a highly symmetric framework of triazolate ligands. Electrochemical studies reveal coupled redox behavior between Ru(II) and Cu(I), while UV–vis spectroscopy shows an overlapping Ru- and Cu-centered metal-to-ligand charge transfer (MLCT) band, redshifted in comparison to its {Ru<sup>II</sup>Zn<sup>II</sup><sub>4</sub>} analog. Despite this, fluorescence lifetime measurements indicate that ultrafast nonradiative relaxation limits electron transfer between the metal centers. Density functional theory (DFT) and time-dependent-DFT calculations confirm that ligand-field effects, rather than direct Ru–Cu interactions, drive the MLCT redshift. These observations offer tentative insights into excited-state dynamics and highlight design aspects for controlling electronic communication in polynuclear systems.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 22","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500190","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144881474","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Three Single-Ion Magnet Candidates from Erbium(III) Squarate Complexes in Relation with a Square-Antiprismatic Coordination Structure","authors":"Rina Takano, Yasutaka Kitagawa, Takayuki Ishida","doi":"10.1002/ejic.202500184","DOIUrl":"https://doi.org/10.1002/ejic.202500184","url":null,"abstract":"<p>Mononuclear [Er(sq)(Hsq)(H<sub>2</sub>O)<sub>6</sub>]•(H<sub>2</sub>O) (sq = squarate, C<sub>4</sub>O<sub>4</sub><sup>2−</sup>) and heteroleptically bridged 3D polymer [Er<sub>2</sub>(sq)<sub>2</sub>(ox)(H<sub>2</sub>O)<sub>4</sub>]<sub><i>n</i></sub> (ox = oxalate, C<sub>2</sub>O<sub>4</sub><sup>2−</sup>) were newly prepared. The Arrhenius plot for the alternating-current magnetic susceptibility data clarified the effective energy barriers for magnetization reversal, <i>U</i><sub>eff</sub>/<i>k</i><sub>B</sub> = 42.0(7) K at a direct-current bias field of 1000 Oe for the former and 21.7(8) K at 800 Oe for the latter. They are greater than that of known 2D [Er<sub>2</sub>(sq)<sub>3</sub>(H<sub>2</sub>O)<sub>8</sub>]<sub><i>n</i></sub>. All of the erbium(III) coordination structures investigated here can be described approximately as a square antiprism with a slight variation in axial compression within a <i>D</i><sub>4d</sub> symmetry framework. To elucidate a suitable degree of <i>D</i><sub>4d</sub> compression, the complete-active-space self-consistent-field calculation was carried out on the discrete neutral molecule [Er(sq)(Hsq)(H<sub>2</sub>O)<sub>6</sub>] and its modifications after anisotropically upto 10% elongation or compression along the principal axis. The calculated energy gap between the ground and the first excited states in the Stark sublevels is 151.5 cm<sup>−1</sup> for the original [Er(sq)(Hsq)(H<sub>2</sub>O)<sub>6</sub>] molecule, and the gap became wider with more compressed as well as elongated ErO<sub>8</sub> structures. The gap is highly sensitive to the compressed/elongated modification, justifying the variety and diversity of the single-ion magnet characteristics observed.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 23","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144905525","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"α,β-Alkylation Reactions Catalyzed by Ruthenium Triphenylphosphine Complexes Bearing Substituted Pyridine–Quinoline Based Ligands","authors":"Nikolaos Zacharopoulos, Panagiotis-Georgios Kanellopoulos, Evangelos Bakeas, Antigoni Cheilari, Gregor Schnakenburg, Athanassios Chrissanthopoulos, Athanassios Philippopoulos","doi":"10.1002/ejic.202500154","DOIUrl":"https://doi.org/10.1002/ejic.202500154","url":null,"abstract":"<p>Herein, a series of ruthenium(II) bis-triphenylphosphine complexes comprising substituted pyridine<b>–</b>quinoline based ligands for the efficient α-alkylation of ketones with primary alcohols, via the borrowing hydrogen methodology, are reported. β-alkylation of secondary alcohols by primary alcohols is also reported. The reactions are catalyzed by the ruthenium complexes [RuCl<sub>2</sub>(8-Mepq)(PPh<sub>3</sub>)] (<b>1</b>), [RuCl<sub>2</sub>(6′-Mepq)(PPh<sub>3</sub>)<sub>2</sub>] (<b>2</b>), [RuCl<sub>2</sub>(4,6′-Me<sub>2</sub>pq)(PPh<sub>3</sub>)<sub>2</sub>)] (<b>3</b>), including [RuCl<sub>2</sub>(4-Mepq)(PPh<sub>3</sub>)<sub>2</sub>] (<b>4</b>), and [RuCl<sub>2</sub>(pq)(PPh<sub>3</sub>)<sub>2</sub>] (<b>5</b>). Mass spectrometry, elemental analysis, and <sup>31</sup>P NMR data reveal that <b>1</b> is a five-coordinate 16-electron ruthenium(II) complex with one triphenylphosphine ligand, as opposed to <b>2</b>–<b>5</b>, which hold two and are six-coordinate. Theoretical calculations suggest that <b>1</b> is stabilized by a nonclassical Ru<span></span>Cl(1)···H(2) interaction between a hydrogen atom of the appended methyl group and an adjacent chlorine atom. By NMR spectroscopy, different isomers of <b>2</b> and <b>3</b> have been detected. For the α-alkylation of benzyl alcohol with acetophenone, all complexes selectively provided 1,3-diphenylpropan-1-one as the sole product, within an hour. The β-alkylation of 1-phenylethanol with benzyl alcohol under the same conditions is less selective. As salient features of this report we could mention that these catalytic systems operate with easily accessible and in high yields air-stable catalysts, within a shorter period compared to known ruthenium complexes.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 22","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500154","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144881148","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Maximilian J. Klingsiek, Loris M. Mendrina, Jan-Hendrik Lamm, Beate Neumann, Norbert W. Mitzel
{"title":"Calyx- and Tub-Shaped Polydentate σ-Hole Systems Revealing Intermolecular Chalcogene···π–Alkyne Interactions","authors":"Maximilian J. Klingsiek, Loris M. Mendrina, Jan-Hendrik Lamm, Beate Neumann, Norbert W. Mitzel","doi":"10.1002/ejic.202500274","DOIUrl":"https://doi.org/10.1002/ejic.202500274","url":null,"abstract":"<p>Poly σ-hole donors, i.e., molecules that contain more than one σ-hole donating function, can interact through weak noncovalent interactions with molecules that have regions of high electron density, like the lone pairs of anions, Lewis bases, and π-systems. Therefore, such mono- and bidentate systems have been intensively studied in recent years and used in host-guest chemistry and catalysis. Here we present the synthesis of tri-, tetra-, and hexadentate systems with CCSb(C<sub>2</sub>F<sub>5</sub>)<sub>2</sub> and CCSeCF<sub>3</sub> functions using tin-element exchange reactions. These systems are based on both the calyx-shaped hexadehydrotribenzo[12]annulene and the tub-shaped dibenzo[<i>a</i>,<i>e</i>]cyclooctatetraene. The molecular structure of the tub-shaped systems shows inter- and intramolecular contacts related to the interaction of the σ-holes with the electron-rich fluorine and alkyne functions.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 24","pages":""},"PeriodicalIF":2.0,"publicationDate":"2025-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500274","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144914945","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Correction to “Ultrafast Structural Dynamics of a Photoexcited Mn−Fe Charge-Transfer Material in the Polaronic and Phase Transition Regimes”","authors":"","doi":"10.1002/ejic.202500152","DOIUrl":"https://doi.org/10.1002/ejic.202500152","url":null,"abstract":"<p>M. Hervé, G. Privault, E. Trzop, S. Akagi, Y. Watier, S. Zerdane, I. Chaban, R. G. Torres Ramírez, C. Mariette, A. Volte, M. Cammarata, M. Levantino, H. Tokoro, S.-i. Ohkoshi, E. Collet, <i>Eur. J. Inorg. Chem.</i> <b>2024</b>, <i>27</i>, e202400371.</p><p>We apologize for this error.</p>","PeriodicalId":38,"journal":{"name":"European Journal of Inorganic Chemistry","volume":"28 20","pages":""},"PeriodicalIF":2.2,"publicationDate":"2025-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ejic.202500152","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144647775","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}