Inorganic ChemistryPub Date : 2025-07-21Epub Date: 2025-07-02DOI: 10.1021/acs.inorgchem.5c01520
Gernot T L Zug, Cäcilia Maichle-Mössmer, Reiner Anwander
{"title":"Scandium─Group 13 Heterobimetallic Methylidene Clusters.","authors":"Gernot T L Zug, Cäcilia Maichle-Mössmer, Reiner Anwander","doi":"10.1021/acs.inorgchem.5c01520","DOIUrl":"10.1021/acs.inorgchem.5c01520","url":null,"abstract":"<p><p>A straightforward synthesis of Cp*<sub>2</sub>Sc(AlMe<sub>4</sub>) (Cp* = C<sub>5</sub>Me<sub>5</sub>) applying Cp*<sub>2</sub>ScCl(thf) and LiAlMe<sub>4</sub>/AlMe<sub>3</sub> is described. Donor-assisted trimethyltriel exchange gives access to Cp*<sub>2</sub>Sc(EMe<sub>4</sub>) (E = Ga, In), which represent the first scandium tetramethylgallate and tetramethylindate complexes. Thermal treatment of Cp*<sub>2</sub>Sc(EMe<sub>4</sub>) (E = Ga, In) in benzene leads to the isolation of methylidene clusters Cp*<sub>6</sub>Sc<sub>4</sub>E<sub>8</sub>(CH<sub>2</sub>)<sub>12</sub>Me<sub>6</sub> (E = Ga, In). This methyl group deprotonation differs from the benzene activation previously observed for Cp*<sub>2</sub>Y(EMe<sub>4</sub>) (E = Al, Ga). Treatment of Cp*<sub>2</sub>Sc(EMe<sub>4</sub>) (E = Al, Ga) with excess GaMe<sub>3</sub> in benzene at elevated temperatures generated Ga<sub>8</sub>(CH<sub>2</sub>)<sub>12</sub>, following the known reactivities of Cp*<sub>2</sub>Ln(GaMe<sub>4</sub>) (Ln = Y, Lu) with GaMe<sub>3</sub>. Analogous reactions of scandocene complexes Cp*<sub>2</sub>Sc(EMe<sub>4</sub>) (E = Al, In) with excess InMe<sub>3</sub> at elevated temperatures did not yield the putative homoleptic indium methylidene. Instead, the methylidene cluster Cp*<sub>4</sub>Sc<sub>4</sub>In<sub>8</sub>(CH<sub>2</sub>)<sub>12</sub>Me<sub>8</sub> was isolated, which features half-sandwich scandium fragments exclusively. A reaction of InMe<sub>3</sub> and HCp* at high temperatures yielded Me<sub>2</sub>InCp*InMe<sub>3</sub>, which might incorporate the missing Cp* ligands in the cluster formations. Rare-earth-metal compounds were analyzed by SC-XRD, ICP-OES and elemental analysis. Compounds Cp*<sub>2</sub>Sc(EMe<sub>4</sub>) (E = Ga, In) and [Cp*<sub>2</sub>Sc(ClAlMe<sub>3</sub>)]<sub>2</sub> were additionally analyzed by <sup>1</sup>H, <sup>13</sup>C{<sup>1</sup>H}, <sup>45</sup>Sc NMR as well as <sup>1</sup>H and <sup>45</sup>Sc variable temperature NMR studies.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":"14031-14040"},"PeriodicalIF":4.3,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12284852/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144551437","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Graham King*, Aydar Rakhmatullin and František Šimko,
{"title":"","authors":"Graham King*, Aydar Rakhmatullin and František Šimko, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"64 28","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":4.3,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.inorgchem.5c02352","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144665288","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Teagan F. M. Sweet, Zoë C. Emory, Brodie S. Barth, Jennifer Neu, Rodney D. Hunt, Ashley E. Shields, Andrew Miskowiec, Thomas E. Proffen, Peter C. Burns and Tyler L. Spano*,
{"title":"","authors":"Teagan F. M. Sweet, Zoë C. Emory, Brodie S. Barth, Jennifer Neu, Rodney D. Hunt, Ashley E. Shields, Andrew Miskowiec, Thomas E. Proffen, Peter C. Burns and Tyler L. Spano*, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"64 28","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":4.3,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.inorgchem.5c00709","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144665300","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Inorganic ChemistryPub Date : 2025-07-21Epub Date: 2025-07-03DOI: 10.1021/acs.inorgchem.5c01656
Werner Oberhauser, Lorenzo Poggini, Laura Capozzoli, Maria V Pagliaro, Serena Coiai, Claudio Evangelisti
{"title":"Pyruvic Acid Hydrogenation in Water by Diamine-Capped Ruthenium Nanoparticles.","authors":"Werner Oberhauser, Lorenzo Poggini, Laura Capozzoli, Maria V Pagliaro, Serena Coiai, Claudio Evangelisti","doi":"10.1021/acs.inorgchem.5c01656","DOIUrl":"10.1021/acs.inorgchem.5c01656","url":null,"abstract":"<p><p>Small-sized (<i>d</i><sub>m</sub> = 2.07 nm) diamine (<b>L</b>)-stabilized ruthenium nanoparticles (NPs) were successfully synthesized upon the reaction of Ru(acetylacetonate)<sub>3</sub> with hydrogen in the presence of <b>L</b> and dichloromethane. The obtained <b>L</b>-capped ruthenium nanoparticles (<b>Ru</b><sup><b>L</b></sup>) were used as-synthesized and after deposition on the surface of carbon (C<sup>K</sup>), featured by a high surface area (<b>Ru</b><sup><b>L</b></sup><b>@C</b><sup><b>K</b></sup>, Ru content of 0.44 wt %) to selectively catalyze the hydrogenation of pyruvic acid in water at reaction temperatures up to 80 °C. The high efficiency of the latter catalyst emerged from parallel catalytic reactions conducted with the reference catalyst <b>Ru@C</b><sup><b>K</b></sup>, which was obtained by applying the same synthesis protocol in the absence of <b>L</b>. The role of <b>L</b> in the catalytic pyruvic acid hydrogenation reactions emerged from catalytic reactions combined with high-resolution transmission electron microscopic, X-ray photoelectron spectroscopic, and electrochemical studies.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":"14382-14394"},"PeriodicalIF":4.3,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144558416","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Inorganic ChemistryPub Date : 2025-07-21Epub Date: 2025-07-04DOI: 10.1021/acs.inorgchem.5c02234
Gao-Peng Li, Jia-Ling Wen, Liu Yang, Yun-Long Fu, Kun Zhang, Xue Mao, Yao-Yu Wang
{"title":"Modulating Local Electron Density in NDI-Based CPs to Accelerate Photoinduced Electron Transfer for Ultrafast Violet Light Detection.","authors":"Gao-Peng Li, Jia-Ling Wen, Liu Yang, Yun-Long Fu, Kun Zhang, Xue Mao, Yao-Yu Wang","doi":"10.1021/acs.inorgchem.5c02234","DOIUrl":"10.1021/acs.inorgchem.5c02234","url":null,"abstract":"<p><p>Realizing rapid photoinduced electron transfer (PET) in donor-acceptor (D-A) systems is crucial. The relative energy levels of donors and acceptors, as well as the local electron density, are two important factors determining the rate of photoinduced electron transfer in donor-acceptor (D-A) systems. However, systematic studies on the structure-functional relationship regarding the local electron density factor, based on precise structural models are rarely reported. Herein, we report a strategy for fabricating donor-acceptor coordination polymers (D-A CPs) that facilitates PET and enables evaluation of reaction kinetics through local electron density modulation, using two NDI-based CPs, [Cd<sub>2</sub>(dtNDI)(HBTC)(DMF)<sub>4</sub>] (<b>1</b>) and [Cd<sub>2</sub>(dtNDI)(H<sub>2</sub>BTEC)(DMF)<sub>4</sub>] (<b>2</b>), as proof-of-concept systems. By tuning carboxylate coordination-site electron density, compound <b>2</b> achieves a 10-fold PET rate increase (0.11953 → 1.15777 s<sup>-1</sup>) compared with <b>1</b> and demonstrates rapid photochromism (4 s coloration). The extra carboxylates in H<sub>2</sub>BTEC<sup>2-</sup> lower the electron density at the coordination site, suppressing charge transfer (CT) while enhancing PET, which establishes that local electron density governs PET efficiency. Compound <b>2</b> also shows exceptional 400 nm violet-light sensitivity, making it ideal for violet-light detection and filtering applications. This work provides a precise structural model for mechanistic insights into PET control.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":"14613-14618"},"PeriodicalIF":4.3,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144564160","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Inorganic ChemistryPub Date : 2025-07-21Epub Date: 2025-07-03DOI: 10.1021/acs.inorgchem.5c02948
Luis Garay, Jose L Gonzalez Jimenez, James C Fettinger, S Olivia Gunther, Jacob A Branson, Stefan G Minasian, Weiwei Xie, Susan M Kauzlarich
{"title":"Correction to \"Interplay of Crystal Structure and Magnetic Properties of the Eu<sub>5.08-<i>x</i></sub>Sr<sub><i>x</i></sub>Al<sub>3</sub>Sb<sub>6</sub> Solid Solution\".","authors":"Luis Garay, Jose L Gonzalez Jimenez, James C Fettinger, S Olivia Gunther, Jacob A Branson, Stefan G Minasian, Weiwei Xie, Susan M Kauzlarich","doi":"10.1021/acs.inorgchem.5c02948","DOIUrl":"10.1021/acs.inorgchem.5c02948","url":null,"abstract":"","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":" ","pages":"14740"},"PeriodicalIF":4.3,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144558411","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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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