{"title":"Diruthenium(IV,IV) Complexes with {Ru2(μ-O)2} Diamond Core Bridged by Acetato or Hydrogenphosphato Ligands.","authors":"Tomoyo Misawa-Suzuki,Ryuta Tanabe,Yuyuko Nagoshi,Nanako Asai,Yusuke Kataoka,Hirotaka Nagao","doi":"10.1021/acs.inorgchem.5c01982","DOIUrl":"https://doi.org/10.1021/acs.inorgchem.5c01982","url":null,"abstract":"The reaction centers of higher-valent metals with a doubly oxido-bridged core, referred to as the \"diamond core {M2(μ-O)2}\", have attracted significant attention primarily owing to their role in oxidation reactions. Acetato- or hydrogenphophato-bridged Ru(IV)-Ru(IV) complexes with the doubly oxido-bridged diamond core, {RuIV2(μ-O)2}, incorporating ethylbis(2-pyridylmethyl)amine (ebpma) [{RuIV(ebpma)}2(μ-O)2(μ-O2L)](ClO4)m (LO2x- = CH3CO2- (acetato); [1(IV,IV)](ClO4)3, HPO42- (hydrogenphosphato); [2(IV,IV)](ClO4)2), were synthesized as structural models for diiron-containing soluble methane monooxygenase (sMMO). Systematic comparison of crystal structures, electrochemical and spectroscopic properties with analogous complexes in the same tridentate ligand (ebpma) system (LO2x- = CO32-; [(CO3)(IV,IV)]2+, HCO3-; [(HCO3)(IV,IV)]3+, and SO42-; [(SO4)(IV,IV)]2+) led to obtain new and deeper insights into the electronic structures of the Ru(IV)-Ru(IV) dimers. The structure of the {RuIV2(μ-O)2} core is dominantly effected by the geometry of the bridging bidentate ligand, whereas the redox features were mainly effected by the electron-donating nature of the bridging bidentate ligands. Furthermore, correlation between the redox potentials and the λmax of the {Ru2(μ-O)2}-{Ru2(μ-O)2}* transition band was demonstrated. Notably, the redox reactions of [2(IV,IV)]2+ were pH-dependent in water and could be rationalized by considering dimerization of the dimer, in part, through the bridging phosphato ligand; a tetramer formation through dimerization of [2(IV,IV)]2+ in water was also proposed. Kinetic and thermochemical analyses of the stoichiometric benzyl alcohol oxidation reactions with [1(IV,IV)]3+ suggested the C-H activation process as a PTET process.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"12 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144678230","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}
Gernot T. L. Zug, Cäcilia Maichle-Mössmer and Reiner Anwander*,
{"title":"","authors":"Gernot T. L. Zug, Cäcilia Maichle-Mössmer and Reiner Anwander*, ","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.5c01520","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144665258","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}
Ghodrat Mahmoudi, Isabel Garcia-Santos*, Tamara Iglesias-Pereiro, Alfonso Castiñeiras, Julio Corredoira-Vázquez, Atash V. Gurbanov, Ennio Zangrando, Rosa M. Gomila, Antonio Frontera* and Damir A. Safin*,
{"title":"","authors":"Ghodrat Mahmoudi, Isabel Garcia-Santos*, Tamara Iglesias-Pereiro, Alfonso Castiñeiras, Julio Corredoira-Vázquez, Atash V. Gurbanov, Ennio Zangrando, Rosa M. Gomila, Antonio Frontera* and Damir A. Safin*, ","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.5c02419","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144665267","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}
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