Academic Journal
Highly Reduced Ruthenium Carbide Carbonyl Clusters: Synthesis, Molecular Structure, Reactivity, Electrochemistry, and Computational Investigation of [Ru6C(CO)15]4-
| العنوان: | Highly Reduced Ruthenium Carbide Carbonyl Clusters: Synthesis, Molecular Structure, Reactivity, Electrochemistry, and Computational Investigation of [Ru6C(CO)15]4- |
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| المؤلفون: | Cesari C., Bortoluzzi M., Funaioli T., Femoni C., Iapalucci M. C., Zacchini S. |
| المساهمون: | Cesari C., Bortoluzzi M., Funaioli T., Femoni C., Iapalucci M.C., Zacchini S. |
| سنة النشر: | 2023 |
| المجموعة: | IRIS Università degli Studi di Bologna (CRIS - Current Research Information System) |
| مصطلحات موضوعية: | ruthenium, cluster, carbonyl ligand, carbide, electrochemistry |
| الوصف: | The reaction of [Ru6C(CO)16]2- (1) with NaOH in DMSO resulted in the formation of a highly reduced [Ru6C(CO)15]4- (2), which was readily protonated by acids, such as HBF4·Et2O, to [HRu6C(CO)15]3- (3). Oxidation of 2 with [Cp2Fe][PF6] or [C7H7][BF4] in CH3CN resulted in [Ru6C(CO)15(CH3CN)]2- (5), which was quantitatively converted into 1 after exposure to CO atmosphere. The reaction of 2 with a mild methylating agent such as CH3,I afforded the purported [Ru6C(CO)14(COCH3)]3- (6). By employing a stronger reagent, that is, CF3SO3CH3, a mixture of [HRu6C(CO)16]− (4), [H3Ru6C(CO)15]− (7), and [Ru6C(CO)15(CH3CNCH3)]− (8) was obtained. The molecular structures of 2-5, 7, and 8 were determined by single-crystal X-ray diffraction as their [NEt4]4[2]·CH3CN, [NEt4]3[3], [NEt4][4], [NEt4]2[5], [NEt4][7], and [NEt4][8]·solv salts. The carbyne-carbide cluster 6 was partially characterized by IR spectroscopy and ESI-MS, and its structure was computationally predicted using DFT methods. The redox behavior of 2 and 3 was investigated by electrochemical and IR spectroelectrochemical methods. Computational studies were performed in order to unravel structural and thermodynamic aspects of these octahedral Ru-carbide carbonyl clusters displaying miscellaneous ligands and charges in comparison with related iron derivatives. |
| نوع الوثيقة: | article in journal/newspaper |
| وصف الملف: | ELETTRONICO |
| اللغة: | English |
| Relation: | info:eu-repo/semantics/altIdentifier/pmid/37646082; info:eu-repo/semantics/altIdentifier/wos/WOS:001065020200001; volume:62; issue:36; firstpage:14590; lastpage:14603; numberofpages:14; journal:INORGANIC CHEMISTRY; https://hdl.handle.net/11585/945653; info:eu-repo/semantics/altIdentifier/scopus/2-s2.0-85170582608 |
| DOI: | 10.1021/acs.inorgchem.3c01711 |
| الاتاحة: | https://hdl.handle.net/11585/945653 https://doi.org/10.1021/acs.inorgchem.3c01711 https://pubs.acs.org/doi/10.1021/acs.inorgchem.3c01711 |
| Rights: | info:eu-repo/semantics/openAccess |
| رقم الانضمام: | edsbas.B8A572DB |
| قاعدة البيانات: | BASE |
| DOI: | 10.1021/acs.inorgchem.3c01711 |
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