Thermal Growth of Au–Fe Heterometallic Carbonyl Clusters Containing N-Heterocyclic Carbene and Phosphine Ligands
| Autor: | Maria Carmela Iapalucci, Beatrice Berti, Cristiana Cesari, Cristina Femoni, Marco Bortoluzzi, Federico Vacca, Rita Mazzoni, Stefano Zacchini |
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| Přispěvatelé: | Berti B., Bortoluzzi M., Cesari C., Femoni C., Iapalucci M.C., Mazzoni R., Vacca F., Zacchini S. |
| Rok vydání: | 2020 |
| Předmět: |
Settore CHIM/03 - Chimica Generale e Inorganica
Thermal growth 010405 organic chemistry Chemistry Iron Metal cluster 010402 general chemistry 01 natural sciences Medicinal chemistry Article 0104 chemical sciences NHC carbene Inorganic Chemistry IMes chemistry.chemical_compound Carbonyl Gold Physical and Theoretical Chemistry Carbene Phosphine |
| Zdroj: | Inorganic Chemistry |
| ISSN: | 1520-510X 0020-1669 |
| Popis: | The thermal reactions of [NEt4][Fe(CO)4(AuNHC)] [NHC = IMes ([NEt4][1]) or IPr ([NEt4][2]); IMes = C3N2H2(C6H2Me3)2; IPr = C3N2H2(C6H3iPr2)2], Fe(CO)4(AuNHC)2 [NHC = IMes (3) or IPr (4)], Fe(CO)4(AuIMes)(AuIPr) (5), and Fe(CO)4(AuNHC)(AuPPh3) [NHC = IMes (6) or IPr (7)] were investigated in different solvents [CH2Cl2, CH3CN, dimethylformamide, and dimethyl sulfoxide (dmso)] and at different temperatures (50–160 °C) in an attempt to obtain higher-nuclearity clusters. 1 and 2 completely decomposed in refluxing CH2Cl2, resulting in [Fe2(CO)8(AuNHC)]− [NHC = IMes (10) or IPr (11)]. Traces of [Fe3(CO)10(CCH3)]− (12) were obtained as a side product. Conversely, 6 decomposed in refluxing CH3CN, affording the new cluster [Au3{Fe(CO)4}2(PPh3)2]− (15). The relative stability of the two isomers found in the solid state structure of 15 was computationally investigated. 4 was very stable, and only after prolonged heating above 150 °C in dmso was limited decomposition observed, affording small amounts of [Fe3S(CO)9]2– (9), [HFe(CO)4]− (16), and [Au16S{Fe(CO)4}4(IPr)4]n+ (17). A dicationic nature for 17 was proposed on the basis of density functional theory calculations. All of the other reactions examined led to species that were previously reported. The molecular structures of the new clusters 11, 12, 15, and 17 were determined by single-crystal X-ray diffraction as their [NEt4][11]·1.5toluene, [Au(IMes)2][15]·0.67CH2Cl2, [NEt4][12], and [17][BF4]n·solvent salts, respectively. The nuclearity of Au−Fe molecular clusters has been increased by thermal methods, resulting in heterometallic species stabilized by CO, NHC, and phosphine ligands. |
| Databáze: | OpenAIRE |
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