期刊
NEW JOURNAL OF CHEMISTRY
卷 47, 期 41, 页码 19289-19303出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/d3nj03478j
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This study investigates the application of hydride carbonyl clusters in catalytic reactions. Through experimental and computational studies, it is found that heterometallic clusters exhibit significant differences in their interactions with substrates compared to homometallic clusters. This has important implications for understanding and designing catalysts.
Reaction of [HRu3(CO)(11)](-) (1) with [Ir(COD)Cl](2) in CH2Cl2 under a H-2 atmosphere afforded dihydride [H2Ru3Ir(CO)(12)](-) (2), which was quantitatively protonated to H3Ru3Ir(CO)(12) (3) by strong acids such as HBF4 center dot Et2O. The related mono-hydride [HRu3Ir(CO)(12)](2-) (4) was obtained by deprotonation of 2 with a strong base such as KOtBu, or by the reaction of 1 with [Ir(CO)(4)](-) in refluxing THF. Hydride carbonyl clusters 2-4 were fully characterized by IR and H-1 NMR spectroscopies, and the molecular structures of 2 and 3 were determined by single-crystal X-ray diffraction (SC-XRD). The location of the hydride ligands within the tetrahedral cages of these clusters was further corroborated by computational studies employing DFT methods. Clusters 2-4 were tested as catalyst precursors for transfer hydrogenation on the model substrate 4-fluoroacetophenone, using iPrOH as a solvent and a hydrogen source. The results obtained using these heterometallic Ru-Ir clusters were compared to those using homometallic 1, evidencing a significant difference, particularly regarding the effect of the base on catalysis. Heterometallic cluster 2 was also tested in the hydrogenation of trans-cinnamaldehyde in iPrOH at refluxing temperature both under N-2 and H-2 atmospheres, and H-2 pressure.
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