Reaction of [HRu3(CO)11]– (1) with [Ir(COD)Cl]2 in CH2Cl2 under H2 atmosphere afforded the dihydride [H2Ru3Ir(CO)12]– (2), which was quantitatively protonated to H3Ru3Ir(CO)12 (3) by strong acids such as HBF4·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 reaction of 1 with [Ir(CO)4]– in refluxing THF. The hydride carbonyl clusters 2-4 were fully characterized by IR and 1H NMR spectroscopy, and the molecular structures of 2 and 3 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 solvent and hydrogen source. The results obtained with these heterometallic Ru-Ir clusters were compared to 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 N2 and H2 atmosphere, as well as H2 pressure.

Heterometallic Ru-Ir carbonyl clusters as catalyst precursors for hydrogenation and hydrogen transfer reactions / Forti F.; Cesari C.; Bortoluzzi M.; Femoni C.; Iapalucci M.C.; Zacchini S.. - In: NEW JOURNAL OF CHEMISTRY. - ISSN 1369-9261. - ELETTRONICO. - 47:(2023), pp. 19289-19303. [10.1039/d3nj03478j]

Heterometallic Ru-Ir carbonyl clusters as catalyst precursors for hydrogenation and hydrogen transfer reactions

Forti F.;Cesari C.
;
Femoni C.;Iapalucci M. C.;Zacchini S.
2023

Abstract

Reaction of [HRu3(CO)11]– (1) with [Ir(COD)Cl]2 in CH2Cl2 under H2 atmosphere afforded the dihydride [H2Ru3Ir(CO)12]– (2), which was quantitatively protonated to H3Ru3Ir(CO)12 (3) by strong acids such as HBF4·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 reaction of 1 with [Ir(CO)4]– in refluxing THF. The hydride carbonyl clusters 2-4 were fully characterized by IR and 1H NMR spectroscopy, and the molecular structures of 2 and 3 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 solvent and hydrogen source. The results obtained with these heterometallic Ru-Ir clusters were compared to 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 N2 and H2 atmosphere, as well as H2 pressure.
2023
Heterometallic Ru-Ir carbonyl clusters as catalyst precursors for hydrogenation and hydrogen transfer reactions / Forti F.; Cesari C.; Bortoluzzi M.; Femoni C.; Iapalucci M.C.; Zacchini S.. - In: NEW JOURNAL OF CHEMISTRY. - ISSN 1369-9261. - ELETTRONICO. - 47:(2023), pp. 19289-19303. [10.1039/d3nj03478j]
Forti F.; Cesari C.; Bortoluzzi M.; Femoni C.; Iapalucci M.C.; Zacchini S.
File in questo prodotto:
File Dimensione Formato  
NJC_2023_RuIr_CAT.pdf

accesso aperto

Tipo: Versione (PDF) editoriale
Licenza: Licenza per Accesso Aperto. Creative Commons Attribuzione - Non commerciale (CCBYNC)
Dimensione 1.46 MB
Formato Adobe PDF
1.46 MB Adobe PDF Visualizza/Apri
Supporting_info.pdf

accesso aperto

Tipo: File Supplementare
Licenza: Licenza per Accesso Aperto. Creative Commons Attribuzione - Non commerciale (CCBYNC)
Dimensione 5.63 MB
Formato Adobe PDF
5.63 MB Adobe PDF Visualizza/Apri

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11585/951025
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 0
  • ???jsp.display-item.citation.isi??? 0
social impact