Revisiting the Preparation and Catalytic Performance of a Phosphine-Modified Co(II) Hydroformylation Precatalyst.
J Am Chem Soc
; 146(28): 19183-19192, 2024 Jul 17.
Article
en En
| MEDLINE
| ID: mdl-38954757
ABSTRACT
In light of recent conflicting reports regarding the hydroformylation catalytic activity derived from cationic Co(II) precatalysts of the form [Co(acac)(bis(phosphine))]BF4, the synthetic procedures and characterization of [Co(acac)(dppBz)]BF4, 1, are evaluated. Leveraging calibrated ESI-TOF MS methodologies, substantial quantities of Co(acac)2(dppBz), 2, were observed within samples of 1. The source of the impurity, 2, is determined to derive from incomplete protonolysis of the Co(acac)2 precursor and ligand scrambling occurring during the synthesis of 1. Revised synthetic procedures using lower temperature conditions and longer reaction times afford analytically pure samples of 1 based on ESI-TOF MS and NMR spectroscopic analysis. Complex 1 is demonstrated to act as a hydroformylation precatalyst for the conversion of 1-hexene to 1-heptanal under relatively mild conditions at 51.7 bar and 140 °C. The presence of impurity 2 is shown to dramatically decrease the catalytic performance derived from 1.
Texto completo:
1
Bases de datos:
MEDLINE
Idioma:
En
Revista:
J Am Chem Soc
Año:
2024
Tipo del documento:
Article
País de afiliación:
Estados Unidos