Hydrogen Activation with Ru-PN3P Pincer Complexes for the Conversion of C1 Feedstocks.
Inorg Chem
; 63(7): 3393-3401, 2024 Feb 19.
Article
en En
| MEDLINE
| ID: mdl-38330919
ABSTRACT
The hydrogenation of C1 feedstocks (CO and CO2) has been investigated using ruthenium complexes [RuHCl(CO)(PN3P)] as the catalyst. PN3P pincer ligands containing amines in the linker between the central pyridine donor and the phosphorus donors with bulky substituents (tert-butyl (1) or TMPhos (2)) are required to obtain mononuclear single-site catalysts that can be activated by the addition of KOtBu to generate stable five-coordinate complexes [RuH(CO)(PN3P-H)], whereby the pincer ligand has been deprotonated. Activation of hydrogen takes place via heterolytic cleavage to generate [RuH2(CO)(PN3P)], but in the presence of CO, coordination of CO occurs preferentially to give [RuH(CO)2(PN3P-H)]. This complex can be protonated to give the cationic complex [RuH(CO)2(PN3P)]+, but it is unable to activate H2 heterolytically. In the case of the less coordinating CO2, both ruthenium complexes 1 and 2 are highly efficient as CO2 hydrogenation catalysts in the presence of a base (DBU), which in the case of the TMPhos ligand results in a TON of 30,000 for the formation of formate.
Texto completo:
1
Colección:
01-internacional
Banco de datos:
MEDLINE
Idioma:
En
Revista:
Inorg Chem
Año:
2024
Tipo del documento:
Article
País de afiliación:
Reino Unido