Significant recent developments in homogeneous palladium catalysis for selective aerobic oxidation have emphasized the importance of developing a thorough comprehension of reactions of palladium complexes with O2. Density functional theory (DFT) calculations, employing the B3LYP exchange-correlation functional, have been performed to probe the mechanism for the insertion reaction of molecular oxygen into the palladium(II) hydride bond of the trans-[PdH(O2Ac)(IMes)2] complex to form the corresponding Pd(II)-hydroperoxide. A crossing between triplet and singlet surfaces occurs before the formation of a stable singlet intermediate from which the reaction straightforwardly proceeds to yield the singlet hydroperoxo complex. Results appear to be different with respect to previous analogous theoretical investigations providing a new minimum energy pathway. © 2008 Elsevier B.V. All rights reserved.
Chowdhury, S., Rivalta, I., Russo, N., Sicilia, E. (2008). The recognition of a new pathway for the reaction of molecular oxygen with a Pd(II)-hydride to produce a Pd(II)-hydroperoxide. CHEMICAL PHYSICS LETTERS, 456(1-3), 41-46 [10.1016/j.cplett.2008.03.013].
The recognition of a new pathway for the reaction of molecular oxygen with a Pd(II)-hydride to produce a Pd(II)-hydroperoxide
Rivalta, Ivan;
2008
Abstract
Significant recent developments in homogeneous palladium catalysis for selective aerobic oxidation have emphasized the importance of developing a thorough comprehension of reactions of palladium complexes with O2. Density functional theory (DFT) calculations, employing the B3LYP exchange-correlation functional, have been performed to probe the mechanism for the insertion reaction of molecular oxygen into the palladium(II) hydride bond of the trans-[PdH(O2Ac)(IMes)2] complex to form the corresponding Pd(II)-hydroperoxide. A crossing between triplet and singlet surfaces occurs before the formation of a stable singlet intermediate from which the reaction straightforwardly proceeds to yield the singlet hydroperoxo complex. Results appear to be different with respect to previous analogous theoretical investigations providing a new minimum energy pathway. © 2008 Elsevier B.V. All rights reserved.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
