TY - JOUR
T1 - Dioxygen insertion into the gold(i)-hydride bond
T2 - spin orbit coupling effects in the spotlight for oxidative addition
AU - Gaggioli, Carlo Alberto
AU - Belpassi, Leonardo
AU - Tarantelli, Francesco
AU - Zuccaccia, Daniele
AU - Harvey, Jeremy N.
AU - Belanzoni, Paola
N1 - Publisher Copyright:
© The Royal Society of Chemistry.
PY - 2016
Y1 - 2016
N2 - O2 insertion into a Au(i)-H bond occurs through an oxidative addition/recombination mechanism, showing peculiar differences with respect to Pd(ii)-H, for which O2 insertion takes place through a hydrogen abstraction mechanism in the triplet potential energy surface with a pure spin transition state. We demonstrate that the spin-forbidden Au(i)-hydride O2 insertion reaction can only be described accurately by inclusion of spin orbit coupling (SOC) effects. We further find that a new mechanism involving two O2 molecules is also feasible, and this result, together with the unexpectedly high experimental entropic activation parameter, suggests the possibility that a third species could be involved in the rate determining step of the reaction. Finally, we show that the O2 oxidative addition into a Au(i)-alkyl (CH3) bond also occurs but the following recombination process using O2 is unfeasible and the metastable intermediate Au(iii) species will revert to reactants, thus accounting for the experimental inertness of Au-alkyl complexes toward oxygen, as frequently observed in catalytic applications. We believe that this study can pave the way for further theoretical and experimental investigations in the field of Au(i)/Au(iii) oxidation reactions, including ligand, additive and solvent effects.
AB - O2 insertion into a Au(i)-H bond occurs through an oxidative addition/recombination mechanism, showing peculiar differences with respect to Pd(ii)-H, for which O2 insertion takes place through a hydrogen abstraction mechanism in the triplet potential energy surface with a pure spin transition state. We demonstrate that the spin-forbidden Au(i)-hydride O2 insertion reaction can only be described accurately by inclusion of spin orbit coupling (SOC) effects. We further find that a new mechanism involving two O2 molecules is also feasible, and this result, together with the unexpectedly high experimental entropic activation parameter, suggests the possibility that a third species could be involved in the rate determining step of the reaction. Finally, we show that the O2 oxidative addition into a Au(i)-alkyl (CH3) bond also occurs but the following recombination process using O2 is unfeasible and the metastable intermediate Au(iii) species will revert to reactants, thus accounting for the experimental inertness of Au-alkyl complexes toward oxygen, as frequently observed in catalytic applications. We believe that this study can pave the way for further theoretical and experimental investigations in the field of Au(i)/Au(iii) oxidation reactions, including ligand, additive and solvent effects.
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U2 - 10.1039/C6SC02161A
DO - 10.1039/C6SC02161A
M3 - Article
AN - SCOPUS:84995602190
SN - 2041-6520
VL - 7
SP - 7034
EP - 7039
JO - Chemical Science
JF - Chemical Science
IS - 12
ER -