Oxidative Addition of Hydrogen Halides and Dihalogens to Pd. Trends in Reactivity and Relativistic Effects

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Abstract
We have theoretically studied the oxidative addition of HX and X2 to palladium for X = F, Cl, Br, I and At, using both nonrelativistic and ZORA-relativistic density functional theory at BLYP/QZ4P. The purpose is 3-fold: (i) to obtain a set of consistent potential energy surfaces (PESs) to infer accurate trends in reactivity for simple, archetypal oxidative addition reactions; (ii) to assess how relativistic effects modify these trends along X = F, Cl, Br, I and At; and (iii) to rationalize the trends in reactivity in terms of the reactants’ molecular-orbital (MO) electronic structure and the H−X and X−X bond strengths. For the latter, we provide full Dirac−Coulomb CCSD(T) benchmarks. All oxidative additions to Pd are exothermic and have a negative overall barrier, except that of HF which is approximately thermoneutral and has a positive overall barrier. The activation barriers of the HX oxidative additions decrease systematically as X descends in group 17 of the periodic table; those of X2 first increase, from F to Cl, but then also decrease further down group 17. On the other hand, HX and X2 show clearly opposite trends regarding the heat of reaction: that of HX becomes more exothermic and that of X2 less exothermic as X descends in group 17. Relativistic effects can be as large as 15−20 kcal/mol but they do not change the qualitative trends. Interestingly, the influence of relativistic effects on activation barriers and heats of reaction decreases for the heavier halogens due to counteracting relativistic effects in palladium and the halogens.