We have studied the palladium-mediated activation of C(sp(n))-X bonds (n = 1-3 and X = H, CH3, Cl) in archetypal model substrates H3C-CH2-X, H2C=CH-X and HC equivalent to C-X by catalysts PdLn with... Show moreWe have studied the palladium-mediated activation of C(sp(n))-X bonds (n = 1-3 and X = H, CH3, Cl) in archetypal model substrates H3C-CH2-X, H2C=CH-X and HC equivalent to C-X by catalysts PdLn with L-n = no ligand, Cl-, and (PH3)(2), using relativistic density functional theory at ZORA-BLYP/TZ2P. The oxidative addition barrier decreases along this series, even though the strength of the bonds increases going from C(sp(3))-X, to C(sp(2))-X, to C(sp)-X. Activation strain and matching energy decomposition analyses reveal that the decreased oxidative addition barrier going from sp(3), to sp(2), to sp, originates from a reduction in the destabilizing steric (Pauli) repulsion between catalyst and substrate. This is the direct consequence of the decreasing coordination number of the carbon atom in C(sp(n))-X, which goes from four, to three, to two along this series. The associated net stabilization of the catalyst-substrate interaction dominates the trend in strain energy which indeed becomes more destabilizing along this same series as the bond becomes stronger from C(sp(3))-X to C(sp)-X. Show less
