Table 1. Free energies of main stationary points for H–E activation by LAu⁺ (at –20 °C, in kcal mol^–1) ^a .

HE	LAu(HE)+	[LAu···H···E···B]+	LAuH + BE+	[LAu]2H+ + BE+
HSiMe3	–5.28	–0.87 b	–7.15	–25.83
HBPin	–0.72	–1.71 c	–4.72	–23.40
H2	+6.21	+9.72 b	+10.51 e	–16.06 f
PyCarH	—	+3.67 b , d	–7.57 d	–26.25
CHDH	—	+16.22 b , d	+15.83 d	–2.85
Ph3CH	—	—	+19.24 d	+0.56
PhCH3	—	g	+45.80 d	+27.12

^aLAu⁺ + HE as reference (0 kcal mol^–1); B = OMe₂; reference energy of LAu(B)⁺ is –8.86 kcal mol^–1 if the reaction is done in presence of ether.

^bTransition state.

^cIntermediate (local minimum).

^dNo assistance by ether.

^eNot separated products but complex LAuH···BE⁺.

^fForming H[OMe₂]₂⁺ instead of HOMe₂⁺.

^gBarrierless to reactants.