Table 1.

Activation (E_a) and reaction energies (E_r) reflecting electronic differentiations in transition structures (ΔE_a^cis-trans) and Pd-ene products relative to Pd-allyl and NH₃ reactands (pb = phosphabenzene; py = pyridine moieties)^[a]

pb-X	py-Y	Ea	TS	ΔEaTS	ErProd	ΔErProd
H	HNMe	cis	8.55	0.03	7.81	0.55
		trans	8.52		8.36
H	H	cis	6.38	0.17	5.14	0.52
		trans	6.21		5.67
H	NO2	cis	4.47	0.27	2.48	0.54
		trans	4.20		3.02
HNMe	HNMe	cis	10.47	-0.20 [b]	10.33	0.65
		trans	10.67		10.98
HNMe	H	cis	8.43	-0.03[b]	7.80	0.60
		trans	8.46		8.40
HNMe	NO2	cis	6.61	0.10	5.34	0.65
		trans	6.51		5.99
NO2	HNMe	cis	6.34	0.08	5.05	0.53
		trans	6.26		5.58
NO2	H	cis	4.24	0.23	2.26	0.43
		trans	4.01		2.70
NO2	NO2	cis	2.52	0.33	-0.25[c]	0.54
		trans	2.19		0.29

[a] B3LYP/6-31G* (C, H, N, P, O), /SDD (Pd) optimized structures. Energies include ZPE corrections scaled by 0.9806; [b] Negative ΔE_a^TS with E_a^cis < E_a^trans; [c] exothermic reaction energy.