Table 1. Kinetic data and product distributions obtained for the gas phase reaction of [Fe^IV(O)(TPFPP⁺˙)]⁺ with selected olefins as determined by FT-ICR MS.

Substrate	IE a	k exp b	k ADO c	Φ d	HT	CT	OAT	Add
Ethene	10.51	8.5 × 10–5	8.5	1 × 10–3	—	—	100	—
Propene	9.73	7.6 × 10–3	9.45	0.080	—	—	100	—
1-Butene	9.55	0.029	9.6	0.30	—	—	100	—
E-2-Butene	9.10	0.080	10.8	0.74	—	—	100	—
2,3-Dimethyl-1-butene	9.07	0.145	9.5	1.5	—	—	100	—
Cyclohexene e	8.95	0.194–0.291	9.7	2–3	—	—	75	25
1,4-Cyclohexadiene	8.82	0.511	9.29	5.5	—	—	90	10
2-Methoxy-1-propene	8.64	0.819	10.5	7.8	—	—	100	—
1,3-Pentadiene	8.60	0.826	9.6	8.6	—	—	100	—
Styrene	8.46	1.40	9.26	15	—	—	100	—
1,3-Cyclohexadiene	8.25	1.58	9.29	17	—	—	100	—
trans-β-Methylstyrene	8.1–8.2	2.97	11.9	25	4	—	96	—
Indene	8.14	3.18	8.6	37	2	12	86	—
β-Pinene f	N/A	4.32–4.7	9.4	46–50	—	—	100	—

^aIonization energies (IE, eV) are from ref. 24. N/A stands for not available.

^bSecond-order rate constants (k_exp) in units of 10^–10 cm³ molecule^–1 s^–1 are measured at a temperature of 300 K in the FT-ICR cell. The estimated error in k_exp is ±30%, although the internal consistency of the data is within ±10%.

^cCollision rate constants (k_ADO) evaluated with the parameterized trajectory theory.

^dReaction efficiency (%), Φ = k_exp/k_ADO × 100.

^eThe reaction with cyclohexene-d₁₀ gave a rate constant within experimental error of that for cyclohexene-h₁₀.

^fThe IE for α-pinene is 8.07 eV.