. Author manuscript; available in PMC: 2013 Jul 18.

Published in final edited form as: J Am Chem Soc. 2012 Jul 6;134(28):11791–11806. doi: 10.1021/ja3046298

Table 6.

Geometric Parameters for 2 and [Fe^IV=O(TMC)(CH₃CN]²⁺ for H-atom Transfer and Oxo-Transfer Transition State Complexes

	[Fe^IV=O(TBC)(CH₃CN)]²⁺ (2)						[Fe^IV=O(TMC)(CH₃CN)]²⁺

	GS / ES		H-Atom Transfer		Oxo-Transfer		GS / ES		H-Atom Transfer		Oxo-Transfer

Measurement	S = 1	S = 2	S = 1	S = 2	S = 1	S = 2	S = 1	S = 2	S = 1	S = 2	S = 1	S = 2
Oxo-H/S (H-C)	- - -	- - -	1.27(1.34)	1.25(1.34)	2.03	2.07	- - -	- - -	1.28(1.33)	1.42(1.23)	1.92	2.07
Fe=Oxo	1.61	1.61	1.75	1.76	1.87	1.78	1.62	1.61	1.75	1.73	1.86	1.80
Fe-N CH₃CN	2.12	2.09	2.10	2.36	2.30	4.08	2.12	2.08	2.09	2.32	2.28	2.51
Ave. Fe-N Equatorial	2.15	2.24	2.16	2.25	2.17	2.21	2.14	2.22	2.13	2.23	2.16	2.23
Fe Out of Plane	−0.06	−0.08	−0.03	0.05	0.01	0.34	−0.05	−0.07	−0.02	0.05	0.04	0.13
O-H Plane Distance	−0.38	−0.40	−0.21	−0.11	−0.04	0.23	−0.37	−0.39	−0.20	−0.14	−0.01	0.03
Ave. O-H Distance	2.37	2.39	2.39	2.41	2.42	2.55	2.41	2.43	2.43	2.45	2.51	2.51
Nitrogen Shell SD	0.03	0.07	0.04	0.06	0.07	0.84	0.01	0.06	0.03	0.04	0.06	0.13

∠ Fe-O-Substrate	- - -	- - -	144.04	176.45	153.07	154.84	- - -	- - -	143.64	176.12	148.98	153.46
∠ θ (Horiz. to O P_x/y)	- - -	- - -	61.24	86.28	44.79	34.57	- - -	- - -	60.75	86.57	52.23	40.79
Δ (Horiz. Offset O P_z)	- - -	- - -	1.24	0.17	0.92	0.88	- - -	- - -	1.26	0.16	0.99	0.93
H-Plane-Sub. Dist.	- - -	- - -	2.14	2.47	1.85	2.15	- - -	- - -	2.15	2.51	1.75	1.95

Geometric parameters for the S = 1 ground state (GS) and the S = 2 excited state (ES) reproduced from Table 4 along with those of the corresponding H-atom abstraction and oxo-transfer transition state complexes of [Fe^IV=O(TBC)(CH₃CN)]²⁺ (2) and [Fe^IV=O(TMC)(CH₃CN)]²⁺. Structures calculated using B3LYP/6-311G(d). All distances are given in Å, all angles (∠) are in degrees, SD = Standard Deviation. Reference SI Figure 12 for descriptions and SI Table 4, 6 and 7 for additional parameters.