. Author manuscript; available in PMC: 2019 Feb 5.

Published in final edited form as: J Am Chem Soc. 2018 Sep 28;140(40):12947–12963. doi: 10.1021/jacs.8b07613

Table 4.

Extended point-dipole approximation analysis of the nuclei coupled to the reduced [2Fe-2S] cluster, in comparison with the experimental parameters of the paramagnetic intermediate.

Nucleus	a_iso (MHz)^a	Exp-T_dip (MHz)^a	T_non-loc (MHz)^b	T_non-loc (MHz)^c
¹⁵N_a	4.99	[−1.33, −0.89, 2.22]	[−1.12, 0.48, 1.60]	[−1.12, −0.86, 1.98]
¹⁵N_b	1.26	[−0.56, 0.02, 0.54]	[−0.50, 0.18, 0.68]	[−0.14, −0.13, 0.27]
¹H1	3.90	[−4.97, −4.97, 9.94]	[−5.34, −5.11, 10.45]	[−4.62, −4.56, 9.18]
¹H2	2.36	[−4.06, −4.06, 8.12]	[−3.00, 2.60, 5.60]	[−3.28, −3.07, 6.35]
¹H3	1.51	[−2.16, −2.16, 4.32]	[−2.49, −2.27, 4.77]	[−2.99, −2.82, 5.81]

Experimental hyperfine parameters of the paramagnetic intermediate.

The calculated through-space dipolar hyperfine (eq. 4, with K_A = 2.333, K_B = −1.333) by using the coordinates of [2Fe-2S] cluster in BioB, adapted from the oxidized X-ray crystal structure (PDB:1r30).

The calculated through-space dipolar hyperfine (eq. 4, with K_A = 2.088, K_B = −1.088) by using the BS-DFT optimized geometry of the reduced [2Fe-2S] cluster in BioB, shown in Figure S13C&S14C.