. Author manuscript; available in PMC: 2016 Apr 29.

Published in final edited form as: J Am Chem Soc. 2015 Apr 16;137(16):5468–5479. doi: 10.1021/jacs.5b01197

Table 1.

EPR Parameters of Nitrene Radical Complex 3^P1_Ns in Frozen Solution at 50 K and in Isotropic Solution at Room Temperature

		50 K		298 K
	g₁₁	g₂₂	g₃₃	g_av	g_iso
Exp	2.0087	2.0049	2.0005	2.0047	2.005
DFT^a
5-coord	2.0490	2.0154	1.9810	2.0150	2.015
5-coord^e	2.0287^e	2.0029^e	1.9816^e	2.0044^e	2.004^e
NsNH⁻^f	2.0311	2.0052	1.9966	2.0109	2.011
OH⁻^g	2.0387	2.0116	2.0022	2.0175	2.018
A^Co	A^Co₁₁^b)	A^Co₂₂^b)	A^Co₃₃^b)	A^Co_av^b)	A^Co_iso^b)
Exp	−50^c)	50^c)	20^c)	7^c)	−25
DFT^a)
5-coord	−98	65	13	−7	−7
5-coord^e	−18^e	−89^e	15^e	−42^e	−31^e
NsNH⁻^g	−59	30	11	−6	−6
OH^−h)	−62	50	67	18	18
A^N	A^N₁₁^b)	A^N₂₂^b)	A^N₃₃^b)	A^N_av^b)	A^N_iso^b)
Exp	n.r.^d)	n.r.^d)	n.r.^d)	n.r.^d)	10
DFT^a)
5-coord	−20	−14	81	15	16
5-coord^e	−23^e	−14^e	84^e	16^e	16^e
NsNH⁻^f	−11	−9	87	22	22
OH⁻^g	−13	−10	84	20	20

Geometry of 3^P1_Ns optimized with Turbomole (full atom model, BP86, def2-TZVP) employing Grimme’s D3-dispersion corrections (disp3); EPR parameters calculated with ORCA, (b3-lyp/def2-TZVP).

MHz.

Data from Q-band Davies ENDOR measurements (see Supporting Information).

Not resolved.

Geometry of 3^P1_Ns (full atom model) optimized with Turbomole at the b3-lyp, def2-TZVP level without dispersion corrections to match the solution data.

Optimized geometry of six-coordinate NsNH⁻ amido adduct of 3^P1_Ns (full atom model, BP86, def2-TZVP) employing Grimme’s D3-dispersion corrections (disp3).

Optimized geometry of six-coordinate OH⁻ hydroxido adduct of 3^P1_Ns (full atom model, BP86, def2-TZVP) employing Grimme’s D3-dispersion corrections (disp3).