. Author manuscript; available in PMC: 2012 Oct 17.

Published in final edited form as: Inorg Chem. 2011 Aug 15;50(20):9794–9803. doi: 10.1021/ic200046k

Table 2.

Experimental and Computed ⁵¹V NMR parameters for VO(hshed)(Cat) (1a)^a,^b

Method	Solid state											Solution
	C_Q/MHz	η_Q	δ_iso/ppm	δ_σ/ppm	η_σ	δ₁₁/ppm	δ₂₂/ppm	δ₃₃/ppm	α/degree	β/degree	γ/degree	δ_iso/ppm

Experiment	4.0 ±0.1	1.00 ±0.05	58 ±5	−243 ±30	0.93 ±0.05	291 ±30	68 ±30	−185 ±30	81 ±10	70 ±15	87 ± 30	221¹⁶
b3lyp/6-311+G (non-optimized)	7.76	0.38	−16.3	−472.0	0.82	413.2	26.2	−488.3	89	109	69
b3lyp/TZV (non-optimized)	7.00	0.39	−51.4	−477.3	0.84	387.7	−13.2	−528.7	87	115	71
b3lyp/6-311++G (proton geometries optimized)	7.97	0.32	−32.0	−461.8	0.77	376.7	21.1	−493.8	149	21	16
b3lyp/TZVP (proton geometries optimized)	7.79	0.32	30.1	−434.0	0.92	446.7	47.5	−403.9	150	24	23
b3lyp/6-311++G (all atom geometries optimized)	10.66	0.45	−233.3	−484.3	0.62	159.0	−141.3	−717.6	92	4	148
*b3lyp/Wachters+f on V, 6-31G on other atoms**	9.92	0.50	61.7	−333.9	0.89	377.2	80.1	−272.2	82	107	64

The chemical shift parameters are defined such that |δ_xx – δ_iso |≤ |δ_yy – δ_iso |≤ |δ_zz – δ_iso | and δ_iso = (δ_xx + δ_yy + δ_zz)/3, δ_σ = δ_zz − δ_iso, η_σ = (δ_yy − δ_xx)/( δ_zz − δ_iso) according to the Haeberlen-Mehring-Spiess convention.16 Here δ_ii denotes the principal components of the chemical shift tensor.

The EFG parameters are C_Q = eQV_ZZ/h and η_Q = (V_XX − V_YY)/V_ZZ where |V_ZZ| ≥ |V_YY| ≥ |V_XX|, e is the electron charge, and h is Planck’s constant.