. 2020 Mar 6;11(14):3592–3603. doi: 10.1039/c9sc06445a

Experimental (Exp.) g values compared to calculated (calc.) ones^a as well as relative electronic energies of the investigated radical cations with different point groups and comparison to the already reported [Cr(CO)₆]⁺˙.

		[Cr(CO)₆]⁺˙		[Mo(CO)₆]⁺˙		[W(CO)₆]⁺˙
		D _3d	D _4h	D _3d	D _4h	D _3d	D _4h
ΔE^b		0.00	136 (1.6)	0.00	204 (2.4)	0.00	710 (8.5)
g _⊥	Exp.	2.185		2.374		1.722
g _⊥	Calc.	2.173	2.434	2.408	2.216	2.701	2.164
g _∥	Exp.	1.947		1.800		2.427
g _∥	Calc.	1.971	1.761	1.848	1.956	0.977	1.212
g _iso	Exp.	2.106^c		2.058^c		2.192^d
g _iso	Calc.^e	2.106^c	2.210^c	2.221^c	2.129^c	2.126	1.847

For details of the g-value calculations please refer to theESI. Values for [Cr(CO)₆]⁺˙ taken from ref. 2.

Electronic energies (in cm⁻¹, in brackets: kJ mol⁻¹) were calculated at the DLPNO-CCSD(T)/def2-TZVPP level of theory using structures optimized with TPSSh-D3BJ/def2-TZVPP.

g _iso = (2g_⊥ + g_∥)/3.

g _iso = (g_⊥ + 2g_∥)/3.

The better accordance of the isotropic g-value of D_4h with experiment must not be misinterpreted: deviations in the calculation of the perpendicular component g_⊥ enter twofold.

Experimental (Exp.) g values compared to calculated (calc.) onesa as well as relative electronic energies of the investigated radical cations with different point groups and comparison to the already reported [Cr(CO)6]+˙.

Experimental (Exp.) g values compared to calculated (calc.) ones^a as well as relative electronic energies of the investigated radical cations with different point groups and comparison to the already reported [Cr(CO)₆]⁺˙.