Table 2 Cyclic voltammetry correlated to [CPCMtoluene/PWPB95/def2-QZVPP(ecp)] redox molecular orbital energies \({E}_{p}^{a}\) and \({E}_{p}^{c}\) versus Fc+/0.[a]

From: Challenging an old paradigm by demonstrating transition metal-like chemistry at a neutral nonmetal center

Complex

\({E}_{p}^{{aI}}\) / V

\({E}_{p}^{{aII}}\) / V

HOMO / eV

\({E}_{p}^{{cIII}}\) / V

LUMO / eV

ΔE / V[b]

H-L / eV

3b

−0.04

+0.17

−5.03

−2.58

−1.54

2.54

3.49

3c

−0.02

+0.20

−5.20

−3.05

−1.33

3.03

3.88

3cCr

−0.07

+0.40

—

−2.95

—

2.87

—

3d

+0.51

—

−5.53[c]

−2.34

−1.81[c]

2.85

3.72[c]

  1. [a] Fc in this paper designates ferrocene; [Fe(η5-C6H5)2] and the ferrocene/ferrocenium redox couple is designated as Fc+/0, set to 0 V according to IUPAC recommendations102. \({E}_{p}^{a}\) and \({E}_{p}^{c}\) designate anodic and cathodic peak potentials, respectively, in standard electrochemical notation. [b] ΔE = \({E}_{p}^{{aI}}-{E}_{p}^{{cIII}}\). [c] Computed for the simplified model complex adduct derived from methylisocyanide (3d’).
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