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. Author manuscript; available in PMC: 2016 Jul 20.
Published in final edited form as: Chemistry. 2015 Jun 18;21(30):10878–10885. doi: 10.1002/chem.201500611

Table 2.

Electrochemical data for dimeric and monomeric 2-Y-DMBI compounds,[a] and adiabatic ionization energies (IEs) and dissociation energies obtained from M06/LANL2DZ/6-31G(d,p) calculations for various 2-Y-DMBI species.

E vs. FeCp2 +/0 / V [a]
IE / eV[d]
ΔUdiss / kJ mol−1 (eV)[d]
Y Epa(D2 +/0)[b] Epc(D+/0)[c] D2→D2•++e[e] D→D++e 0.5D2→D++e[f] D2→2D D2•+ →D+ + D [e]
Cyc −0.64 −2.45 5.06 3.72 4.81 210 (2.17) 81 (0.84)
Fc −0.89 −2.24 4.69 3.93 4.79 165 (1.71) 91 (0.94)
Rc −0.59 −2.29 4.68 3.80 4.73 181 (1.87) 97 (1.00)
[a]

In THF / 0.1 M nBu4NPF6.

[b]

Peak potential for the irreversible oxidation of D2 measured at 100 mV s−1.

[c]

Peak potential for the partially reversible reduction of D+ at 100 mV s−1.

[d]

Gas-phase adiabatic IEs and dissociation energies obtained from DFT calculations.

[e]

These results should be treated with caution owing to the tendency of DFT to artificially over-delocalize odd-electron systems such as these cations due to self-interaction error[22] Indeed the optimized structures for the D2 •+species are all characterized by spuriously long central C—C bonds (3.23-3.34 Å).

[f]

IEeff(0.5D2→D++e) = IE(D) + 0.5ΔUdiss(D2).