N4 Functionalisation

All Values Have Been Computed at the PBEO Level Using Two Different Basis Sets (a) CEP-121G on Co and 6 31G(d) on C,N and H (small basis), (b) CEP-12IG on Co and 6-31 lG(d,p) on C,N and H (large basis) 

Neutron diffractions studies allow for an experimental estimation of the charge density on the central Co and, in particular, of the d-orbital electron population Anyway, a quantitative comparison between our NBO analysis and the experimental results (obtained through a least-square fitting of the density) is not strictly rigorous, since the procedure of partitioning the total electron density is different. Nevertheless, the agreement of the PBEO calculations with the experiments is qualitatively satisfactory. For instance, the X-ray analysis of 

Slightly different values are found from neutron experiments, The 

We recall that a low value for the hardness implies greater interactions between donor and acceptor species, corresponding to a small energy gap between the donor HOMO orbital and the LUMO of acceptor. Some trends appear from the 

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Here we review our work aimed at correlating the reactivity of a series of M(II) N4-ligands, see Figure 12.1, (M = Co, Fe, Mn and N4 = porphyrin (P), phthalocyanine (Pc), teraphenylporphyrin (TPP), tetrabenzoporphyrin (TBP) and tetraazaporphyrin (TAP)) towards the electrocatalytic oxidation of 2-mercaptoethanol. Different effects will be analysed, namely the role of the metal atoms, the role of the N4 functionalisation, solvent and the impact of the adsorption on the electrode on the electrochemical activity. The whole machinery of DFT and the notions of hardness, chemical potential, intramolecular hardness and elec-trophilicity are used to better quantify these effects and discriminate between the examined molecular complexes. 

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