Large Molecules

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From these typical ligandfield arguments it becomes clear that the porphyrin ligands act towards their central ions as a "hard" base although they contain a highly polarizable "soft" ~-electron core. g. no anion with MnIII and CN- with Fe III [Pearson (148), Boucher (11)]. (see also section 113). 41 t'O Mg II ~$, ~ + , Na I, ~-" Ca II Sr II Ba II Ra (~-') K I Rb I Cs Fr I Be II Li Ac La Y Sc III Hf IV Zr IV Ti IV Ta V Nb V V IV W V Mo IV, V Cr II, I I I , (IV) Os II Re I, V Ir I I I , (I) Rh I, I I , Ru II, I I I , ~ Tc (~$) Fe Co I, I I , I, I I , III,(IV) III, Mn II, I I I , (IV) Pt II Pd II, Ni II, III, a~ Au III Ag II, I I I Cu II, ~$ Hg II Cd II ~=,~- Zn II, ~$,a2+ T h e R o m a n n u m b e r s give t h e o x i d a t i o n n u m b e r s f o u n d for t h e c e n t r a l ions, t h e z~ s i g n s i n d i c a t e t h e o x i d a t i o n s t a t e s ( e x c e p t zero) of t h e p o r p h y r i n z¢ s y s t e m s i n v e s t i g a t e d so far.

5. Summary The reversible porphyrin ligand reductions and oxidations are governed by the activation or deactivation of the a-electron conjugated system through the electrostatic action of the framework containing the more or less polar metal-nitrogen bands.

G. CrII, MnIII, Col, Rh I, AgIII, no Sn II] and the numerical values of the potentials in Table 7. A more detailed analysis will not be possible until we have new and more precise models because the existing ligand-field and extended Hiickel calculations do not reproduce correctly the relative energies of metal-d and porphyrin-~r orbitals. The simplicity of the redox patterns produced by metal ions in the porphyrin cavity also renders superfluous the various models for porphyrins which, being usually not very rigid and unsymmetrical macrocycles, tend to complicate rather than clarify the situation ETang (772), Tokd (174)].

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