Structural, spectroscopic and magnetic properties of M[R2P(E)NP(E)R′2]2 complexes, M = Co, Mn, E = S, Se and R, R′ = Ph or iPr.: Covalency of M-S bonds from experimental data and theoretical calculations

The S/Se-containing bidentate ligands LH of the type R2P(E) NHP(E) R '(2), E = S, Se and R, R' = Ph or Pr-i have been employed to synthesize ML2 (M = Mn, Co) complexes which contain the biologically important MS4 core. Theoretical calculations on the LH and L- forms of the ligands probe the geometric and electronic changes induced by the deprotonation of the LH form, which are correlated with structural data from X-ray crystallography. These results reflect the flexibility of the ligands, which enables them to be rather versatile with respect to the formation of ML2 complexes with varied geometries and MEPNPE metallacycle conformations. A series of old and new ML2 complexes have been synthesized and their structural, spectroscopic and magnetic properties characterized in detail. The nephelauxetic ratio beta of the CoL2 complexes provides evidence of covalent interactions, whereas the EPR properties of the MnL2 complexes are interpreted on the basis of predominant ionic interactions, between the metal center and the ligands, respectively. Additional evidence for the existence of covalent interactions in the CoL2 complexes (R = Ph, Pr-i, or mixed Ph/Pr-i), is offered by comparisons between their P-31 NMR. The aforementioned notations are supported by extensive theoretical calculations on the ML2 ( E = S, R = Me) modelled structures, which probe the covalent and ionic character of the M - S bonds when M = Co or Mn. Wider implications of the findings of the present study on the M - S covalency and its importance in the active sites of various metalloenzymes are also discussed.