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Folding of ene-diamido chelates in d0 metal complexes is generally  attributed to a saturating π interaction of the metal with  the central CC linkage. A MO analysis of selected models (DFT  and EHMO levels) shows that the latter interaction is negligible  (negative M–C overlap populations). Moreover, a detailed  analysis of the orbital interactions highlights a two-electron  flow from filled pπ orbitals of the nitrogen atoms toward  the metal consequent to ligand folding. Conversely, it is evident that the CC π-electron cloud is only barely affected  by the contacts with the metal atom.

Nature of the metal–carbon contacts in ene-diamido d0 metal complexes