Advances in organometallic C-C bond forming reactions require judicious modulation of both the ligand geometry about the metal catalyst, as well as intricate control of the electronic structure of the reacting orbitals.  While not catalytic by nature, metal-mediate Bergman cyclization of diyn-3-ene functionalities requires intimate control of those same geometric and electronic parameters to produce the most facile cyclization and C-C bond formation.  To this end, we illustrate two cases: one where s-coordination and ligand geometry are controlled by in situ two-electron oxidation of a thermally robust, tetrahedral Pt(0)-phosphine metalloenediyne with instantaneous generation of a Pt(II) complex reactive toward Bergman cyclization, and another where s/p hybrid systems derived from nitrogen pincers for robust s-metal coordination with simultaneous metal activation of their macrocyclic enediyne p-bonds.  These constructs engender the same principles required for catalytic organometallic cyclization events, but their air and water stabilities enhance potential for subsequent reactions with biological substrates.

s/p Metal-mediated enediyne activation to promote diradical generation and C-C bond formation

247th National Meeting (2014)

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