摘要: The concept of outer-sphere coordination (OSC) is surveyed in the context bioinorganic chemistry. A distinction made between electronic and structural OSC, both arising from interaction protein matrix with inner sphere ligands. Electronic OSC entails polypeptide inner-sphere These effects principally arise hydrogen-bonding interactions, though through-space dipolar interactions are also encountered. Structural comprises primarily steric that do not necessarily impact ligand electronics but rather influence topology. Additionally, can be envisioned as a local “solvent” whose bulk dielectric point charges metal center. Recurring themes highlighted where regulates properties various metalloproteins distinguished by cofactors and/or function. Finally, cases presented has guided molecular design.