Abstract
Electrochemistry is employed both as an analytical instrumental technique and as a method of inducing changes in the structure and reactivity of organometallic complexes. It is the primary implement for expanding the applications of organometallic electron-transfer (ET) chemistry and is at its most powerful when blended with the use of spectroscopy, DFT calculations of molecular structure, and chemical redox agents. Examples are given of how electrochemistry has traditionally been employed to probe changes in the structure and reactivity of organometallic complexes. Continued advances are expected for all areas in which organometallic ET processes play a role, including catalysis of small-molecule reactions, energy storage and conversion, bio-organometallic chemistry, redox polymers, and analytical and molecular devices. Particular opportunities for redox-active “hybrid” complexes in which organometallic moieties are fused with noninnocent chelate ligands or tagged onto molecular targets are discussed.
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