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Chemistry · L5 · Outer-sphere vs inner-sphere electron transfer

Whether a bridging ligand bond forms between donor and acceptor determines outer-sphere (Marcus theory's target) vs inner-sphere electron transfer, with Taube's Cr–Cl–Co experiment as the classic inner-sphere example.

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Electron transferbetween two speciesDo donor and acceptorform a bridging bond?Outer-sphere ETno bond breaks or formsMarcus theory applies directlyInner-sphere ETbond forms, then breaksExample: Fe(H2O)6 2+/3+self-exchangeExample: Taube bridgeCr2+ + Co(NH3)5Cl 2+No — only close approachYes — a ligand bridges them

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