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2.6.4.2.1 Variation 1: One-Electron Oxidative Additions

DOI: 10.1055/sos-SD-002-00315

Poli, R.; Smith, K. M.Science of Synthesis, (20032307.

Chromium(II) precursors react with al­kyl halide reagents to afford a 1:1 mixture of chromium(III) halide and al­kyl­chromium(III) products. The mechanism involves single-electron-transfer steps and radical intermediates (Scheme 24). Other radical sources may be used instead, including hy­dro­per­ox­ides or alkane/hy­dro­gen per­ox­ide mixtures under thermal, flash photolysis, or pulse radiolysis conditions.[‌109‌] This procedure has been used to produce the al­kyl­pentaaquachromium(III) ion 61.[‌110‌] The latter is long-lived but cannot be isolated and must be generated in situ. Activated al­kyl halides react thermally with the chromium(III) ion, while other al­kyls require photolytic or radiolytic conditions. The addition of ligands such as eth­yl­ene­di­amine or saturated tet­ra­aza macrocycles makes the process more favorable for both thermodynamic and kinetic reasons.

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