Synthesis, Structure, and Oxidative Additions of a Fluorous Analogue of Vaska's Complex, <i>trans</i>‐[IrCl(CO){P[CH₂CH₂(CF₂)₅CF₃]₃}₂]— Altered Reactivity in Fluorocarbons and Implications for Catalysis

Abstract

The most highly fluorinated aliphatic species crystallized to date is 1 an exceptionally interesting molecule with regard to its structure and from a mechanistic standpoint. Four of the fluroalkyl groups form raftlike domains, which pack back-to-back in a motif that maximizes parallel chains (depicted on the right). Complex 1 and CH3I react by a free redical chain mechanism in CF3C6F11, as opposed to the polar pathway for Vaska's complex in organic solvents. Although O2 is highly soluble in CF3C6F11, its additions to 1 slower than in common organic solvents.