Synthesis and Structural Characterization of an Unusual Platinum π‑Arene Complex: (η<sup>6</sup>‑C<sub>6</sub>H<sub>3</sub>Me<sub>3</sub>)Pt[(C<sub>2</sub>F<sub>5</sub>)<sub>2</sub>PMe]Me<sup>+</sup>
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Treatment of cis-(dfmp)2PtMe2 (dfmp = (C2F5)2PMe) with the mesitylenium acid (C6Me3H4)+B(C6F5)4– in 1,2-difluorobenzene cleanly produces an unusually stable arene complex, [(η6-C6Me3H3)Pt(dfmp)(CH3)]+(B(C6F5)4)− (1). Facile arene exchange and competitive binding equilibria have been quantified for mesitylene relative to toluene (K = 0.0030(3)) and durene (K = 20(2)). Reaction of 1 with H2 at 80 °C results in hydrogenolysis to form the arene hydride (η6-C6Me3H3)Pt(dfmp)(H)+ (2), while treatment of 1 with CO gives trans-(dfmp)2Pt(CO)Me+ as the major phosphine product. Addition of excess Me3P to 1 results in both arene and dfmp displacement to form (Me3P)3PtMe+. (η6-C6Me3H3)Pt(dfmp)(CH3)+ is a moderately active ethylene dimerization catalyst to form 2-butenes (∼7 TO h–1, 20 °C).
