Oxidative Addition of MeI to a Rollover Complex of
Platinum(II): Isolation of the Kinetic Product
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Abstract
A pair of new Pt(II)/Pt(IV) 2,2′-bipyridine
cyclometalated
rollover complexes have been synthesized and characterized. [Pt(bpy-H)(CH<sub>3</sub>)(PMe<sub>3</sub>)] (<b>1</b>), where bpy-H = κ<sup>2</sup><i>N</i>,<i>C</i>-2,2′-bipyridine,
was
obtained from the electron-rich precursor <i>cis</i>-[Pt(CH<sub>3</sub>)<sub>2</sub>(DMSO)<sub>2</sub>] with a one-pot, two step
synthesis; its reactivity has been tested with CH<sub>3</sub>I, giving
the corresponding Pt(IV) complex <i>cis</i>-[Pt(bpy-H)(CH<sub>3</sub>)<sub>2</sub>(I)(PMe<sub>3</sub>)] (<b>2</b>), which
was fully characterized. Crystals suitable for X-ray analysis were
obtained and allowed the determination of the structure of isomer <b>2A</b> which is the product of the <i>trans</i> addition
of CH<sub>3</sub>I, usually thought of as the <i>kinetic</i> product
