10.1021/ja981670w.s001 Alan R. Brown Alan R. Brown Zijian Guo Zijian Guo Fred W. J. Mosselmans Fred W. J. Mosselmans Simon Parsons Simon Parsons Martin Schröder Martin Schröder Lesley J. Yellowlees Lesley J. Yellowlees Structural and Voltammetric Studies on the Reduction of the Bis(2,2‘-bipyridyl)platinum(II) Cation in Aprotic Media American Chemical Society 1998 EXAFS couple bpy Pt 2 NMR scan cation 1998-08-18 00:00:00 Journal contribution https://acs.figshare.com/articles/journal_contribution/Structural_and_Voltammetric_Studies_on_the_Reduction_of_the_Bis_2_2_-bipyridyl_platinum_II_Cation_in_Aprotic_Media/3670989 The reduction of the bis(2,2‘-bipyridyl)platinum(II) cation, [Pt(bpy)<sub>2</sub>]<sup>2+</sup>, in aprotic media has been studied electrochemically. Voltammetry at scan rates above 500 V s<sup>-1</sup> reveals three reversible reductions at −1.14, −1.45, and −2.07 V versus the ferrocenium/ferrocene couple. The first of these couples shows only a moderately fast electron transfer. At lower scan rate, e.g., 0.1 V s<sup>-1</sup>, or on the time scale of an electrosynthesis, the product of the first one-electron reduction is shown to be the previously unknown homoleptic platinum(I) dimeric cation (μ<sub>2</sub>-2,2‘-bipyridyl)bis(2,2‘-bipyridyl)bisplatinum(I), [Pt<sub>2</sub>(bpy)<sub>3</sub>]<sup>2+</sup>, an X-ray crystal structure of which is presented along with 2-D NMR and EXAFS results showing this is also the major species in solution. The formation of [Pt<sub>2</sub>(bpy)<sub>3</sub>]<sup>2+</sup> is shown by digital simulation of voltammetric results to be by a first-order process initiated by one-electron reduction of [Pt(bpy)<sub>2</sub>]<sup>2+</sup>, and subsequent ligand loss before insertion into the Pt−N bond of another molecule of reduced monomer. Electrolysis in the absence of inert electrolyte is shown to be a viable means of producing pure samples of the products of electrode reactions, even in cases where these are delicate or unstable.