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.