Role of Axial Ligation in Gating the Reactivity of Dimethylplatinum(III) Diimine Radical Cations

Electrochemical methods are coupled with chemical oxidant-based analytical strategies to evaluate the oxidative reactivity of the platinum­(II) diimine complex (bpy)­PtII(CH3)2 (bpy = 2,2′-bipyridine) in coordinating and noncoordinating media. Through this mechanistic analysis, we show that the one-...

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Bibliographic Details
Published in:Organometallics 2021-02, Vol.40 (3), p.333-345
Main Authors: Huffman, Brittany L, Lee, Katherine J, Geer, Ana M, McKeown, Bradley A, Jia, Xiaofan, Dickie, Diane A, Gunnoe, T. Brent, Dempsey, Jillian L
Format: Article
Language:English
Subjects:
Cations
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Oligomers
Oxidation
Platinum
Redox reactions
SOLAR ENERGY
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Summary:Electrochemical methods are coupled with chemical oxidant-based analytical strategies to evaluate the oxidative reactivity of the platinum­(II) diimine complex (bpy)­PtII(CH3)2 (bpy = 2,2′-bipyridine) in coordinating and noncoordinating media. Through this mechanistic analysis, we show that the one-electron oxidation of (bpy)­PtII(CH3)2 generates a highly reactive, 15-electron PtIII radical cation and identify three reaction pathways that can follow this oxidation: radical–substrate dimerization, radical–radical dimerization, and oxidative disproportionation. Axial ligation of the initially generated [(bpy)­PtIII(CH3)2]•+ species is a critical driver of this reactivity, gating the available mechanistic pathways and tuning the competition between radical–radical dimerization and oxidative disproportionation.
ISSN:0276-7333
1520-6041
DOI:10.1021/acs.organomet.0c00663