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Updated: Jun 10, 2025

Combining Solid-state and Solution-based Techniques: Synthesis and Reactivity of ChalcogenidoplumbatesII or IV
Published on: December 29, 2016
Novel Silicate Platform as Weakly-Coordinating Anions for Diverse Organometallic and Electrochemical Applications
Tianyi He1, Meaghan A Bruening1, Matthew Espinosa1
1Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125, USA.
Abstract:
Weakly-coordinating anions (WCAs) are employed in a wide range of applications, but limitations remain, including high reactivity, limited redox window, complicated synthesis, high cost, low solublity, and low structural tunabililty. Herein, we report a new class of WCA based on alkyl or aryl (R) substituted silicates bearing fluorinated pinacolate ligands, "[RSiF 24]-". Anions bearing a variety of R groups were prepared, enabling facile tuning of sterics and solubility. A range of cations employed in chemical reactivity has been supported by these anions, including ether-free alkali cations, Ag+, Ph3C+, Fc+, [NiI(COD)2]+. [Pd(dppe)(NCMe)Me]+ has been generated by salt metathesis or protonation of a metal-alkyl bond, showcasing the ability of the [RSiF 24]- anions to support applications in coordination chemistry and catalysis. Electrochemical studies on the [Bu4N]+ variant show an exceptionally wide stability window for the [MeSiF 24]- anion of 7.5 V in MeCN. CV experiments demonstrate reversible Mg deposition and stripping.
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