Novel Silicate Platform as Weakly‐Coordinating Anions for Diverse Organometallic and Electrochemical Applications

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 si licates bearing f luorinated pinacolate ligands, “[ R Si F 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 + , Ph 3 C + , Fc + , [Ni I (COD) 2 ] + . [Pd(dppe)(NCMe)Me] + has been generated by salt metathesis or protonation of a metal‐alkyl bond, showcasing the ability of the [ R Si F 24 ] − anions to support applications in coordination chemistry and catalysis. Electrochemical studies on the [Bu 4 N] + variant show an exceptionally wide stability window for the [ Me Si F 24 ] − anion of 7.5 V in MeCN. CV experiments demonstrate reversible Mg deposition and stripping.