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Agarwal – Pd-Sn Bond Enables the Formation of Pd-Aryl Bonds through Oxidative Addition of Aryl Halides

 

Pd-Sn Bond Enables the Formation of Pd-Aryl Bonds through Oxidative Addition of Aryl Halides (2024)

Undergraduate: Amil Agarwal


Faculty Advisor: Michel Gagne
Department: Chemistry

A palladium silyl cation species was developed by the Gagne Lab. The palladium silyl cation complex was able to reduce (sp3)C-O bonds. Tin is the next most electronegative element behind silicon and hence has a lower oxophilicity (the affinity of an element to bind to oxygen). In this work, a (XantPhos)Pd-SnBu3+ complex was synthesized and characterized with a BArF24- counterion. The complex was found to be air-stable, and a crystal structure was obtained. The complex was unable to complete the C-O bond reductions, yet it was found that carbon nucleophiles attack the palladium and cleave the Pd-Sn bond. This work also presents the (XantPhos)Pd-SnBu3 complex cleaving aryl halide bonds to form a Pd-Aryl bond with the elimination of SnBu3, where electron-poor rings better reacted with the complex. This occurred due to the nature of the Pd(II) complex potentially going through a high-valent Pd(IV) species for this oxidative addition and sequential reductive elimination. This work shows the characteristics of the Pd-Sn bond as the Sn-O bond doesn’t form, yet when Pd-C bonds form, the energy of the formation of the bond is large enough to cleave Pd-Sn bonds.