84. Garduño, J. A.; Glueck, D. S.; Hernandez, R. E.; Figueroa, J. S.; Rheingold, A. L. Protonolysis of the [B(Ar_F)₄]⁻ Anion Mediated by Nucleophile/Electrophile/Water Cooperativity in a Platinum–PMe₂OH Complex. Organometallics 2022, 41, 1475–1479.

Abstract

The weakly coordinating fluorinated tetraarylborate anion [B(Ar_F)₄]⁻ (Ar_F = 3,5-(CF₃)₂C₆H₃), which is routinely used to stabilize highly electrophilic cations, is prized for its resistance to decomposition; B–C cleavage requires extremely strong acids. However, cooperation between an electrophilic Pt dication, a nucleophilic PMe₂OH ligand, and the weak acid water resulted in protonolysis of three [B(Ar_F)₄]⁻ B–C bonds at room temperature. Treatment of [Pt((R,R)-Me-FerroLANE)(PMe₂OH)][OTf]₂ (2) with water and 2 equiv of [Na][B(Ar_F)₄] gave 3 equiv of the arene Ar_FH and the metallacycle [Pt((R,R)-Me-FerroLANE)(PMe₂OB(Ar_F)O)][B(Ar_F)₄] (4) via the isolated intermediate metallacycle [Pt((R,R)-Me-FerroLANE)(PMe₂OB(Ar_F)₂OH)][B(Ar_F)₄] (3).