Syntheses, Solution Multi-NMR Characterization, and Reactivities of [C<sub>6</sub>F<sub>5</sub>Xe]<sup>+</sup> Salts of Weakly Coordinating Borate Anions, [BY<sub>4</sub>]<sup>-</sup> (Y = CF<sub>3</sub>, C<sub>6</sub>F<sub>5</sub>, CN, or OTeF<sub>5</sub>) Karsten Koppe Vural Bilir Hermann-J. Frohn Hélène P. A. Mercier Gary J. Schrobilgen 10.1021/ic7010138.s001 https://acs.figshare.com/articles/journal_contribution/Syntheses_Solution_Multi_NMR_Characterization_and_Reactivities_of_C_sub_6_sub_F_sub_5_sub_Xe_sup_sup_Salts_of_Weakly_Coordinating_Borate_Anions_BY_sub_4_sub_sup_sup_Y_CF_sub_3_sub_C_sub_6_sub_F_sub_5_sub_CN_or_OTeF_sub_5_sub_/2978206 New examples of [C<sub>6</sub>F<sub>5</sub>Xe]<sup>+</sup> salts of the weakly coordinating anions [B(CF<sub>3</sub>)<sub>4</sub>]<sup>-</sup>, [B(C<sub>6</sub>F<sub>5</sub>)<sub>4</sub>]<sup>-</sup>, [B(CN)<sub>4</sub>]<sup>-</sup>, and [B(OTeF<sub>5</sub>)<sub>4</sub>]<sup>-</sup> have been synthesized by metathesis reactions of [C<sub>6</sub>F<sub>5</sub>Xe][BF<sub>4</sub>] with the corresponding M<sup>I</sup>[BY<sub>4</sub>] salts (M<sup>I</sup> = K or Cs; Y = CF<sub>3</sub>, C<sub>6</sub>F<sub>5</sub>, CN, or OTeF<sub>5</sub>). The salts were characterized in solution by multi-NMR spectroscopy. Their stabilities in prototypic solvents (CH<sub>3</sub>CN and CH<sub>2</sub>Cl<sub>2</sub>) and decomposition products are reported. The influence of the coordinating nature of [BY<sub>4</sub>]<sup>-</sup> on the decomposition rate of [C<sub>6</sub>F<sub>5</sub>Xe]<sup>+</sup> as well as the presence of the weakly nucleophilic [BF<sub>4</sub>]<sup>-</sup> ion has been studied. The electrophilic pentafluorophenylation of C<sub>6</sub>H<sub>5</sub>F by [C<sub>6</sub>F<sub>5</sub>Xe][BY<sub>4</sub>] in solvents of different coordinating abilities (CH<sub>3</sub>CN and CH<sub>2</sub>Cl<sub>2</sub>) and the effects of stronger nucleophiles (fluoride and water) on the pentafluorophenylation process have been investigated. Simulations of the <sup>19</sup>F and <sup>129</sup>Xe NMR spectra of [C<sub>6</sub>F<sub>5</sub>Xe]<sup>+</sup> have provided the complete set of aryl <sup>19</sup>F−<sup>19</sup>F and <sup>129</sup>Xe−<sup>19</sup>F coupling constants and their relative signs. The <sup>19</sup>F NMR parameters of the [C<sub>6</sub>F<sub>5</sub>Xe]<sup>+</sup> cation in the present series of salts are shown to reflect the relative degrees of cation−solvent interactions. 2007-10-29 00:00:00 BF BY 129 Xe NMR spectra C 6F cation MI CH 2Cl 19 F NMR parameters C 6F Salts CF C 6F salts 6H C 6F CH 3CN Weakly Coordinating Borate Anions