- [C6F5Xe]+ and [C6F 5XeNCCH3]+ salts of the weakly coordinating borate anions, [BY4]- (Y = CN, CF3, or C 6F5)
-
New examples of [C6F5Xe]+ salts of the weakly coordinating [BY4]- (Y = CN, CF3, or C6F5) anions were synthesized by metathesis of [C 6F5Xe][BF4] with MI[BY4] (MI = K or Cs; Y = CN, CF3, or C6F5) in CH3CN at -40°C, and were crystallized from CH 2Cl2 or from a CH2Cl2/CH 3CN solvent mixture. The low-temperature (-173°C) X-ray crystal structures of the [C6F5Xe]+ cation and of the [C6F5XeNCCH3]+ adduct-cation are reported for [C6F5Xe][B(CF3)4], [C6F5XeNCCH3][B(CF3)4], [C6F5Xe][B(CN)4], and [C6F 5XeNCCH3][B(C6F5)4]. The [C6F5Xe]+ cation, in each structure, interacts with either the anion or the solvent, with the weakest cation-anion interactions occurring for the [B(CF3)4]- anion. The solid-state Raman spectra of the [C6F5Xe]+ and [C6F5XeNCCH3]+ salts have been assigned with the aid of electronic structure calculations. Gas-phase thermodynamic calculations show that the donor-acceptor bond dissociation energy of [C6F5XeNCCH3]+ is approximately half that of [FXeNCCH3]+. Coordination of CH3CN to [C6F5Xe]+ is correlated with changes in the partial charges on mainly Xe, the ipso-C, and N, that is, the partial charge on Xe increases and those on the ipso-C and N decrease upon coordination, typifying a transition from a 2c-2e to a 3c-4e bond.
- Koppe, Karsten,Frohn, Hermann-J.,Mercier, Helene P. A.,Schrobilgen, Gary J.
-
p. 3205 - 3217
(2009/02/01)
-
- Syntheses, solution multi-NMR characterization, and reactivities of [C 6F5Xe]+ salts of weakly coordinating borate anions, [BY4]- (Y = CF3, C6F 5, CN, or OTeF5
-
New examples of [C6F5Xe]+ salts of the weakly coordinating anions [B(CF3)4]_, [B(C6F5)4]-, [B(CN) 4]-, and [B(OTeF5/s
- Koppe, Karsten,Bilir, Vural,Frohn, Hermann-J.,Mercier, Helene P. A.,Schrobilgen, Gary J.
-
p. 9425 - 9437
(2008/10/09)
-