Inorganic Chemistry, Vol.34, No.13, 3453-3464, 1995
Weakly Coordinating Anions M(Otef5)(6)(-) (M=nb,Sb) and M(Otef5)(6)(2-) (M=ti,Zr,HF) - 2-Step Synthesis, Characterization, Stability, and Use in the Isolation of the Dihaloalkane Complex Cations Ag(CH2Cl2)(3)(+), Ag(Ch2Br2)(3)(+), and Catena-Poly(Ag(1,2-C2H4Br2)(2)-Mu-(1,2-C2H4Br2)-Br-Br’)(+)
The syntheses of silver(I) salts of the weakly coordinating anions Nb(OTeF5)(6)(-), Sb(OTeF5)(6)(-), Ti(OTeF5)(6)(2-), Zr(OTeF5)(6)(2-), and Hf(OTeF5)(6)(2-) are reported. The reactions took place in high yields in two steps using commerically available HOTeF5, AgF, and either NbCl5, SbCl5, TiCl4, ZrCl4, or HfCl4. Metathesis reactions of some of the silver(I) salts with CPh(3)Cl and [N(n-Bu)(4)][Cl] afforded [CPh(3)][Nb(OTeF5)(6)], [CPh(3)][Sb(OTeF5)(6)], [N(n-Bu)(4)][Nb(OTeF5)(6)], [N(n-Bu)(4)][Sb(OTeF5)(6)], and [N(n-Bu)(4)](2)[Ti(OTeF5)(6)]. Recrystallization of Ag2Ti(OTeF5)(6), AgNb(OTeF5)(6), and AgSb(OTeF5)(6) from dichloromethane,dibromomethane, and 1,2-dibromoethane, respectively, afforded diffraction-quality crystals of the dihaloalkane complexes [Ag(CH2Cl2)(3)](2)[Ti(OTeF5)(6)], [Ag(CH2Br2)(3)][Nb(OTeF5)(6)], and [catena-poly[Ag(1,2-C2H4Br2)(2)-mu-(1,2-C2H4Br2)-Br.Br’]][Sb(OTeF5)(6)]. Crystallographic data for [Ag(CH2Cl2)(3)](2)[Ti(OTeF5)(6)] : triclinic, P ($) over bar 1, a = 10.944(2) Angstrom, b = 10.989(2) Angstrom, c = 11.144(2) Angstrom, alpha = 66.83(3)degrees, beta = 75.09(3)degrees, gamma = 83.44(3)degrees, Z = 1, T = -135(1) degrees C, R = 0.068. Crystalloographic data for [Ag(CH2Br2)(3)][Nb(OTeF5)(6)] : monoclinic, C2/c, a = 14.302(3) Angstrom, b = 13.224(3) Angstrom, c = 21.537(4) Angstrom, beta = 96.16(3)degrees, Z = 4, T = -128(1)degrees C, R = 0.059.
Keywords:CRYSTAL-STRUCTURE;ETHYLENE POLYMERIZATION;OTEF5 LIGAND;SILVER SALT;LEWIS-ACIDS;CHEMISTRY;DICHLOROMETHANE;DERIVATIVES;CATALYSIS;SOLVENT