No abstract

No abstract

No abstract

The syntheses of silver(1) salts of the weakly coordinating anions Nb(OTeF&-, Sb(OTeF&-, Ti(OTeF5)62-, zr(OTeF5)~~-, and Hf(OTeF5)62-are reported. The reactions took place in high yields in two steps using commerically available HOTeF5, AgF, and either NbC15, SbC15, TiCb, ZrCb, or HfC4. Metathesis reactions of some of the silver (1) salts with CPh3C1 and [N(n-Bu)4][Cl] afforded [CPh3][Nb(OTeF&], [CPh3][Sb(OTeF5)6], [N(n-Bu)4][Nb(OTeFs)6], [N(n-Bu)41[Sb(OTeF~)6], and [N(n-B~)4]2[Ti(OTeF5)6]. Recrystallization of AgzTi-(OTeF5)6, AgNb(OTeF&, and AgSb(OTeF& from dichloromethane, dibromomethane, and 1 ,Zdibromoethane, respectively, afforded diffraction-quality crystals of the dihaloalkane complexes [Ag(CH2C12)~]2[Ti(OTeFs)6], [Ag(CH2Br2)31 [Nb(OTeFM, and [catena-poly [Ag( 1,2-C2H4Br2)2-p-( 1 ,Z!-C~H~B~~)-B~:BI']] [ Sb(OTeF5)6]. Crystallographic data for [Ag(CH2C12)3]2[Ti(OTeF5)6]: triclinic, Pi, a = 10.944(2) A, b = 10.989(2) A, c = 11.144(2) A, a = 66.83(3)", p = 75.09(3)", y = 83.44(3)", Z = 1, T = -135(1) "C, R = 0.068. Crystalloographic data for [Ag(CH2Br2)3][Nb(OTeF&,]: monoclinic, C2/c, a = 14.302(3) A, b = 13.224(3) A, c =21.537(4) A, p = 96.16(3)", Z = 4, T = -128(1)"C, R = 0.059. -Crystallographic data for [catena-poly[Ag(l,2-C2H4Br2)2-,uu-(1,2-C2H4Br2)-Br:Br']][Sb(0TeF5)6]: triclinic, P1, a = 9.772(1) A, b = 9.784(1) A, c = 10.992(1) A, a = 86.85(1)", p = 87.07(1)", y = 84.21(1)", Z = 1, T = -97(1) "C, R = 0.062. The latter two structures, with AgBr6 coordination spheres, are the first two examples of bromoalkane complexes of any metal. The stability of the anions toward reaction with various solvents, other weakly coordinating anions, and the electrophiles HOTeF5 and AgOTeF5 was investigated. The Nb(OTeF5)C anion reacted with acetonitrile or OTeF5-to form F5TeOTeF5 and NbO(OTeF5)4(CH3CN)-or Nb0(OTeF5)52-, respectively. The order of stability of the anions with respectto the electrophiles is Sb(OTeF&-> Nb(OTeF&->> Ti(OTeF5),j2--B(OTeF5)4-. It was concluded that the Sb(OTeF5)C anion will probably be the most useful weakly coordinating anion in its class.

No abstract