POLYFLUORINATED TRIS(PYRAZOLYL)BORATES - SYNTHESES AND SPECTROSCOPIC AND STRUCTURAL CHARACTERIZATION OF GROUP-1 AND GROUP-11 METAL-COMPLEXES OF [HB(3,5-(CF3)(2)PZ)(3)](-) AND [HB(3-(CF3)PZ)(3)](-)

The fluorinated tris(pyrazolyl)borate ligands [HB(3,5-(CF3)(2)Pz)(3)]( -) and [HB(3-(CF3)Pz)(3)](-) (where Pz = pyrazolyl) have been synthesi zed as their sodium salts from the corresponding pyrazoles and NaBH4 i n high yield. These sodium complexes and the related [HB(3,5-(CF3)(2)P z)(3)]K(DMAC) were used as ligand transfer agents in the preparation o f the copper and silver complexes [HB(3,5-(CF3)(2)Pz)(3)]Cu(DMAC), [HB (3,5-(CF3)(2)Pz)(3)]CuPPh(3), [HB(3,5-(CF3)(2)Pz)(3)]AgPPh(3), and [HB (3-(CF3)Pz)(3)]AgPPh(3). Metal complexes of the fluorinated [HB(3,5-(C F3)(2)Pz)(3)](-) ligand have highly electrophilic metal sites relative to their hydrocarbon analogs. This is evident from the formation of s table adducts with neutral oxygen donors such as H2O, dimethylacetamid e, or thf. Furthermore, the metal compounds derived from fluorinated l igands show fairly long-range coupling between fluorines of the triflu oromethyl groups and the hydrogen, silver, or phosphorus. The solid st ate structures show that the fluorines are in close proximity to these nuclei, thus suggesting a possible through-space coupling mechanism. Crystal structures of the sodium adducts exhibit significant metal-flu orine interactions. The treatment of [HB(3,5-(CF3)(2)Pz)(3)]Na(H2O) wi th Et(4)NBr led to [Et(4)N][HB(3,5-(CF3)(2)Pz)(3)], which contains a w ell-separated [Et(4)N](+) cation and the [HB(3,5-(CF3)(2)Pz)(3)](-) an ion in the solid state. Crystal data with Mo K alpha (lambda = 0.710 7 3 Angstrom) at 193 K: [HB(3,5-(CF3)(2)Pz)(3)]Na(H2O), C15H6BF18N6NaO, a = 7.992(2) Angstrom, b = 15.049(2) Angstrom, c = 9.934(2) Angstrom, beta = 101.16(2)degrees, monoclinic, P2(1)/m, Z = 2; [{HB(3-(CF3)Pz)(3 )}Na(thf)](2), C32H30B2F18N12Na2O2, a = 9.063(3) Angstrom, b = 10.183( 2) Angstrom, c = 12.129(2) Angstrom, alpha = 94.61(1)degrees, beta = 1 01.16(2)degrees, gamma = 95.66(2)degrees, triclinic, <P(1)over bar>, Z = 1; [HB(3,5-(CF3)(2)Pz)(3)]Cu(DMAC), C19H13BCuF18N7O, a = 15.124(4) Angstrom, b = 8.833(2) Angstrom, c = 21.637(6) Angstrom, beta = 105.29 1(14)degrees, monoclinic, P2(1)/n, Z = 4; [HB(3,5-(CF3)(2)Pz)(3)]CuPPh (3), C33H19BCuF18N6P, a = 9.1671(8) Angstrom, b = 14.908(2) Angstrom, c = 26.764(3) Angstrom, beta = 94.891(1)degrees, monoclinic, P2(1)/c, Z = 4; [HB(3,5-(CF3)(2)Pz)(3)]AgPPh(3) . 0.5C(6)H(14), C36H26AgBF18N6P , a = 13.929(2) Angstrom, b = 16.498(2) Angstrom, c = 18.752(2) Angstr om, beta = 111.439(6)degrees, monoclinic, P2(1)/c, Z = 4; [Et(4)N][HB( 3,5-(CF3)(2)Pz)(3)], C23H24BF18N7, a = 10.155(2) Angstrom, b = 18.580( 4) Angstrom, c = 16.875(5) Angstrom, beta = 99.01(2)degrees, monoclini c, P2(1)/n, Z = 4.