多氟代三（吡唑基）硼酸盐。[HB(3,5-(CF(3))(2)Pz)(3)](-)和[HB(3-(CF(3))Pz)(3)](-)的第1族和第11族金属配合物的合成、光谱及结构表征
Polyfluorinated Tris(pyrazolyl)borates. Syntheses and Spectroscopic and Structural Characterization of Group 1 and Group 11 Metal Complexes of [HB(3,5-(CF(3))(2)Pz)(3)](-) and [HB(3-(CF(3))Pz)(3)](-).
作者信息
Dias H. V. Rasika, Jin Wiechang, Kim Hyoung-Juhn, Lu Hui-Ling
机构信息
Department of Chemistry & Biochemistry, The University of Texas at Arlington, Arlington, Texas 76019.
出版信息
Inorg Chem. 1996 Apr 10;35(8):2317-2328. doi: 10.1021/ic951361w.
The fluorinated tris(pyrazolyl)borate ligands HB(3,5-(CF(3))(2)Pz)(3) and HB(3-(CF(3))Pz)(3) (where Pz = pyrazolyl) have been synthesized as their sodium salts from the corresponding pyrazoles and NaBH(4) in high yield. These sodium complexes and the related [HB(3,5-(CF(3))(2)Pz)(3)]K(DMAC) were used as ligand transfer agents in the preparation of the copper and silver complexes [HB(3,5-(CF(3))(2)Pz)(3)]Cu(DMAC), [HB(3,5-(CF(3))(2)Pz)(3)]CuPPh(3), [HB(3,5-(CF(3))(2)Pz)(3)]AgPPh(3), and [HB(3-(CF(3))Pz)(3)]AgPPh(3). Metal complexes of the fluorinated HB(3,5-(CF(3))(2)Pz)(3) ligand have highly electrophilic metal sites relative to their hydrocarbon analogs. This is evident from the formation of stable adducts with neutral oxygen donors such as H(2)O, dimethylacetamide, or thf. Furthermore, the metal compounds derived from fluorinated ligands show fairly long-range coupling between fluorines of the trifluoromethyl groups and the hydrogen, silver, or phosphorus. The solid state 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-fluorine interactions. The treatment of [HB(3,5-(CF(3))(2)Pz)(3)]Na(H(2)O) with Et(4)NBr led to [Et(4)N][HB(3,5-(CF(3))(2)Pz)(3)], which contains a well-separated Et(4)N cation and the HB(3,5-(CF(3))(2)Pz)(3) anion in the solid state. Crystal data with Mo Kalpha (lambda = 0.710 73 Å) at 193 K: [HB(3,5-(CF(3))(2)Pz)(3)]Na(H(2)O), C(15)H(6)BF(18)N(6)NaO, a = 7.992(2) Å, b = 15.049(2) Å, c = 9.934(2) Å, beta = 101.16(2) degrees, monoclinic, P2(1)/m, Z = 2; {HB(3-(CF(3))Pz)(3)}Na(thf), C(32)H(30)B(2)F(18)N(12)Na(2)O(2), a = 9.063(3) Å, b = 10.183(2) Å, c = 12.129(2) Å, alpha = 94.61(1) degrees, beta = 101.16(2) degrees, gamma = 95.66(2) degrees, triclinic, &Pmacr;1, Z = 1; [HB(3,5-(CF(3))(2)Pz)(3)]Cu(DMAC), C(19)H(13)BCuF(18)N(7)O, a = 15.124(4) Å, b = 8.833(2) Å, c = 21.637(6) Å, beta = 105.291(14) degrees, monoclinic, P2(1)/n, Z = 4; [HB(3,5-(CF(3))(2)Pz)(3)]CuPPh(3), C(33)H(19)BCuF(18)N(6)P, a = 9.1671(8) Å, b = 14.908(2) Å, c = 26.764(3) Å, beta = 94.891(1) degrees, monoclinic, P2(1)/c, Z = 4; [HB(3,5-(CF(3))(2)Pz)(3)]AgPPh(3).0.5C(6)H(14), C(36)H(26)AgBF(18)N(6)P, a = 13.929(2) Å, b = 16.498(2) Å, c = 18.752(2) Å, beta = 111.439(6) degrees, monoclinic, P2(1)/c, Z = 4; [Et(4)N][HB(3,5-(CF(3))(2)Pz)(3)], C(23)H(24)BF(18)N(7), a = 10.155(2) Å, b = 18.580(4) Å, c = 16.875(5) Å, beta = 99.01(2) degrees, monoclinic, P2(1)/n, Z = 4.
已由相应的吡唑和硼氢化钠高产率地合成了氟化三（吡唑基）硼酸根配体HB(3,5-(CF(3))(2)Pz)(3)和HB(3-(CF(3))Pz)(3)（其中Pz = 吡唑基）的钠盐。这些钠配合物以及相关的[HB(3,5-(CF(3))(2)Pz)(3)]K(DMAC)在制备铜和银配合物[HB(3,5-(CF(3))(2)Pz)(3)]Cu(DMAC)、[HB(3,5-(CF(3))(2)Pz)(3)]CuPPh(3)、[HB(3,5-(CF(3))(2)Pz)(3)]AgPPh(3)和[HB(3-(CF(3))Pz)(3)]AgPPh(3)时用作配体转移剂。相对于它们的烃类类似物，氟化HB(3,5-(CF(3))(2)Pz)(3)配体的金属配合物具有高度亲电的金属位点。这从与中性氧供体如H(2)O、二甲基乙酰胺或四氢呋喃形成稳定加合物中可以明显看出。此外，衍生自氟化配体的金属化合物在三氟甲基的氟与氢、银或磷之间显示出相当长程的耦合。固态结构表明氟与这些原子核紧密相邻，因此暗示了一种可能的空间耦合机制。钠加合物的晶体结构表现出显著的金属 - 氟相互作用。用四乙基溴化铵处理[HB(3,5-(CF(3))(2)Pz)(3)]Na(H(2)O)得到[Et(4)N][HB(3,5-(CF(3))(2)Pz)(3)]，其在固态中包含分离良好的Et(4)N阳离子和HB(3,5-(CF(3))(2)Pz)(3)阴离子。在193 K下用Mo Kα（λ = 0.710 73 Å）的晶体数据：[HB(3,5-(CF(3))(2)Pz)(3)]Na(H(2)O)，C(15)H(6)BF(18)N(6)NaO，a = 7.992(2) Å，b = 15.049(2) Å，c = 9.934(2) Å，β = 101.16(2)°，单斜晶系，P2(1)/m，Z = 2；{HB(3-(CF(3))Pz)(3)}Na(thf)，C(32)H(30)B(2)F(18)N(12)Na(2)O(2)，a = 9.063(3) Å，b = 10.183(2) Å，c = 12.129(2) Å，α = 94.61(1)°，β = 101.16(2)°，γ = 95.66(2)°，三斜晶系，&Pmacr;1，Z = 1；[HB(3,5-(CF(3))(2)Pz)(3)]Cu(DMAC)，C(19)H(13)BCuF(18)N(7)O，a = 15.124(4) Å，b = 8.833(2) Å，c = 21.637(6) Å，β = 105.291(14)°，单斜晶系，P2(1)/n，Z = 4；[HB(3,5-(CF(3))(2)Pz)(3)]CuPPh(3)，C(33)H(19)BCuF(18)N(6)P，a = 9.1671(8) Å，b = 14.908(2) Å，c = 26.764(3) Å，β = 94.891(1)°，单斜晶系，P2(1)/c，Z = 4；[HB(3,5-(CF(3))(2)Pz)(3)]AgPPh(3).0.5C(6)H(14)，C(36)H(26)AgBF(18)N(6)P，a = 13.929(2) Å，b = 16.498(2) Å，c = 18.752(2) Å，β = 111.439(6)°，单斜晶系，P2(1)/c，Z = 4；[Et(4)N][HB(3,5-(CF(3))(2)Pz)(3)]，C(23)H(24)BF(18)N(7)，a = 10.155(2) Å，b = 18.580(4) Å，c = 16.875(5) Å，β = 99.01(2)°，单斜晶系，P2(1)/n，Z = 4。
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