School of Science and Technology, Chemistry Division, Università di Camerino, via S. Agostino 1, 62032, Camerino, Macerata, Italy.
Dalton Trans. 2010 Oct 14;39(38):8937-44. doi: 10.1039/c0dt00474j. Epub 2010 Aug 16.
Two scorpionates sodium trihydro(3-nitro-pyrazol-1-yl)borate (Na[H(3)B(3-(NO(2))pz)]) and sodium hydrotris(3-nitro-pyrazol-1-yl)borate (Na[HB(3-(NO(2))pz)(3)]), featuring electron withdrawing substituents, have been synthesized in high yield starting from 3(5)-nitropyrazole and sodium borohydride. The treatment of CuX (X = (CH(3)CN)(4)PF(6), Cl or I) with Na[H(3)B(3-(NO(2))pz)], Na[HB(3-(NO(2))pz)(3)] or the related bis(pyrazolyl)borate Na[H(2)B(3-(NO(2))pz)(2)] in the presence of triphenylphosphine or tert-butyl isocyanide afforded the corresponding (azolyl)borate supported copper(I) triphenylphosphine or tert-butyl isocyanide adducts. These compounds have been characterized by elemental analyses, FT-IR, ESI-MS and multinuclear NMR spectroscopy. X-Ray crystal structures of [H(3)B(3-(NO(2))pz)]CuP(C(6)H(5))(3), [H(2)B(3-(NO(2))pz)]Cu(CNt-Bu)(2), and [HB(3-(NO(2))pz)(3)]Cu[P(C(6)H(5))(3)], as well as that of the {[HB(3-(NO(2))pz)(3)]Na}(4) are also reported. The latter displays a particularly interesting tetrameric structure with each tris(pyrazolyl)borate adopting an unusual inverted configuration and serves as a bridging ligand for three different sodium ions.
两种带有吸电子取代基的硼酸盐，即三羟（3-硝基-吡唑-1-基）硼酸钠（Na[H(3)B(3-(NO(2))pz)]) 和 氢三（3-硝基-吡唑-1-基）硼酸钠（Na[HB(3-(NO(2))pz)(3)]），是从 3(5)-硝基吡唑和硼氢化钠合成而来，产率较高。CuX（X = (CH(3)CN)(4)PF(6), Cl 或 I）与 Na[H(3)B(3-(NO(2))pz)], Na[HB(3-(NO(2))pz)(3)]或相关的双（吡唑基）硼酸钠 Na[H(2)B(3-(NO(2))pz)(2)]在三苯基膦或叔丁基异氰酸酯存在下反应，生成相应的（唑基）硼酸盐负载的一价铜（I）三苯基膦或叔丁基异氰酸酯加合物。这些化合物通过元素分析、FT-IR、ESI-MS 和多核 NMR 光谱进行了表征。[H(3)B(3-(NO(2))pz)]CuP(C(6)H(5))(3)、[H(2)B(3-(NO(2))pz)]Cu(CNt-Bu)(2)和[HB(3-(NO(2))pz)(3)]Cu[P(C(6)H(5))(3)]的 X 射线晶体结构以及{[HB(3-(NO(2))pz)(3)]Na}(4)的结构也已报道。后者显示出一种特别有趣的四聚体结构，每个三（吡唑基）硼酸盐采用不寻常的倒置构型，并作为三个不同钠离子的桥连配体。
