一种高度氟化的双（吡唑基）硼酸盐配体的铜（II）、锌（II）和钾配合物的合成与表征

Synthesis and Characterization of Copper(II), Zinc(II), and Potassium Complexes of a Highly Fluorinated Bis(pyrazolyl)borate Ligand.

作者信息

Dias H. V. Rasika, Gorden John D.

机构信息

Department of Chemistry & Biochemistry, The University of Texas at Arlington, Arlington, Texas 76019.

出版信息

Inorg Chem. 1996 Jan 17;35(2):318-324. doi: 10.1021/ic951101e.

DOI:10.1021/ic951101e

PMID:11666211

Abstract

Highly fluorinated, dihydridobis(3,5-bis(trifluoromethyl)pyrazolyl)borate ligand, H(2)B(3,5-(CF(3))(2)Pz)(2) has been synthesized and characterized as its potassium salt. The copper(II) and zinc(II) complexes, H(2)B(3,5-(CF(3))(2)Pz)(2)Cu and H(2)B(3,5-(CF(3))(2)Pz)(2)Zn, have been prepared by metathesis of [H(2)B(3,5-(CF(3))(2)Pz)(2)]K with Cu(OTf)(2) and Zn(OTf)(2), respectively. All the new metal adducts have been characterized by X-ray diffraction. The potassium salt is polymeric and shows several K.F interactions. The Cu center of H(2)B(3,5-(CF(3))(2)Pz)(2)Cu adopts a square planar geometry, whereas the Zn atom in H(2)B(3,5-(CF(3))(2)Pz)(2)Zn displays a tetrahedral coordination. Bis(pyrazolyl)borate ligands in the Zn adduct show a significantly distorted boat conformation. The nature and extent of this distortion is similar to that observed for the methylated analog, H(2)B(3,5-(CH(3))(2)Pz)(2)Zn. This ligand allows a comparison of electronic effects of bis(pyrazolyl)borate ligands with similar steric properties. Crystallographic data for [H(2)B(3,5-(CF(3))(2)Pz)(2)]K: triclinic, space group P&onemacr;, with a = 8.385(1) Å, b = 10.097(2) Å, c = 10.317(1) Å, alpha = 104.193(9) degrees, beta = 104.366(6) degrees, gamma = 91.733(9) degrees, V = 816.5(3) Å(3), and Z = 2. H(2)B(3,5-(CF(3))(2)Pz)(2)Cu is monoclinic, space group C2/c with a = 25.632(3) Å, b = 9.197(1) Å, c = 17.342(2) Å, beta = 129.292(5) degrees, V = 3164.0(6) Å(3), and Z = 4. H(2)B(3,5-(CF(3))(2)Pz)(2)Zn is triclinic, space group P&onemacr;, with a = 9.104(1) Å, b = 9.278(1) Å, c = 18.700(2) Å, alpha = 83.560(6) degrees, beta = 88.200(10) degrees, gamma = 78.637(9) degrees, V = 1538.8(3) Å(3), and Z = 2. H(2)B(3,5-(CH(3))(2)Pz)(2)Zn is monoclinic, space group C2/c with a = 8.445(1) Å, b = 14.514(2) Å, c = 19.983(3) Å, beta = 90.831(8) degrees, V = 2449.1(6) Å(3), and Z = 4.

摘要

已合成了高氟化的二氢双（3,5-双（三氟甲基）吡唑基）硼酸盐配体[H₂B(3,5-(CF₃)₂Pz)₂]⁻，并将其表征为钾盐。通过[H₂B(3,5-(CF₃)₂Pz)₂]K分别与Cu(OTf)₂和Zn(OTf)₂进行复分解反应，制备了铜（II）和锌（II）配合物[H₂B(3,5-(CF₃)₂Pz)₂]₂Cu和[H₂B(3,5-(CF₃)₂Pz)₂]₂Zn。所有新的金属加合物均通过X射线衍射进行了表征。钾盐是聚合物，显示出几种K···F相互作用。[H₂B(3,5-(CF₃)₂Pz)₂]₂Cu中的铜中心采用平面正方形几何构型，而[H₂B(3,5-(CF₃)₂Pz)₂]₂Zn中的锌原子呈现四面体配位。锌加合物中的双（吡唑基）硼酸盐配体显示出明显扭曲的船式构象。这种扭曲的性质和程度与甲基化类似物[H₂B(3,5-(CH₃)₂Pz)₂]₂Zn中观察到的相似。该配体允许比较具有相似空间性质的双（吡唑基）硼酸盐配体的电子效应。[H₂B(3,5-(CF₃)₂Pz)₂]K的晶体学数据：三斜晶系，空间群P-1，a = 8.385(1) Å，b = 10.097(2) Å，c = 10.317(1) Å，α = 104.193(9)° = 104.193(9)度，β = 104.366(6)° = 104.366(6)度，γ = 91.733(9)° = 91.733(9)度，V = 816.5(3) Å³，Z = 2。[H₂B(3,5-(CF₃)₂Pz)₂]₂Cu是单斜晶系，空间群C2/c，a = 25.632(3) Å，b = 9.197(1) Å，c = 17.342(2) Å，β = 129.292(5)° = 129.292(5)度，V = 3164.0(6) Å³，Z = 4。[H₂B(3,5-(CF₃)₂Pz)₂]₂Zn是三斜晶系，空间群P-1，a = 9.104(1) Å，b = 9.278(1) Å，c = 18.700(2) Å，α = 83.560(6)° = 83.560(6)度，β = 88.200(10)° = 88.200(10)度，γ = 78.637(9)° = 78.637(9)度，V = 1538.8(3) Å³，Z = 2。[H₂B(3,5-(CH₃)₂Pz)₂]₂Zn是单斜晶系，空间群C2/c，a = 8.445(1) Å，b = 14.514(2) Å，c = 19.983(3) Å，β = 90.831(8)° = 90.831(8)度，V = 2449.1(6) Å³，Z = 4。