thallium hydrotris-(3-phenylpyrazol-1-yl)borate

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: thallium hydrotris-(3-phenylpyrazol-1-yl)borate
• 英文别名: thallium hydrotris(3-phenylpyrazol-1-yl)borate；thallium hydrotris(3-phenylpyrazolil)borate；thallium tris(3-phenylpyrazolyl)borate；thallium(1+);tris(3-phenylpyrazol-1-yl)boranuide
• 化学式: C₂₇H₂₂BN₆*Tl
• 分子量: 645.706
• InChiKey: XMSGXRIPNILLCI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.56
• 重原子数：
  35
• 可旋转键数：
  6
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  53.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  thallium hydrotris-(3-phenylpyrazol-1-yl)borate 以 四氢呋喃 、 乙醚 为溶剂， 生成 bis[hydrotris(3-phenyl-1-pyrazolyl)borato]cadmium(II)
  参考文献：
  名称：

  Mixed-ligand complexes of cadmium(II) containing bulky polydentate nitrogen-based ligands

  摘要：

  The reaction of equimolar amounts of CdCl2, Tl[H2B(3-Bu(1)pz)(2)] (pz = pyrazolyl ring) and Na[Et2NCS2] yields [H2B(3-Bu(1)pz)(2)]Cd(S2CNEt2) (1) and a similar reaction using Tl[HB(3-Bu(1)pz)(3)] yields [HB(3-Bu(1)pz)(3)]Cd(S2CNEt2) (2). The solid state structure of [HB(3-Bu(1)pz)(3)]Cd(S2CNEt2) shows the arrangement of the donor atoms is a distorted trigonal bipyramid, an unusual geometry for a molecule containing a tridentate [HB(3-Bu(1)pz)(3)](-) ligand. Mixing CdCl2 with 2 equiv. of MeLi yields the Me2Cd intermediate that reacts with Tl[HB(3-Phpz)(3)] to yield [HB(3-Phpz)(3)]CdCH3 (3). Compound 3 reacts with thiotoluene to yield [HB(3-Phpz)(3)]CdS(p-C6H4CH3) (4) and mercaptopyridine to yield [HB(3-Phpz)(3)]Cd(SNC6H4) (5). The neutral 2,6-bis(2,6-dimethylphenylimino)pyridine ligand (pydim) reacts with CdCl2 in equimolar amounts to yield the adduct (pydim)CdCl2 (6). The cadmium(II) is in a five-coordinate arrangement that is best described as a distorted trigonal bipyramid. The three nitrogen atoms of the planar pyridine ligand occupy an equatorial and both axial sites, but the intrinsic bite angle of the ligand forces a significant distortion in the axial bond angle. Compound 6 reacts with an equimolar amount of Na[Et2NCS2] to yield [(pydim)Cd(S2CNEt2)][Cl] (7). The reaction of equimolar amounts of pydimMe(2) and Cd(NO3)(2) yields (pydimMe(2))Cd(NO3)(2) (8). In the structure of this complex, one nitrate ligand is bidentate and the other monodentate. If the bidentate ligand is considered as occupying one site of a polyhedron, the structure of 8 can be considered as a trigonal bipyramid, very similar to that of 6. (C) 2002 Elsevier Science B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(02)00735-1
• 作为产物：
  描述：

  thallium(I) nitrate 、 potassium hydridotris(3-phenylpyrazol-1-yl)borate 以 四氢呋喃 、 水 为溶剂， 以80%的产率得到thallium hydrotris-(3-phenylpyrazol-1-yl)borate
  参考文献：
  名称：

  杂蝎形三吡唑基硼酸盐配体的配合物。第十一部分。通过 X 射线晶体学研究氢三（3-苯基吡唑基）硼铊（I）和氢双（5-甲基-3-苯基吡唑基）（3,5-二甲基吡唑基）硼铊（I）晶体中的弱 CH/π 相互作用

  摘要：

  用晶体学研究了杂蝎酸氢双 (3-苯基-5-甲基吡唑基)(3,5-二甲基吡唑基) 硼酸盐和氢三(3-苯基吡唑-1-基) 硼酸盐的铊 (I) 配合物。两种配体通过吡唑-1-基部分的N 2 原子以κ 3 方式配位。两种化合物都结晶为中心对称二聚体，其中弱 CH/π 内和二聚体间相互作用是晶体结构排列的原因。

  DOI：

  10.1016/j.molstruc.2003.12.002

文献信息

• A New, Efficient and Direct Preparation of TlTp and Related Complexes with TlBH ₄
  作者：Masato Kitamura、Yuta Takenaka、Tomoko Okuno、Ralph Holl、Bernhard Wünsch

  DOI：10.1002/ejic.200701366

  日期：2008.3

  Establishment of a highly reliable and safe procedure for the preparation of TlBH4 has led to, for the first time, a simple approach to TlTp-related complexes, which are known as mild and efficient Tp-transfer reagents to a variety of metals. The practical use of this method has been demonstrated by the efficient synthesis of (S,S,S)-TlTp4Bo3MeCpenta from a new and hard-to-obtain chiral pyrazole (HPz). In view

  建立了高度可靠和安全的 TlBH4 制备程序，这首次导致了一种简单的方法来制备 TlTp 相关配合物，这些配合物被称为对各种金属的温和高效的 Tp 转移试剂。该方法的实际用途已通过从一种新的且难以获得的手性吡唑 (HPz) 有效合成 (S,S,S)-TlTp4Bo3MeCpenta 得到证明。鉴于蝎子的重要性，这种新方法应该引起广泛科学技术领域研究人员的关注。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)
• Investigation of the C−H Activation Potential of [Hydrotris(1H-pyrazolato-κN1)borato(1−)]iridium (IrTpx) Fragments Featuring Aromatic Substituentsx at the 3-Position of the Pyrazole Rings, The Choice of the Precursor
  作者：Christian Slugovc、Kurt Mereiter、Swiatoslaw Trofimenko、Ernesto Carmona

  DOI：10.1002/1522-2675(20011017)84:10<2868::aid-hlca2868>3.0.co;2-p

  日期：2001.10.17

  (Tpx=TpPh and TpTh) and their capability to activate C−H bonds is presented. As a test reaction, the double C−H activation of cyclic-ether substrates leading to the corresponding Fischer carbene complexes was chosen. Under the reaction conditions employed, the parent compound [Ir(TpPh)(ethene)2] was not isolable; instead, (OC-6-25)-[Ir(TpPhκCPh,κ3N,N′,N″)(ethyl)(η2-ethene)] (1) was formed diastereoselectively

  一系列吡唑取代的 [hydrotris(1H-pyrazolato-κN1)borato(1-)] 铱配合物，具有一般组成 [Ir(Tpx)(烯烃)2] (Tpx=TpPh 和 TpTh) 及其激活 C 的能力呈现-H键。作为测试反应，选择环醚底物的双 C-H 活化导致相应的 Fischer 卡宾配合物。在所采用的反应条件下，母体化合物[Ir(TpPh)(乙烯)2]是不可分离的；相反，(OC-6-25)-[Ir(TpPhκCPh,κ3N,N',N")(乙基)(η2-乙烯)] (1) 是非对映选择性形成的。进一步加热后，1 可以专门转化为 (OC-6-24)-[Ir(TpPhκ2CPh,CPh,κ3N,N',N")(η2-乙烯)] (2)。配合物 1（而非 2）与 THF 反应生成 (OC-6-35)-[Ir(TpPhκ3N,N',N")H(dihydrofuran-2(3H)-ylidene)]
• Catalytic Copolymerization of Ethene and Carbon Monoxide on Nickel Complexes
  作者：Bernd Domhöver、Wolfgang Kläui、Andreas Kremer-Aach、Ralf Bell、Dietrich Mootz

  DOI：10.1002/(sici)1521-3773(19981116)37:21<3050::aid-anie3050>3.0.co;2-m

  日期：1998.11.16

  Can palladium be replaced by nickel? For the industrial copolymerization of carbon monoxide and ethene a palladium catalyst is used which cannot be recovered-a cheaper procedure would be desirable. The presented complex 1 is the first structurally characterized nickel compound which does not polymerize ethene but a mixture from carbon monoxide and ethene unter mild conditions to give a perfectly alternating

  钯可以用镍代替吗？对于一氧化碳和乙烯的工业共聚，使用不能回收的钯催化剂，将需要更便宜的方法。提出的配合物1是第一种在结构上具有特征的镍化合物，该化合物在不温和的条件下不会聚合乙烯，而是一氧化碳和乙烯的混合物，以得到完全交替的聚酮。
• Molecular Design of Single-Site Metal Alkoxide Catalyst Precursors for Ring-Opening Polymerization Reactions Leading to Polyoxygenates. 1. Polylactide Formation by Achiral and Chiral Magnesium and Zinc Alkoxides, (η³-L)MOR, Where L = Trispyrazolyl- and Trisindazolylborate Ligands
  作者：Malcolm H. Chisholm、Nancy W. Eilerts、John C. Huffman、Suri S. Iyer、Martha Pacold、Khamphee Phomphrai

  DOI：10.1021/ja002160g

  日期：2000.12.1

  Single-site achiral and chiral C-3-symmetric complexes LMOR, where M = Mg and Zn, L = an eta (3)-trispyrazolyl- or eta (3)-trisindazolyl-borate ligand and R = Et, Bu-t, Ph, or SiMe3, have-been synthesized and employed in the ring-opening polymerization of L-, rac-, and meso-lactide in CH2Cl2 at 25 degreesC and below. The polymerization occurs by acyl cleavage and gives rise to polylactide, PLA, with PDI of 1.1-1.25 up to 90% conversion. Studies of the kinetics of polymerization reveal first order behavior in both lactide and metal catalyst. For L = tris(3-tert-butylpyrazolyl)borate, ((t)Bupz)(3)BH, polymerization of similar to 500 equiv of L-lactide proceeds to 90% conversion within 1 h and 6 d for the magnesium and zinc catalysts, respectively. The zinc complexes are, however, more tolerant to air and moisture and solid samples where R = SiMe3 are persistent in air for several days. The rate of polymerization is also significantly influenced by the nature of the eta (3)-L spectator li,ligand. Chiral C-3-symmetric catalysts, where L = tris(indazolyl)borates derived:from camphor and menthone, show only slight enantioselectivity in their polymerization of rac-lactide but do show significant diastereoselectivity in their ability to preferentially polymerize meso-lactide from a mixture of rac- and meso-lactide. The poly(mesolactide) shows a modest preference for syndiotactic junctions, RSRSRS. The molecular structures, deduced from single-crystal X-ray crystallography, are reported for eta (3)-HB(3-Phpz)(3)MgEt(THF), [eta (3)-HB((7R)-Pr-i-(4R)-Me-4,5,6,7-tetrahydro-2H-indazolyl)(3)]ZnMe and [eta (3)-HB(3-(t)Bupz)(3,5-(CF3)(2)pz)(2)]-ZnOSiMe3 and serve as structural models for activated and ground-state configurations of the metal ions during the polymerization reaction. The molecular structure of meso-lactide is also reported. These results are compared with polymerizations of lactide by other coordinate catalysts.
• Structural characterization and electrochemical properties of nickel (II) complexes bearing sterically bulky hydrotris(3-phenyl)- and hydrotris(3-tert-butylpyrazol-1-yl)borato ligands
  作者：Alycia K. Frampton、Kathryn Gartland、Nicholas A. Piro、W. Scott Kassel、William G. Dougherty

  DOI：10.1016/j.poly.2015.11.032

  日期：2016.8

  Two series of pseudo-tetrahedral nickel (II) complexes bearing the bulky hydrotris(3-phenyl)- or hydrotris(3-tert-butylpyrazol-1-yl)borato ligands, (TeNiL)-Ni-Ph and (TrNiL)-Ni-tBu respectively, have been synthesized and characterized with the intent of investigating the affects of substituent size on the redox properties of the nickel center (L = Cl, Br, I, NCS, NO3). X-ray analysis reveals both Tp ligands bind in a kappa(3) fashion with the R groups pointing out towards the metal producing a pocket in which the 4th ligand, L, resides. The Tp(Ph) ligand results in a larger pocket and produces nickel complexes with distorted solid-state geometries, specifically bent B center dot center dot center dot Ni center dot center dot center dot L angles, unlike the corresponding Tp(tBu) complexes which show much less variation in structure. Cyclic voltammetry experiments indicate all complexes undergo a Ni2+/1+ reduction at large negative potentials vs. ferrocene with varying levels of reversibility. The NCS complexes are the most reversible and the easiest to reduce with an average reduction potential of -1.51 V due to the slightly electron withdrawing nature of the thiocyanate ligand. The strong donor properties of the bidentate nitrate ligand result in complexes that are the most difficult to reduce at an average of -1.80 V. Overall, the Tp(Ph)NiL complexes are easier to reduce than their corresponding Tp(tBu)NiL complexes resulting from the weakened donor ability of the Tp(Ph) ligand. While the two ligands do produce different structural motifs, the electrochemical trends are more in line with the electronic properties of the complexes than structural differences. (C) 2015 Elsevier Ltd. All rights reserved.