thallium hydrotris(3-isopropyl-4-bromopyrazol-1-yl)borate | 119010-19-4

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 芳基卤化物
• 英文名称: thallium hydrotris(3-isopropyl-4-bromopyrazol-1-yl)borate
• 英文别名: Tl[hydrotris(3-isopropyl-4-bromopyrazolyl)borate]；thallium(I) tris(Br(i-C3H7)pyrazolylborate)；thallium(1+);tris(4-bromo-3-propan-2-ylpyrazol-1-yl)boranuide
• CAS: 119010-19-4
• 化学式: C₁₈H₂₅BBr₃N₆*Tl
• 分子量: 780.343
• InChiKey: GZFOBDDIOLACHH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.21
• 重原子数：
  29.0
• 可旋转键数：
  6.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  53.46
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  [RuCl2(hexamethylbenzene)]2 、 thallium hydrotris(3-isopropyl-4-bromopyrazol-1-yl)borate 以 二氯甲烷 为溶剂， 反应 3.0h， 以87%的产率得到[RuCl(hmb)(Tp^iPr,4Br)]
  参考文献：
  名称：

  具有卤素取代的双和三（吡唑-1-基）硼酸酯配体的新型RuII（芳烃）配合物

  摘要：

  [RuCl（arene）（μ‐Cl）] 2二聚体以摩尔比为1：2的双和三（吡唑基）硼酸酯配体[Na（Bp ）]，[Tl（Tp ）]的钠盐或al盐处理，和[Tl（Tp i Pr，4Br）]。单核中性配合物将[RuCl（芳烃）（κ 2 -BP ）]（1：芳烃= p -cymene（CYM）; 2：芳烃=六甲基苯（HMB）; 3：芳烃=苯（BZ）），将[RuCl（芳烃）（κ 2 -TP ）]（4：芳烃= CYM; 6：芳烃= BZ），以及将[RuCl（芳烃）（κ 2 -TP我PR，4BR）]（7：芳烃= CYM，8：芳烃= HMB，9：芳烃= BZ）已经与外被始终得到的离子型的[Ru 2（HMB）2（μ-Cl）的3 ] [TP （5' ），其独立地形成的比的反应物和使用的反应条件。离子的[Ru（CH 3 OH）（CYM）（κ 2 -BP ）] [X]（10：X = PF 6，12：X = O 3

  DOI：

  10.1002/chem.201304406
• 作为产物：
  描述：

  4-溴-3-异丙基-1H-吡唑 以 四氢呋喃 、 水 为溶剂， 生成 thallium hydrotris(3-isopropyl-4-bromopyrazol-1-yl)borate
  参考文献：
  名称：

  Trofimenko, Swiatoslaw; Calabrese, Joseph C.; Domaille, Peter J., Inorganic Chemistry, 1989, vol. 28, # 6, p. 1091 - 1101

  摘要：

  DOI：

文献信息

• Variable Coordination Modes of Hydrotris(3-isopropyl-4-bromopyrazolyl)borate (Tp‘) in Fe(II), Mn(II), Cr(II), and Cr(III) Complexes:  Formation of MTp‘Cl (M = Fe and Mn), Structural Isomerism in CrTp‘₂, and the Observation of Tp‘ ^- as an Uncoordinated Anion
  作者：Tim J. Brunker、Tony Hascall、Andrew R. Cowley、Leigh H. Rees、Dermot O'Hare

  DOI：10.1021/ic010125k

  日期：2001.6.1

  The syntheses of the 4-coordinate Tp'MCl complexes (where M = Fe (1), Mn (2); and Tp' = hydrotris(3-isopropyl-4-bromopyrazolyl)borate) are described. The single-crystal X-ray structures show that the metal centers have distorted tetrahedral coordination. Analogous reaction of CrCl(2)(MeCN)(2) with TlTp' gave Cr(kappa(3)-Tp')(kappa(2)-Tp') (3) as the initial product. The 5-coordinate structure was assigned

  描述了4-配位的Tp'MC1配合物（其中M = Fe（1），Mn（2）； Tp'=氢三（3-异丙基-4-溴吡唑基）硼酸酯）的合成。X射线单晶结构表明，金属中心的四面体配位变形。CrCl（2）（MeCN）（2）与TlTp'的类似反应得到Cr（kappa（3）-Tp'）（kappa（2）-Tp'）（3）作为初始产物。通过单晶X射线晶体学确定5坐标结构，发现kappa（3）配体已异构化为氢（3-异丙基-4-溴吡唑基）（2）（5-异丙基-4-溴吡唑基）硼酸酯）。3在溶液中不稳定：在戊烷中缓慢转化为六坐标异构体Cr（kappa（3）-Tp'）（2）（4），其结构由X射线晶体学确定。在4个中，两个配体均被异构化。3和4均显示Jahn-Teller扭曲的结构，适用于高旋转d（4）配置。可变温度磁化率测量结果确认1、2和3均具有5-300 K范围内的高自旋电子构型。在苯溶液3中分解；通过X射线晶体学鉴定了
• Efficient mechanochemical synthesis of tris(pyrazolylborate) complexes of manganese(II), cobalt(II) and nickel(II)
  作者：Sergey V Kolotilov、Anthony W Addison、Swiatoslaw Trofimenko、William Dougherty、Vitaly V Pavlishchuk

  DOI：10.1016/j.inoche.2004.01.009

  日期：2004.4

  Abstract A mechanochemical synthesis of Mn(II), Co(II) and Ni(II) tris(pyrazolylborates) (Tp−) was developed, which enabled preparation of metal complexes of the type TpMCl and TpMCl · Hpz type (Hpz is the substituted pyrazole generated by hydrolysis of the corresponding Tp− ligand). The X-ray structure of a new Co(II) tris(pyrazolylborate) and the electronic spectra of these coordination compounds

  摘要 开发了 Mn(II)、Co(II) 和 Ni(II) 三（吡唑基硼酸盐）（Tp−）的机械化学合成方法，能够制备 TpMCl 和 TpMCl·Hpz 型（Hpz 是取代的相应的 Tp-配体水解产生的吡唑）。讨论了新的 Co(II) 三（吡唑基硼酸酯）的 X 射线结构和这些配位化合物的电子光谱。
• Synthesis and Reactivity of Hydridotris(pyrazolyl) Borate Dihydrogen Ruthenium Complexes
  作者：Beatriz Moreno、Sylviane Sabo-Etienne、Bruno Chaudret、Ana Rodriguez、Felix Jalon、Swiatoslaw Trofimenko

  DOI：10.1021/ja00133a017

  日期：1995.7

  The reaction of various hydridotris(pyrazolyl) borate salts with RuHCl(COP)(bpm) (3) (bpm = bispyrazolylmethane; COD = 1,5-cyclooctadiene) produces LRuH(COD) (L = hydridotris(3,5-dimethylpyrazolyl) borate, Tp*, 4a; hydridotris(3-isopropyl-4-bromopyrazoly) borate, Tp',4b). Hydrogenation of 4a,b under 3 bar of dihydrogen in pentane yields LRuH(H-2)(2) in high yield (L = Tp*, 5a; L = Tp', 5b). 5a,b were characterized by classical analytical and spectroscopic methods including T-1 measurements (5a, T-1min = 26 ms at 163 K, 400 MHz; 5b, T-1min = 28 ms at 182 K, 300 MHz) and by partial deuteration leading to the sequential observation of the series of isotopomers LRuH(5-x)D(x) (x = 1-4). The observed J(H-D) coupling constant in these isotopomers of 5a and 5b, respectively 5.4 and 5.2 Hz, allows the calculation of J(H-D) of coordinated hydrogen deuteride, namely 27 and 26 Hz, in agreement with two unstretched dihydrogen ligands. Hydrogenation of 4a or 4b in the presence of a ligand L' or substitution of H-2 by L' in 5a or 5b leads to the new hydrido dihydrogen complexes LRuH(H-2)L' (L' = PCy(3), L = Tp*, 6a; L = Tp', 6b; L' = THT, L = Tp*, 7a; L = Tp', 7b; L' = py, L = Tp*, 8a; L = Tp', 8b; L' = NHEt(2), L = Tp*, 9a). Hydrogenation of 4a in the presence of excess ligand L' leads to the disubstituted complexes Tp*RuH-(L')(2) (L' = py, 10a; L' = THT, 11a). T-1 measurements for 10a and 11a allow the determination of the relaxation for a monohydride in these systems, and thus the calculation of the H-H distance of the coordinated dihydrogen molecules in 5a-9a yields values in each case near 0.9 Angstrom. Substitution of H-2 in 5a occurred with CO to yield Tp*RuH(CO)(2) (12a). Surprisingly, 5a does not react with CH3I, CH3COOH, and CF3COOH but does with HBF4 . Et(2)O and CF3SO3H. The latter reaction leads in the presence of MeCN to [Tp*Ru(MeCN)(3)](CF3SO3) (14a). Finally, both 5a and 5b readily undergo H/D exchange at room temperature between deuterated aromatic solvents (C6D6 or C6D5CD3) and both the ruthenium bound hydrogens and the methyl and pyrazolyl groups of the ligands, thus demonstrating the high reactivity of these compounds for C-H activation.