tris[2-isopropylimidazole-4(5)-yl]phosphane | 678140-25-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: tris[2-isopropylimidazole-4(5)-yl]phosphane
• 英文别名: tris(2-isopropyl-1H-imidazol-4-yl)phosphane；tris(2-isopropylimidazol-4(5)-yl)phosphane；4-TIP(i-Pr)；5,5',5''-Phosphanetriyltris[2-(propan-2-yl)-1H-imidazole]；tris(2-propan-2-yl-1H-imidazol-5-yl)phosphane
• CAS: 678140-25-5
• 化学式: C₁₈H₂₇N₆P
• 分子量: 358.426
• InChiKey: IJYZFQNNSPWOTB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  86
• 氢给体数：
  3
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  tris[2-isopropylimidazole-4(5)-yl]phosphane 在 sulfur 作用下， 以 乙醇 为溶剂， 以85%的产率得到4-TIPS(i-Pr)
  参考文献：
  名称：

  咪唑基磷烷配体的三羰基锰 (I) 和铼 (I) 配合物：取代模式对 CO 释放特性的影响

  摘要：

  咪唑基膦配体三（咪唑-2-基）膦（2-TIPH）、三（N-甲基咪唑-2-基）膦（2-TIPNMe）和三[制备了 2-异丙基咪唑-4(5)-基] 膦 (4-TIPiPr) 以及氧化膦 (4-TIPOiPr) 和硫化物 (4-TIPSiPr) 配体。这些三（咪唑基）配体充当 N,N,N-三足螯合配体。锰配合物 [(2-TIPNMe)Mn(CO)3]OTf 和 [(4-TIPSiPr)Mn(CO)3]OTf 以及铼化合物 [(4-TIPOiPr)Re( CO)3]OTf 通过 X 射线衍射测定。使用基于紫外/可见光谱的肌红蛋白测定法研究了这些复合物作为可光活化 CO 释放分子 (CORM) 的潜力。在制备的一系列化合物中，发现咪唑基的取代模式显着影响 CO 释放效率和化学计量。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany

  DOI：

  10.1002/ejic.200900650
• 作为产物：
  描述：

  2-异丙基咪唑 在 正丁基锂 、 对甲苯磺酸 、 三氯化磷 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 24.0h， 生成 tris[2-isopropylimidazole-4(5)-yl]phosphane
  参考文献：
  名称：

  作为锌酶 Tris（组氨酸）基序模型的新型水溶性三足咪唑基配体：镍、钴和锌配合物以及与碳酸酐酶中金属结合的比较

  摘要：

  Tris[2-isopropylimidazol-4(5)-yl]phosphane (4-TIPiPr) 是许多锌酶的三（组氨酸）基序的新型模型配体，已制备。4-TIPiPr 水解稳定，可溶于质子溶剂。它很容易在甲醇水溶液中形成氯-和硝基钴、-镍和-锌配合物。溶剂化物的晶体结构 [(4-TIPiPr)Co(MeOH)(NO3)]NO3·2Et2O (3·2Et2O), [(4-TIPiPr)Ni(MeOH)(NO3)]NO3·Et2O·MeOH (4 ·Et2O·MeOH)、[(4-TIPiPr)CoCl]Cl·MeOH·2.5H2O(5·MeOH·2.5H2O)和[(4-TIPiPr)ZnCl]Cl·MeOH·2.5H2O(6·MeOH·2.5) H2O) 已确定。复合物 3 与钴取代的人碳酸酐酶 II (HCA II) 的碳酸氢盐复合物显示出惊人的结构相似性。(© Wiley-VCH

  DOI：

  10.1002/ejic.200300228

文献信息

• Imidazole-based phosphane gold(I) complexes as potential agents for cancer treatment: Synthesis, structural studies and antitumour activity
  作者：Peter C. Kunz、Matthias U. Kassack、Alexandra Hamacher、Bernhard Spingler

  DOI：10.1039/b902748c

  日期：——

  The reaction of the imidazolyl-4(5)-phosphane ligands 2-isopropylimidazol-4(5)yl-diphenylphosphane (4-MIPiPr) and tris(2-isopropylimidazol-4(5)yl)phosphane (4-TIPiPr) towards gold(I) has been explored and compared to those of analogous 1-methylimidazol-2-ylphosphane ligands. The structure of [(4-MIPiPr)AuCl] (4) shows a linear P–Au–Cl coordination, whereas the 4-TIPiPr ligand forms a dinuclear complex [(4-TIPiPr)Au}2]Cl2 (5). Here, 4-TIPiPr bridges two gold(I) atoms in a head-to-tail P,N fashion. Complex 5 forms in the presence of the hard Lewis acid ZnCl2 the bimetallic complex [AuCl(4-TIPiPr)ZnCl]Cl (6), in which 4-TIPiPr bridges the two metal centers. In accordance with the HSAB concept the Au(I) atom is coordinated by the P atom and the zinc(II) by three N atoms in a N,N,N fashion. The solid-state structures of the complexes 4–6 have been elucidated by single-crystal X-ray analysis. The Au(I)–Au(I) contact in 5 is 2.8821(15) Å. The biological activities of all imidazol-2-yl- and imidazol-4(5)-ylphosphane gold(I) complexes towards nine human cancer cell lines including seven ovarian cancer cell lines of different sensitivity towards cisplatin and two leukemia cell lines have been explored.

  咪唑基-4(5)-膦配体2-异丙基咪唑-4(5)基-二苯基膦(4-MIPiPr)和三(2-异丙基咪唑-4(5)基)膦(4-TIPiPr)对金的反应(I) 已被探索并与类似的 1-甲基咪唑-2-基膦配体进行比较。 [(4-MIPiPr)AuCl] (4) 的结构显示出线性 P-Au-Cl 配位，而 4-TIPiPr 配体形成双核配合物 [(4-TIPiPr)Au}2]Cl2 (5)。此处，4-TIPiPr 以头尾相连的 P,N 方式桥接两个金 (I) 原子。配合物 5 在硬路易斯酸 ZnCl2 存在下形成双金属配合物 [AuCl(4-TIPiPr)ZnCl]Cl (6)，其中 4-TIPiPr 桥接两个金属中心。根据 HSAB 概念，Au(I) 原子由 P 原子配位，锌(II) 原子由三个 N 原子以 N、N、N 方式配位。配合物 4-6 的固态结构已通过单晶 X 射线分析阐明。 5 中的 Au(I)-Au(I) 接触面积为 2.8821(15) Å。已探索所有咪唑-2-基-和咪唑-4(5)-基膦金(I)复合物对九种人类癌细胞系（包括七种对顺铂具有不同敏感性的卵巢癌细胞系和两种白血病细胞系）的生物活性。
• Structural flexibility in complexes bearing a tripodal nitrogen ligand
  作者：Peter C. Kunz、Markus Börgardts、Fabian Mohr

  DOI：10.1016/j.ica.2011.11.011

  日期：2012.1

  Abstract Complexes of the divalent metal ions of zinc, cobalt and nickel and a tripodal imidazol-based ligand were investigated for their solution chemistry in protic solvents of varying steric demand. Changes in the coordination number from 4 to 6 are observed depending on solvents, temperature and ions present in solution. With bio-relevant N,O ligands, e.g. amino acids as glycine and alanine, five-coordinate

  摘要研究了锌，钴和镍的二价金属离子与三脚架咪唑基配体的配合物在不同空间需求的质子溶剂中的溶液化学性质。根据溶剂，温度和溶液中存在的离子，观察到配位数从4变为6。与生物相关的N，O配体，例如氨基酸如甘氨酸和丙氨酸，形成五配位络合物。五配位配合物[LNi（H2O）Cl] Cl（3a'）和[LZn（pic）] NO3的固态结构（L =三（2-异丙基咪唑-4（5）-基）膦，pic = picolinato）被确定。
• Gold(I) Catalysts with Bifunctional P, N Ligands
  作者：Corinna Wetzel、Peter C. Kunz、Indre Thiel、Bernhard Spingler

  DOI：10.1021/ic2011259

  日期：2011.8.15

  A series of phosphanes with imidazolyl substituents were prepared as hemilabile PN ligands. The corresponding gold(I) complexes were tested as bifunctional catalysts in the Markovnikov hydration of 1-octyne, as well as in the synthesis of propargylamines by the three component coupling reaction of piperidine, benzaldehyde, and phenylacetylene. While the activity in the hydration of 1-octyne was low, the complexes are potent catalysts for the three component coupling reaction. In homogeneous solution the conversions to the respective propargylamine were considerably higher than under aqueous biphasic conditions. The connectivity of the imidazolyl substituents to the phosphorus atom, their substitution pattern, as well as the number of heteroaromatic substituents have pronounced effects on the catalytic activity of the corresponding gold(I) complexes. Furthermore, formation of polymetallic species with Au-2, Au-3, and Au-4 units has been observed and the solid-state structures of the compounds [(5)(2)Au3Cl2]Cl and [(3c)(2)Au4Cl2]Cl-2 (3c = tris(2-isopropylimidazol-4(5)-yl phosphane, 5 = 2-tert-butylimidazol-4(5)-yldiphenyl phosphane) were determined. The gold(I) complexes of imidazol-2-yl phosphane ligands proved to be a novel source for bis(NHC)gold(I) complexes (NHC = N-heterocyclic carbene).
• Tricarbonylmanganese(I) and –rhenium(I) Complexes of Imidazol‐Based Phosphane Ligands: Influence of the Substitution Pattern on the CO Release Properties
  作者：Peter C. Kunz、Wilhelm Huber、Alfonso Rojas、Ulrich Schatzschneider、Bernhard Spingler

  DOI：10.1002/ejic.200900650

  日期：2009.12

  Tricarbonylmanganese(I) and -rhenium(I) complexes of the imidazolylphosphane ligands tris(imidazol-2-yl)phosphane (2-TIPH), tris(N-methylimidazol-2-yl)phosphane (2-TIPNMe), and tris[2-isopropylimidazol-4(5)-yl]phosphane (4-TIPiPr) as well as the phosphane oxide (4-TIPOiPr) and sulfide (4-TIPSiPr) ligands were prepared. These tris(imidazolyl) ligands act as N,N,N-tripodal chelating ligands. The solid-state structures

  咪唑基膦配体三（咪唑-2-基）膦（2-TIPH）、三（N-甲基咪唑-2-基）膦（2-TIPNMe）和三[制备了 2-异丙基咪唑-4(5)-基] 膦 (4-TIPiPr) 以及氧化膦 (4-TIPOiPr) 和硫化物 (4-TIPSiPr) 配体。这些三（咪唑基）配体充当 N,N,N-三足螯合配体。锰配合物 [(2-TIPNMe)Mn(CO)3]OTf 和 [(4-TIPSiPr)Mn(CO)3]OTf 以及铼化合物 [(4-TIPOiPr)Re( CO)3]OTf 通过 X 射线衍射测定。使用基于紫外/可见光谱的肌红蛋白测定法研究了这些复合物作为可光活化 CO 释放分子 (CORM) 的潜力。在制备的一系列化合物中，发现咪唑基的取代模式显着影响 CO 释放效率和化学计量。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany
• A Novel Water‐Soluble Tripodal Imidazolyl Ligand as a Model for the Tris(histidine) Motif of Zinc Enzymes: Nickel, Cobalt and Zinc Complexes and a Comparison with Metal Binding in Carbonic Anhydrase
  作者：Peter C. Kunz、Guido J. Reiß、Walter Frank、Wolfgang Kläui

  DOI：10.1002/ejic.200300228

  日期：2003.11

  (4·Et2O·MeOH), [(4-TIPiPr)CoCl]Cl·MeOH·2.5H2O (5·MeOH·2.5H2O), and [(4-TIPiPr)ZnCl]Cl·MeOH·2.5H2O (6·MeOH·2.5H2O) have been determined. The complex 3 shows striking structural similarities to the hydrogencarbonate complex of cobalt-substituted human carbonic anhydrase II (HCA II). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

  Tris[2-isopropylimidazol-4(5)-yl]phosphane (4-TIPiPr) 是许多锌酶的三（组氨酸）基序的新型模型配体，已制备。4-TIPiPr 水解稳定，可溶于质子溶剂。它很容易在甲醇水溶液中形成氯-和硝基钴、-镍和-锌配合物。溶剂化物的晶体结构 [(4-TIPiPr)Co(MeOH)(NO3)]NO3·2Et2O (3·2Et2O), [(4-TIPiPr)Ni(MeOH)(NO3)]NO3·Et2O·MeOH (4 ·Et2O·MeOH)、[(4-TIPiPr)CoCl]Cl·MeOH·2.5H2O(5·MeOH·2.5H2O)和[(4-TIPiPr)ZnCl]Cl·MeOH·2.5H2O(6·MeOH·2.5) H2O) 已确定。复合物 3 与钴取代的人碳酸酐酶 II (HCA II) 的碳酸氢盐复合物显示出惊人的结构相似性。(© Wiley-VCH