[Pt(2,2':6',2''-terpyridine)Cl]ClO4 | 166268-05-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: [Pt(2,2':6',2''-terpyridine)Cl]ClO4
• 英文别名: [Pt(tpy)Cl]ClO₄；[Pt(terpy)Cl]ClO4；[Pt(2,2':6',6''-terpyridine)Cl]ClO4；[platinum(II) (2,2':6,2''-terpyridine) (chloride)] perchlorate；[ClPt(2,2':6,2''-tpy)]ClO4；chloroplatinum(1+);2,6-dipyridin-2-ylpyridine;perchlorate
• CAS: 166268-05-9
• 化学式: C₁₅H₁₁ClN₃Pt*ClO₄
• 分子量: 563.256
• InChiKey: DXZWINKWXRDACB-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [Pt(2,2':6',2''-terpyridine)Cl]ClO4 在 LiClO₄ 、 CH₃SO₃Na 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 生成
  参考文献：
  名称：

  The reactivity of neutral nitrogen donors in planar d8 metal complexes. Part 3. The system chloro(2,2′ : 6′,2″-terpyridine)platinum(II) cation with pyridines and ammonia in methanol. Effect of basicity, π-acceptor capacity and steric hindrance

  摘要：

  The kinetics of the forward and reverse steps of the process [Pt(NNN)Cl](+) + am reversible arrow [Pt(NNN)(am)](2+) + Cl- (NNN = 2,2':6',2 "-terpyridine; am =, one of a number of pyridines and NH, covering a wide range of basicity) have been studied in methanol at 25 degrees C. Both forward and reverse reactions obey the usual two-term rate law observed in square-planar substitution. The reactivity and the ability of the chloro-complex to discriminate among the nucleophiles, as well as the sensitivity of the rate of the chloro entry upon the nature of the displaced base and the steric factors in both the forward and reverse processes are discussed in terms of intimate mechanism and compared with data for a number of different Pt-II systems. The equilibrium constants for the reactions have been determined from the ratio of the rate constants. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0277-5387(97)00357-4
• 作为产物：
  描述：

  [Pt(2,2′;6′,2″-terpyridine)Cl]perchlorate*(water) 生成 [Pt(2,2':6',2''-terpyridine)Cl]ClO4
  参考文献：
  名称：

  Between red and yellow: evidence of intermediates in a vapochromic Pt(ii) salt

  摘要：

  由于 Pt⋯Pt 距离增加，脱水时[Pt(tpy)Cl]ClO4·H2O (1·H2O) 从红色变为黄色。光谱、衍射、重量和量热数据证明了水合和脱水过程中中间体的存在，这意味着气色响应中令人惊讶的机械复杂性。

  DOI：

  10.1039/c3cc45418e

文献信息

• Reactivity of neutral nitrogen donors in square-planar d8 metal complexes: The system chloro(2,2′:6′,2″-terpyridine)platinum(II) cation with five-membered N-donor heterocycles in methanol
  作者：Bruno Pitteri、Marco Bortoluzzi

  DOI：10.1016/j.poly.2006.03.017

  日期：2006.10

  series of pyridines reacting with the [Pt(terpy)Cl]+ cation under the same experimental conditions. Both in the forward and in the reverse reaction, the reactivity depends not only upon the ligand basicity but also upon the nature of the nucleophile in the order: (thiazoles, oxazole, isoxazole, imidazole, pyrazoles) > pyridines for the entry of N-donors and on the contrary for the displacement by Cl−

  摘要[Pt（terpy）Cl] + + nu⇌[Pt（terpy）（nu）] 2+ + Cl−（terpy = 2,2′：6′，2″ -吡啶，nu =噻唑，恶唑，异恶唑，咪唑，吡唑和3,5-二甲基吡唑中的一种，涵盖了广泛的碱度）已在25°C的甲醇中进行了研究。正向和反向反应都遵守在平面替代中观察到的通常的二项速率定律。正向反应的二级速率常数k 2 f稍微依赖于进入的nu的碱性，而由于α原子上一个甲基存在于氮上而导致的空间位阻显着降低了反应性。逆反应的二级速率常数k 2 r，对离去基团的性质非常敏感，log k 2 r对无阻碍的五元N供体的共轭酸的pKa的图呈线性，斜率为-0.51。将结果与文献中有关在相同实验条件下与[Pt（terpy）Cl] +阳离子反应的一系列吡啶的数据进行比较。在正向和反向反应中，反应性不仅取决于配体的碱性，而且还取决于亲核试剂的性质，顺序依次为：（噻唑，恶唑，异恶唑
• Terpyridine-platinum(ii) acetylide complexes bearing pendent coordination units
  作者：Raymond Ziessel、St?phane Diring、Pascal Retailleau

  DOI：10.1039/b603603a

  日期：——

  Platinum(II) complexes bearing various alkyne–pyrene, alkyne–4′-terpyridine and alkyne–dibutoxyphenylacetylide–terpyridine units were constructed in a step-by-step procedure based on copper-promoted cross-coupling reactions with preconstructed modules; formation of bis(ligand) complexes of Fe(II) and Zn(II) by binding of the pendent terpyridine units provided heterotrinuclear derivatives, all of which exhibit highly structured absorption features in solution and display a rich electrochemistry due to the presence of various redox active modules.

  在铜促进的交叉耦合反应基础上，通过预先构建的模块，逐步构建了含有各种烷基苯乙烯、烷基-4′-三吡啶和烷基二丁氧基苯乙酰三吡啶单元的铂(II)配合物；通过与下垂的三吡啶单元结合，形成铁（II）和锌（II）的双（配体）配合物，从而提供了异三核苷衍生物，由于存在各种氧化还原活性模块，所有这些配合物在溶液中都表现出高度结构化的吸收特征，并显示出丰富的电化学特性。
• Pitteri, Bruno; Marangoni, Giampaolo; Cattalini, Lucio, Journal of the Chemical Society, Dalton Transactions, 1995, p. 3853 - 3860
  作者：Pitteri, Bruno、Marangoni, Giampaolo、Cattalini, Lucio、Bobbo, Tatiana

  DOI：——

  日期：——
• Electronic Spectroscopy of Chloro(terpyridine)platinum(II)
  作者：James A. Bailey、Michael G. Hill、Richard E. Marsh、Vincent M. Miskowski、William P. Schaefer、Harry B. Gray

  DOI：10.1021/ic00122a015

  日期：1995.8

  The electronic spectrum of [Pt(tpy)Cl](+) (tpy = 2,2':6',2''-terpyridine) is influenced dramatically by intermolecular stacking interactions in solution and in the solid state. The crystal structure of [Pt(tpy)Cl]ClO4 (monoclinic, P2(1)/c (No. 14); a = 7.085(2), b = 17.064(5), c = 26.905(8) Angstrom; beta = 90.0(1)degrees; Z = 8) consists of discrete Pt-2 units (Pt-Pt = 3.269(1) Angstrom) arranged along an infinite tpy-pi stack (spacing similar to 3.35 Angstrom. Variable-temperature and concentration studies of the absorption and emission spectra of [Pt(tpy)Cl](+) suggest that similar metal-metal and ligand-ligand interactions persist in the solution phase. The high concentration, low-temperature emission spectrum (5:5:1 ethanol:methanol:DMF) reveals a 740-nm band indicative of M-M oligomerization, a 650-nm band attributable to tpy pi-pi interactions, and a 470-nm band characteristic of mononuclear [Pt(tpy)Cl](+) pi-pi* emission. Concentration-dependent absorption spectra were fit to a ''two-dimer'' model, yielding equilibrium constants for the formation of Pt-Pt-, and tpy-tpy-bound dimers of 1.3(1) x 10(3) and 1.0(1) x 10(3) M(-1), respectively, in 0.1 M aqueous NaCl. The low temperature solid-state luminescence of [Pt(tpy)Cl](+) is assigned to a (3)(MMLCT) (MMLCT = metal-metal-to-ligand charge transfer) transition. The energy of this band is highly dependent on the counterion (PF6-, ClO4-, Cl-, CF3SO3-), in line with the different colors of these various salts, In contrast, the room-temperature solid-state emission spectra are more difficult to interpret. While the red perchlorate salt exhibits a relatively narrow emission band at 725 nm (red-shifted from the 77-K maximum at 695 nm), consistent with a (3)(MMLCT) transition, the orange (Cl-, ClO4-, CF3SO3-) and yellow (PF6-) salts have extremely broad room-temperature emission bands that all appear at nearly the same energy (lambda(max) similar to 640 nm). We assign this luminescence to an eximeric intraligand transition resulting from pi-pi interactions and propose that the temperature dependent emissions from the orange and yellow solid materials originate from multiple electronic states.