[Pt(II)(4,4′-di(tert-butyl)-6-phenyl-2,2′-bipyridine(1-))Cl] | 693782-72-8

• 英文名称: [Pt(II)(4,4′-di(tert-butyl)-6-phenyl-2,2′-bipyridine(1-))Cl]
• 英文别名: (4,4′-di(tert-butyl)-6-phenyl-2,2′-bipyridine)platinum(II) chloride；chloro[2-(4,4'-di-tert-butyl-2,2'-bipyridin-6-yl)phenyl] platinum；4,4'-di(tert-butyl)-6-phenyl-2,2'-bipyridine platinum chloride；[Pt(κ3-6-phenyl-4,4'-di-tert-butyl-2,2'-bipyridine(-1H))Cl]；[Pt(Cl)(4,4'-bis(tert-butyl)-6-phenyl-2,2'-bipyridine)]；[Pt(4,4'-di(tert-butyl)-6-phenyl-2,2'-bipyridine-H)Cl]
• CAS: 693782-72-8
• 化学式: C₂₄H₂₇ClN₂Pt
• 分子量: 574.025
• InChiKey: VMOYOHGSCXDKGB-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 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(II)(4,4′-di(tert-butyl)-6-phenyl-2,2′-bipyridine(1-))Cl] 在 aluminum oxide 、 copper(l) iodide 、 potassium carbonate 作用下， 以 甲醇 、 二氯甲烷 、 二氯甲烷-D2 、 甲苯 为溶剂， 反应 18.0h， 生成 [tetra-n-butylammonium][Pt(II)(4,4′-di(tert-butyl)-6-phenyl-2,2′-bipyridine(1-))(CC-C₆H₄-CH(CN)-C(CN)₂)]
  参考文献：
  名称：

  Switching of Reverse Charge Transfers for a Rational Design of an OFF–ON Phosphorescent Chemodosimeter of Cyanide Anions

  摘要：

  A rational approach to luminescence turn-on sensing of cyanide by a dicyanovinyl-substituted acetylide Pt(II) complex, which primarily relies on the nucleophilic addition reaction of cyanide anions to the alpha-position of the dicyanovinyl group, is described. The strategy used for the design of this cyanide-selective sensor takes advantage of a switch of charge transfer from ML'CT to MLCT/L'LCT in this acetylicle Pt(II) sensor. As a result, this chromophore that exhibits almost no basal luminescence displays observable changes in its UV-visible spectrum and acquires strong phosphorescence upon addition of cyanide anions. DFT computations reveal that the frontier molecular orbitals of the anionic system obtained after addition of CN- are drastically different from those of the neutral initial species. TD-DFT computations permitted a full assignment of the observed absorption bands and explained well the emissive properties of the species under consideration.

  DOI：

  10.1021/ic302478e
• 作为产物：
  描述：

  [Pt(κ3-6-phenyl-4,4'-di-tert-butyl-2,2'-bipyridine(-1H))(trifluoroacetate)] 、 lithium chloride 以 三氟乙酸 为溶剂， 生成 [Pt(II)(4,4′-di(tert-butyl)-6-phenyl-2,2′-bipyridine(1-))Cl]
  参考文献：
  名称：

  Heterolytic CH Activation with a Cyclometalated Platinum(II) 6-Phenyl-4,4‘-di-tert-butyl-2,2-Bipyridine Complex

  摘要：

  The more electron-rich, thermally, air, and protic stable, cyclometalated Pt(II)(NNC) trifluoroacetate complex (3) (NNC = kappa(3)-6-phenyl-4,4'-di-tert-butyl-2,2'-bipyridine) was synthesized with the expectation that it would be less susceptible to H2O inhibition than the Pt(bpym)(TFA)(2) system (bpym = kappa(2)-2,2'-bipyrimidine) for the catalytic oxidation of hydrocarbons. Complex 3 was found to catalyze the H/D exchange between benzene and trifluoroacetic acid Via CH activation but at a rate slower than the Pt(bpym) complex. Experimental and theoretical studies show that while the use of the more electron-rich NNC ligand motif lowered the Delta H for substrate coordination relative to the Pt(bpym) system, a larger increase in the barrier for CH cleavage led to an increase in the overall barrier for CH activation.

  DOI：

  10.1021/om060410h

文献信息

• Electron transfer and hydrogen generation from a molecular dyad: platinum(ii) alkynyl complex anchored to [FeFe] hydrogenase subsite mimic
  作者：Wen-Guang Wang、Feng Wang、Hong-Yan Wang、Chen-Ho Tung、Li-Zhu Wu

  DOI：10.1039/c1dt11923k

  日期：——

  A PS–Fe2S2 molecular dyad 1a directly anchoring a platinum(II) alkynyl complex to a Fe2S2 active site of a [FeFe] H2ase mimic, and an intermolecular system of its reference complexes 1b and 2, have been successfully constructed. Time-dependence of H2 evolution shows that PS–Fe2S21a as well as complex 2 with 1b can produce H2 in the presence of a proton source and sacrificial donor under visible light irradiation. Spectroscopic and electrochemical studies on the electron transfer event reveal that the reduced FeIFe0 species generated by the first electron transfer from the excited platinum(II) complex to the Fe2S2 active site in PS–Fe2S21a and complex 2 with 1b is essential for photochemical H2 evolution, while the second electron transfer from the excited platinum(II) complex to the protonated FeIFe0 species is thermodynamically unfeasible, which might be an obstacle for the relatively small amount of H2 obtained by PS–Fe2S2 molecular dyads reported so far.

  成功构建了一种A PS-Fe2S2分子二聚体1a，其直接将一个铂(II)炔配合物锚定在[FeFe] H2ase模拟物的Fe2S2活性位点上，以及其参考配合物1b和2的分子间体系。在可见光照射下，H2生成的随时间变化显示，PS-Fe2S21a以及1b的配合物2在存在质子和牺牲供体的情况下可以产生H2。光谱学和电化学研究电子转移事件揭示，从激发态铂(II)配合物向Fe2S2活性位点首次电子转移生成的还原态FeIFe0物种对于光化学H2生成是至关重要的，而从激发态铂(II)配合物向质子化的FeIFe0物种的第二次电子转移在热力学上不可行，这可能是目前为止报道的PS-Fe2S2分子二聚体产生相对较少H2的障碍。
• Phosphorescent Zwitterionic Pt( <scp>II</scp> ) <scp> <i>N</i> ‐Heterocyclic </scp> Allenylidene Complexes: Metallophilicity and Ionic <scp>Self‐Assembly</scp> ^†
  作者：Qin Gao、Fei Peng、Chuanfei Wang、Jinqiang Lin、Xiaoyong Chang、Chao Zou、Wei Lu

  DOI：10.1002/cjoc.202000674

  日期：2021.5

  ascribed to the resonance structures of zwitterionic acetylide. The zwitterionic and analogue cationic NHA Pt(II) monomers showed similar steady‐state photoluminescent properties in dilute fluid solution. Highly efficient solid‐state phosphorescent emissions (quantum yield up to 20%) of these NHA Pt(II) complexes are correlated with their dispersive metallophilic Pt···Pt interactions. HR‐MS spectrum indicated

  制备了三种两性离子和一种阳离子N杂环烯基（NHA）铂（II）配合物，并通过NMR，HR-MS和FT-IR等进行了表征。单晶结构分析揭示了通过多个非共价相互作用（短Pt···Pt接触，π-π相互作用）。光谱数据表明，亚烯基金属配合物的稳定性很大程度上归因于两性离子乙炔的共振结构。两性离子和类似物阳离子NHA Pt（II）单体在稀液溶液中显示出相似的稳态光致发光特性。这些NHA Pt（II）配合物的高效固态磷光发射（量子产率高达20％）与其分散的嗜金属Pt···Pt相互作用相关。HR-MS光谱表明，两性离子单体可以在混合的H 2中自组装成低聚物，例如二聚体，三聚体甚至六聚体O / MeOH溶剂。同时，通过控制两性离子NHA铂（II）配合物自组装中的浓度，温度，时间和溶剂，分子聚集体显示出可变的红移磷光。
• Cyclometallated platinum(ii) complexes containing pyridyl-acetylide ligands: the selective influence of lead binding on luminescence
  作者：Pierre-Henri Lanoë、Hubert Le Bozec、J. A. Gareth Williams、Jean-Luc Fillaut、Véronique Guerchais

  DOI：10.1039/b914957k

  日期：——

  The design, synthesis, photophysical properties, and the ion-binding properties of cyclometallated platinum(II) complexes containing pyridyl-appended alkynyl ligands are described. When the pyridyl group is incorporated into an azamacrocycle, a specific response towards lead(II) cations involves a change in the nature of the excited charge transfer state, resulting in the appearance of a low-energy absorption band and a partial quenching of luminescence.

  本文介绍了含有吡啶基附加炔基配体的环金属化铂(II)配合物的设计、合成、光物理性质和离子结合特性。当吡啶基并入氮杂环时，对铅（II）阳离子的特定反应涉及激发电荷转移态性质的改变，导致出现低能吸收带和部分熄灭发光。
• Switching of excited states in cyclometalated platinum complexes incorporating pyridyl-acetylide ligands (Pt–CC–py): a combined experimental and theoretical study
  作者：Camille Latouche、Pierre-Henri Lanoë、J. A. Gareth Williams、Véronique Guerchais、Abdou Boucekkine、Jean-Luc Fillaut

  DOI：10.1039/c1nj20225a

  日期：——

  platinum(II) complexes incorporating pyridyl-appended acetylide ligands of the form Pt–CC–py, acting either as sites for protonation or methylation reactions or as a host receptor for binding metal cations. The complexes studied are Pt(t-Bu2phbpy)(–CC–py), 2, which can undergo protonation at the pyridyl N; its cationic N-methylated derivative [Pt(t-Bu2phbpy)(–CC–pyMe)]+, 4, which serves as a model of the

  本文介绍了环金属化铂（II）配合物的设计，该配合物掺入了吡啶基附加的PT–C C–py形式的乙炔配体，可作为质子化或甲基化反应的位点，或作为结合金属阳离子的主体受体。所研究的络合物是PT（吨-Bu 2 phbpy）（ - Visual C C-PY），2，它可以在吡啶基N-经历质子化; 其阳离子Ñ甲基化的衍生物[PT（吨-Bu 2 phbpy）（ - Visual C C-pyMe）] +，4，其用作模型Ñ-质子化的物种；以及其中吡啶基环结合到大环二酰胺-冠醚配体（3）中的衍生物。所述共配体吨-Bu 2 phbpy是环金属化，N⁁N⁁C协调phenylbipyridine配体携带叔在吡啶基环的4-位丁基的基团。已将中性化合物2和3的光物理性质与吡啶鎓，甲基吡啶或金属络合物种（即2-H + +，4和3-Pb 2+ 2+）。详细的TD-DFT计算提供了理论依据，可说明质子化/甲基化/络合过程中
• Structural and Spectroscopic Studies on Pt···Pt and π−π Interactions in Luminescent Multinuclear Cyclometalated Platinum(II) Homologues Tethered by Oligophosphine Auxiliaries
  作者：Wei Lu、Michael C. W. Chan、Nianyong Zhu、Chi-Ming Che、Chuannan Li、Zheng Hui

  DOI：10.1021/ja039727o

  日期：2004.6.23

  The synthesis and structural, spectroscopic, and electrochemical properties of a series of trinuclear tridentate cyclometalated platinum(II) complexes tethered by bis(diphenylphosphinomethyl)phenylphosphine (dpmp) have been studied and compared with their mono- and binuclear homologues and a propeller-like congener. The X-ray crystal structures of several derivatives show the presence of a variety

  研究了一系列由双(二苯基膦甲基)苯基膦 (dpmp) 束缚的三核三齿环金属化铂 (II) 配合物的合成和结构、光谱和电化学性质，并与它们的单核和双核同系物和类似螺旋桨的同系物进行了比较. 几种衍生物的 X 射线晶体结构显示存在各种分子内 Pt.Pt、pi-pi 和 CH...O（冠醚）和分子间 pi-pi 相互作用。三核复合物在 400-600 nm 区域显示出强吸收，并在流体和玻璃溶液以及固态中显示出强烈的红色至近红外磷光，具有微秒的寿命。这些排放通常被指定为 (3) MMLCT [dsigma-->pi(CNN)]。乙腈溶液和 298 K 固态下的发射能量之间的密切相似性表明，在两种介质中都保持了相当的 Pt.Pt 和 pi-pi 构型，因此这些发光体的光物理行为与其固态之间存在关系。提出了状态结构特征。吸收和发射能量从单核到线性系留双核和三核 Pt(II) 物种红移的趋势是显而易见的。已经证明了使用三核