Pt(tbbpy)(OTf )2 | 177593-36-1

• 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(tbbpy)(OTf )2
• 英文别名: 4-Tert-butyl-2-(4-tert-butylpyridin-2-yl)pyridine;platinum(2+);trifluoromethanesulfonate
• CAS: 177593-36-1
• 化学式: C₂₀H₂₄F₆N₂O₆PtS₂
• 分子量: 761.623
• InChiKey: VEFADHLWFKGVIK-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  4.84
• 重原子数：
  37
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  157
• 氢给体数：
  0
• 氢受体数：
  14

反应信息

• 作为反应物：
  描述：

  Pt(tbbpy)(OTf )2 在 NaN(Si(CH₃)3)2 作用下， 以 乙醚 、 二氯甲烷 、 苯 为溶剂， 生成 (4,4'-di-tert-butyl-2,2'-dipyridyl)Pt(NHPh)(Cl)
  参考文献：
  名称：

  Pt(II) and Pt(IV) Amido, Aryloxide, and Hydrocarbyl Complexes: Synthesis, Characterization, and Reaction with Dihydrogen and Substrates that Possess C−H Bonds

  摘要：

  The PO) amido and phenoxide complexes ((t)bpy)Pt(Me) (X), ((t)bpy)Pt(X)(2), and [((t)bpy)Pt(X)(py)][BAr'(4)] (X = NHPh, OPh; py = pyridine) have been synthesized and characterized. To test the feasibility of accessing Pt(IV) complexes by oxidizing their Pt(II) precursors, the previously reported ((t)bpy)Pt(R)(2) (R = Me and Ph) systems were oxidized with I-2 to yield ((t)bpy)Pt(R)(2)(I)(2). The analogous reaction with ((t)bpy)Pt(Me)(NHPh) and MeI yields the corresponding ((t)bpy)Pt(Me)(2)(NHPh)(I) complex. Reaction of ((t)bpy)Pt(Me)(NHPh) and phenylacetylene at 80 degrees C results in the formation of the Pt(II) phenylacetylene complex ((t)bpy)Pt(Me)(C CPh). Kinetic studies indicate that the reaction of ((t)bpy)Pt(Me)(NHPh) and phenylacetylene occurs via a pathway that involves [((t)bpy)Pt(Me)(NH2Ph)] [TEA] as a catalyst. The reaction of H-2 with ((t)bpy)Pt(Me)(NHPh) ultimately produces aniline, methane, (t)bpy, and elemental Pt. For this reaction, mechanistic studies reveal that 1,2-addition of dihydrogen across the Pt-NHPh bond to initially produce ((t)bpy)Pt(Me)(H) and free aniline is catalyzed by elemental Pt. Heating the cationic complexes [((t)bpy)Pt(NHPh)(py)][BAr'(4)] and [((t)bpy)Pt(OPh)(py)][BAr'(4)] in C6D6 does not result in the production of aniline and phenol, respectively. Attempted synthesis of a cationic system analogous to [((t)bpy)Pt(NHPh)(py)][BAr'(4)] with ligands that are more labile than pyridine (e.g., NC5F5) results in the formation of the dimer [((t)bpy)Pt(mu-NHPh)](2)[BAr'(4)](2). Solid state X-ray diffraction studies of the complexes [((t)bpy)Pt(Me)(NHPh), [((t)bpy)Pt(NH2Ph)(2)][OTf](2), [((t)bpy)Pt(NHPh)(2), ((t)bpy)pt(OPh)(2), ((t)bpy)pt(Me)(2)(I)(2), and ((t)bpy)pt(Ph)(2)(I)(2) are reported.

  DOI：

  10.1021/ic200153n
• 作为产物：
  描述：

  dichloro(4,4'-di-tert-butyl-2,2'-bipyridine)platinum(II) 、 silver trifluoromethanesulfonate 以 二氯甲烷 为溶剂， 以96%的产率得到Pt(tbbpy)(OTf )2
  参考文献：
  名称：

  降冰片烯与亲电铂配合物加氢胺化的机理研究：质子转移的作用

  摘要：

  使用 L2Pt(OTf)2 (L2 = (t)Bu2bpy, (t)BuC6H4N== C(CH3)C( CH3)==NC6H4(t)Bu、(C6H5)2PCH2CH2P(C6H5)2、(C6F5)2PCH2CH2P(C6F5)2、S​​-BINAP)。伪一级动力学表明反应速率几乎不依赖于辅助配体。机理研究不支持烯烃配位机制，而是与涉及磺酰胺配位和产生转移到降冰片烯的酸性质子的机制一致。据推测，所得降冰片基阳离子随后被游离磺酰胺攻击，并且从该加合物中损失质子完成加氢胺化。铂-磺酰胺络合物很容易发生去质子化，得到从反应溶液中分离出来的μ-酰氨基铂桥二聚体。这些研究还涉及使用 Me3SiPh 和 Me3SnPh 作为非亲核质子陷阱。Ph-E 键的断裂用于检测酸性催化活性物质。

  DOI：

  10.1021/ja8030104

文献信息

• Diimine supported group 10 hydroxo, oxo, amido, and imido complexes
  作者：Anupam Singh、U. Anandhi、Maria Agostina Cinellu、Paul R. Sharp

  DOI：10.1039/b715663d

  日期：——

  A series of L2 = diimine (Bian = bis(3,5-diisopropylphenylimino)acenapthene, But2bpy = 4,4′-di-tert-butyl-2,2′-bipyridine) supported aqua, hydroxo, oxo, amido, imido, and mixed complexes have been prepared. Deprotonation of [L2Pt(μ-OH)]22+ with 1,8-bis(dimethylamino)naphthalene, NaH, or KOH yields [(L2Pt)2(μ-OH)(μ-O)]+ as purple (Bian) or red (But2bpy) solids. Excess KOH gives dark blue [(Bian)Pt(μ-O)]2. MeOTf addition to [(But2bpy)2Pt2(μ-OH)(μ-O)]+ gives [(But2bpy)2Pt2(μ-OH)(μ-OMe)]2+ while [(Bian)Pt(μ-O)]2 yields [(Bian)2Pt2(μ-OMe)(μ-O)]+. Treatment of [(Bian)Pt(μ-O)]2 with “(Ph3P)Au+” gives deep purple [(Bian)2Pt2(μ-O)(μ-OAuPPh3)]+ while (COD)Pt(OTf)2 gives a low yield of [(Bian)Pt3(μ-OH)3(COD)2](OTf)3. Ni(But2bpy)Cl2 and [(Ph3PAu)3(μ-O)]+ in a 3 : 2 ratio yield red [Ni3(But2bpy)3(μ-O)2]2+. M(But2bpy)Cl2 (M = Pd, Pt) and [(Ph3PAu)3(μ-O)]+ give [M(But2bpy)(μ-OAuPPh3)]22+ and [Pd4(But2bpy)4(μ-OAuPPh3)]3+. Addition of ArNH2 to [M(But2bpy)(μ-OH)]22+ (M = Pd, Pt) gives [Pt2(But2bpy)2(μ-NHAr)(μ-OH)]2+ (Ar = Ph, 4-tol, 4-C6H4NO2) and [M(But2bpy)(μ-NHAr)]22+ (Ar = Ph, tol). Deprotonation of [Pt2(But2bpy)2(μ-NH-tol)(μ-OH)]2+ with 1,8-bis(dimethylamino)naphthalene or NaH gives [Pt2(But2bpy)2(μ-NH-tol)(μ-O)]+. Deprotonation of [Pt(But2bpy)(μ-NH-tol)]22+ with KOBut gives deep green [Pt(But2bpy)(μ-N-tol)]2. The triflate complexes M(But2bpy)(OTf)2 (M = Pd, Pt) are obtained from M(But2bpy)Cl2 and AgOTf. Treatment of Pt(But2bpy)(OTf)2 with water gives the aqua complex [Pt(But2bpy)(H2O)2](OTf)2.

  一系列L2（Bian=双(3,5-二异丙基苯亚胺)苊，But2bpy=4,4'-二叔丁基-2,2'-联吡啶）配位的水合、羟基、氧合、氨基、亚氨基以及混合型络合物已被制备。用1,8-双(二甲基氨基)萘、NaH或KOH去质子化 [L2Pt(μ-OH)]22+ 得到紫色（Bian）或红色（But2bpy）固体 [(L2Pt)2(μ-OH)(μ-O)]+。过量KOH得到深蓝色 [(Bian)Pt(μ-O)]2。将MeOTf加入 [(But2bpy)2Pt2(μ-OH)(μ-O)]+ 得到 [(But2bpy)2Pt2(μ-OH)(μ-OMe)]2+，而 [(Bian)Pt(μ-O)]2 则生成 [(Bian)2Pt2(μ-OMe)(μ-O)]+。用“(Ph3P)Au+”处理 [(Bian)Pt(μ-O)]2 得到深紫色 [(Bian)2Pt2(μ-O)(μ-OAuPPh3)]+，而使用(COD)Pt(OTf)2 则得到低产率的 [(Bian)Pt3(μ-OH)3(COD)2](OTf)3。使用 Ni(But2bpy)CL2 和 [(Ph3PAu)3(μ-O)]+ 按3:2比例反应生成红色 [Ni3(But2bpy)3(μ-O)2]2+。M(But2bpy)CL2（M=Pd, Pt）和 [(Ph3PAu)3(μ-O)]+ 生成 [M(But2bpy)(μ-OAuPPh3)]22+ 和 [Pd4(But2bpy)4(μ-OAuPPh3)]3+。向 [M(But2bpy)(μ-OH)]22+（M=Pd, Pt）中加入ArNH2 得到 [Pt2(But2bpy)2(μ-NHAr)(μ-OH)]2+（Ar=Ph, 4-tol, 4-C6H4NO2）和 [M(But2bpy)(μ-NHAr)]22+（Ar=Ph, tol）。用1,8-双(二甲基氨基)萘或NaH去质子化 [Pt2(But2bpy)2(μ-NH-tol)(μ-OH)]2+ 得到 [Pt2(But2bpy)2(μ-NH-tol)(μ-O)]+。使用KOBut去质子化 [Pt(But2bpy)(μ-NH-tol)]22+ 得到深绿色 [Pt(But2bpy)(μ-N-tol)]2。通过M(But2bpy)CL2和AgOTf反应得到三氟甲磺酸盐络合物 M(But2bpy)(OTf)2（M=Pd, Pt）。处理 Pt(But2bpy)(OTf)2 与水得到水合络合物 [Pt(But2bpy)(H2O)2](OTf)2。
• Highly Emissive Self-Assembled BODIPY-Platinum Supramolecular Triangles
  作者：Jiong Zhou、Yuzhen Zhang、Guocan Yu、Matthew R. Crawley、Cressa Ria P. Fulong、Alan E. Friedman、Sanghamitra Sengupta、Jifu Sun、Qing Li、Feihe Huang、Timothy R. Cook

  DOI：10.1021/jacs.8b04929

  日期：2018.6.20

  supramolecular coordination complexes (SCCs) have been widely studied for applications in the chemical and biological sciences. Herein, we report the coordination-driven self-assembly of two highly emissive platinum(II) supramolecular triangles (1 and 2) containing BODIPY-based bridging ligands. The metallacycles exhibit favorable anticancer activities against HeLa cells (IC50 of 6.41 and 2.11 μM).

  发光超分子配位配合物 (SCC) 已被广泛研究用于化学和生物科学。在此，我们报告了包含基于 BODIPY 的桥接配体的两个高发射铂 (II) 超分子三角形（1 和 2）的配位驱动自组装。金属环对 HeLa 细胞表现出良好的抗癌活性（IC50 为 6.41 和 2.11 μM）。金属环中硼二吡咯亚甲基 (BODIPY) 部分的特征~570 nm 荧光允许使用共聚焦显微镜对其进行细胞内可视化。此外，BODIPY 荧光团是一种出色的光动力剂，使金属环成为光动力疗法 (PDT) 和化学疗法的理想疗法。体外研究表明，对 HeLa 细胞的组合指数为 0.56 和 0。1 和 2 分别为 48，证实了它们的协同抗癌作用。更重要的是，这些 SCC 还通过结合 PDT 和化学疗法对顺铂耐药的 A2780cis 细胞系表现出优异的抗癌功效，显示出克服耐药性的希望。本研究采用多组分方法自组装金属溶瘤，能够设计有
• Self-Assembly Reactions between the Cis<i>-</i>Protected Metal Corners (N−N)M^II (N−N = Ethylenediamine, 4,4‘-Substituted 2,2‘-Bipyridine; M = Pd, Pt) and the Fluorinated Edge 1,4-Bis(4-pyridyl)tetrafluorobenzene
  作者：Montserrat Ferrer、Albert Gutiérrez、Mounia Mounir、Oriol Rossell、Eliseo Ruiz、Alexander Rang、Marianne Engeser

  DOI：10.1021/ic062373s

  日期：2007.4.1

  nitrogen-protected palladium(II) and platinum(II) complexes have been investigated. While dynamic equilibria between molecular triangles and squares were observed when the diimine compounds 4,4'-R2bipy (bipy = 2,2'-bipyridine; R = H, Me, t-Bu) were employed as ancillary ligands, only square species were obtained from ethylenediamine (en) derivatives. Characterization of the obtained metallomacrocycles was accomplished

  研究了氟化的对位配体1,4-双（4-吡啶基）四氟苯（A）与不同的氮保护钯（II）和铂（II）配合物之间的自组装反应。当使用二亚胺化合物4,4'-R2bipy（bipy = 2,2'-联吡啶； R = H，Me，t-Bu）作为辅助配体时，观察到分子三角形和正方形之间的动态平衡。从乙二胺（en）衍生物获得。通过1H和19F NMR光谱结合电喷雾电离傅立叶变换离子回旋共振质谱（ESI-FT-ICR）对获得的金属大环化合物进行表征。已经执行了分子动力学模拟（UFF）来解释氟化环对方形/三角形相对稳定性的影响。使用GIAO方法的密度函数计算已用于解释化学位移分配。对这些化合物充当富电子芳族客体的主体的能力的研究表明，乙二胺钯方剂能够仅在水性介质中建立这种类型的分子间相互作用。主客体的化学计量和缔合常数已通过1 H NMR光谱法确定。
• Cationic platinum(<scp>II</scp>) complexes: platinum–alkyl bond cleavage by a powerful Lewis acid
  作者：Geoffrey S. Hill、Louis M. Rendina、Richard J. Puddephatt

  DOI：10.1039/dt9960001809

  日期：——

  2′-bipyridine) with AgX (X = SO3CF3 or O2CCF3) gave the complexes [PtMe(SO3CF3)(dbbipy)]1, [Pt(SO3CF3)2(dbbipy)]2 and [Pt(O2CCF3)2(dbbipy)]5. The complexes [PtCl(SO3CF3)(dbbipy)]3 and [PtMe(O2CCF3)(dbbipy)]4 were prepared by the addition of HX to [PtCl2(dbbipy)] or [PtMe2(dbbipy)], respectively. Complex 1 reacted with CO to give the cationic carbonyl complex [PtMe(CO)(dbbipy)][SO3CF3]6a, which reacted with

  [氯铂酸（ME）（dbbipy）]或[氯铂酸的治疗2（dbbipy）]（dbbipy = 4,4'-二-叔与卤化银丁基-2,2'-联吡啶）（X = SO 3 CF 3或O 2 CCF 3）给出络合物[PtMe（SO 3 CF 3）（dbbipy）] 1，[Pt（SO 3 CF 3）2（dbbipy）] 2和[Pt（O 2 CCF 3）2（dbbipy）] 5。[PtCl（SO 3 CF 3）（dbbipy）] 3和[PtMe（O 2 CCF 3）通过向[PtCl 2（dbbipy）]或[PtMe 2（dbbipy）]中添加HX分别制备）（（dbbipy）] 4。配合物1与CO反应生成阳离子羰基配合物[PtMe（CO）（dbbipy）] [SO 3 CF 3 ] 6a，其与NEt 2 H反应生成与相应的氨基甲酸酯配合物[Pt（CONEt 2）Me （（dbbipy）] 7。在通过强路易斯酸B（C
• Photophysical Enhancement of Triplet Emitters by Coordination-Driven Self-Assembly
  作者：Yuzhen Zhang、Cressa Ria P. Fulong、Cory E. Hauke、Matthew R. Crawley、Alan E. Friedman、Timothy R. Cook

  DOI：10.1002/chem.201700614

  日期：2017.4.3

  3‐dihexyl‐2‐H‐imidazol‐2‐ylidene), was used along with other linear donors 4,4′‐bipyridine (D2) and 1,4‐bis(4‐pyridyl ethynyl)benzene (D3) in self‐assembly reactions with Pt(dtbpy)X2 acceptors (dtbpy=4,4′‐di‐tert‐butyl‐2,2′‐bipyridine) to afford three metallacycles. Photophysical investigations revealed that, although the building blocks used to construct M1 have relatively low quantum yields (Φ=1.2 and <1 %

  在配位驱动的自组装中用作施主的有机荧光团的量子产率通常受到附近金属位点的重原子效应的影响。在这里，系统间从停用过程过渡到传递发光三重态的过程的角色被颠倒了。磷光反式双N杂环卡宾铂（II）化合物Pt（dhim）2（C≡C-4-py）2（D1 ; dhim = 1,3-二己基-2-H-咪唑-2-亚基）与其他线性供体4,4'-联吡啶（D2）和1,4-双（4-吡啶基乙炔基）苯（D3）在与Pt（dtbpy）X 2的自组装反应中一起使用受体（dtbpy = 4,4'-二叔丁基-2,2'-联吡啶）提供三个金属环。光物理研究表明，尽管用于构建M1的结构单元具有相对较低的量子产率（对于D1和2分别为Φ = 1.2和<1％），但金属环化合物的量子产率却为14％。这种增加反映了在辐射速率常数为3.6×10的变化4 小号-1为D1至2.1×10 5 小号-1为M1。