1,5-cyclooctadienebis(trifluoromethanesulfonate)platinum(II) | 353796-98-2

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: 1,5-cyclooctadienebis(trifluoromethanesulfonate)platinum(II)
• 英文别名: Pt(COD)(OTf)2；(1,5-cyclooctadiene)Pt(SO3CF3)2；[1,5-cyclooctadiene)Pt(OTf)2]；[(1,5-cyclooctadiene)Pt(triflate)2]；Pt(1,5-cyclooctadiene)(OTf)2；[(cod)platinum(II)(CF3SO3)2]；(COD)Pt(OTf)2；(1Z,5Z)-cycloocta-1,5-diene;platinum(2+);trifluoromethanesulfonate
• CAS: 353796-98-2
• 化学式: C₁₀H₁₂F₆O₆PtS₂
• 分子量: 601.404
• InChiKey: NQBTZXVJKIMWKF-PHFPKPIQSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  2.77
• 重原子数：
  25
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  131
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  四氢呋喃 、 1,5-cyclooctadienebis(trifluoromethanesulfonate)platinum(II) 以 二氯甲烷 为溶剂， 生成 [1,5-cyclooctadiene)Pt(OTf)(THF)](OTf)
  参考文献：
  名称：

  消除铂（II）上三氟乙酸的烯烃偶联

  摘要：

  Pt（II）配合物（1,5-COD）Pt（OTf）2和[（COD）Pt（THF）（OTf）] OTf易于与烯烃（乙烯，环戊烯，降冰片烯）反应，通过消除HOTf产生偶联产物。用丙烯得到简单的烯丙基配合物。

  DOI：

  10.1021/om0507631
• 作为试剂：
  描述：

  2-norbornene 在 1,5-cyclooctadienebis(trifluoromethanesulfonate)platinum(II) 作用下， 以 邻二氯苯 、 苯 为溶剂， 生成 三环(2.2.1.02,6)庚烷
  参考文献：
  名称：

  Disambiguation of Metal and Brønsted Acid Catalyzed Pathways for Hydroarylation with Platinum(II) Catalysts

  摘要：

  The hydroarylation of unactivated olefins effected by Pt(II) precatalysts was found to proceed through the in situ production of protic acid followed by a Friedel Crafts mechanism. The reaction was investigated using the hindered base 2,6-di-tert-butyl-4-methylpyridine and a variety of substrates.

  DOI：

  10.1021/om2000458

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。
• Selective Oxidative Cleavage of Cp* from Coordinated GaCp*: Naked Ga⁺in [GaNi(GaCp*)₄]⁺and [(μ₂-Ga)<i>n</i>M₃(GaCp*)₆]<i>n</i>+
  作者：Markus Halbherr、Timo Bollermann、Christian Gemel、Roland A. Fischer

  DOI：10.1002/anie.200905920

  日期：2010.3.1

  The naked and the edge: The selective oxidative cleavage of Cp* from coordinated GaCp* ligands lead to the cluster cations [(μ2‐Ga)2Pd3(GaCp*)6]2+ and [(μ2‐Ga)Pt3(GaCp*)6]+ (see structure) which are the first examples of the edge‐bridging coordination mode of “naked” Ga+. This chemistry is a step towards a rational synthesis of metal‐rich molecules as discrete models for intermetallic phases.

  肉眼和边缘：CP的选择性氧化裂解*从协调的GACP *配体导致集群阳离子[（μ 2 -Ga）2的Pd 3（GACP *）6 ] 2+和[（μ 2 -Ga）铂3（GaCP *）6 ] +（请参见结构），这是“裸” Ga +的边缘桥接协调模式的第一个示例。这种化学反应是朝着合理合成富金属分子作为金属间相的离散模型迈出的一步。
• Platinum-Based Catalysts for the Hydroamination of Olefins with Sulfonamides and Weakly Basic Anilines
  作者：Dmitry Karshtedt、Alexis T. Bell、T. Don Tilley

  DOI：10.1021/ja052836d

  日期：2005.9.1

  Electrophilic Pt(II) complexes catalyze efficient hydroaminations of olefins by sufforiamides and weakly basic anilines. Catalysts include the structurally characterized complex (COD)Pt(OTf)(2) (1) and the known dimer [PtCl2(C2H4)](2), activated by AgBF4. Experiments with substituted anilines establish an empirical pK(a) cutoff (conjugate acid pKa < 1) for the participation of nitrogen-containing substrates in this catalysis, Arylsulfonamides (conjugate acid pK(a). approximate to -6) with various para substituents hydroaminate olefins such as cyclohexene in yields greater than 95% at 90 degrees C. Hydroamination of propylene by p-toluenesulfonamide proceeds with Markovnikov selectivity, suggesting a mechanism that involves olefin activation at Pt. With norbornene and p-toluenesulfonamide as the substrates and 1 as the catalyst, intermediate [(COD)Pt(norbornene)(2)][OTf](2) (3) was identified and characterized by F-19 and Pt-195 NMR spectroscopies and mass spectrometry. Kinetic studies provide the empirical rate law, rate = k(obs)[Pt][sulfonamide], and are consistent with: a mechanism in which attack of a sulfonamide on the Pt-coordinated olefin is the rate-determining step.