[Pt2(dppp)2(μ-S)2] | 442518-74-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [Pt2(dppp)2(μ-S)2]
• 英文别名: [Pt2(μ3-S)2(1,3-bis(diphenylphosphino)propane)2]；[Pt2(μ-S)2(1,3-bis(diphenylphosphino)propane)2]；[Pt2(1,3-bis(diphenylphosphino)propane)2(μ-S)2]；Pt bis[bis(diphenylphosphino)propane](μ-Cl)2；[Pt2(μ-S)2(dppp)2]
• CAS: 442518-74-3
• 化学式: C₅₄H₅₂P₄Pt₂S₂
• 分子量: 1279.19
• InChiKey: ZOJJLCUHNZZIFU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.27
• 重原子数：
  62.0
• 可旋转键数：
  8.0
• 环数：
  11.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  [Pt2(dppp)2(μ-S)2] 以 二氯甲烷 、 苯 为溶剂， 生成 [Pt(dppp)(S2CH2)]*MeCN
  参考文献：
  名称：

  [[Ph（2）P（CH（2））（n）PPh（2）] Pt（mu-S）（2）Pt [Ph（2（P）（CH（2））（n）PPh （2）]]（n = 2、3）CH（2）Cl（2）中的金属配体。

  摘要：

  [[Ph（2）P（CH（2））（n）PPh（2）] Pt（mu-S）（2）Pt [Ph（ 2）P（CH（2））（n）PPh（2）]]]（n = 3，dppp（1）； n = 2，dppe（2））金属配体朝向CH（2）Cl（2）溶剂具有经过深入研究。配合物1，已获得并通过X射线衍射表征，在结构上与2有关，由具有铰链[Pt（2）S（2）]中心环的双核分子组成。1和2与CH（2）Cl（2）的反应已通过（31）P，（1）H和（13）C NMR，电喷雾电离质谱和X射线数据进行了跟踪。尽管两个反应均以不同的速率进行，但第一步很常见，并导致相应的单核络合物[Pt [Ph（2）P（CH（2））（n）PPh（2）]（S（2）的混合物CH（2））]，n = 3（7），2（8），和[Pt [Ph（2）P（CH（2））（n）PPh（2）] Cl（2）]，n = 3（9），2（10）。理论计算为[Pt（2）S（2）

  DOI：

  10.1021/ic0107173
• 作为产物：
  描述：

  sodiumsulfide nonahydrate 、 [1,3-bis(diphenylphosphino)propane]dichloroplatinum(II) 以 苯 为溶剂， 以84%的产率得到[Pt2(dppp)2(μ-S)2]
  参考文献：
  名称：

  [[Ph（2）P（CH（2））（n）PPh（2）] Pt（mu-S）（2）Pt [Ph（2（P）（CH（2））（n）PPh （2）]]（n = 2、3）CH（2）Cl（2）中的金属配体。

  摘要：

  [[Ph（2）P（CH（2））（n）PPh（2）] Pt（mu-S）（2）Pt [Ph（ 2）P（CH（2））（n）PPh（2）]]]（n = 3，dppp（1）； n = 2，dppe（2））金属配体朝向CH（2）Cl（2）溶剂具有经过深入研究。配合物1，已获得并通过X射线衍射表征，在结构上与2有关，由具有铰链[Pt（2）S（2）]中心环的双核分子组成。1和2与CH（2）Cl（2）的反应已通过（31）P，（1）H和（13）C NMR，电喷雾电离质谱和X射线数据进行了跟踪。尽管两个反应均以不同的速率进行，但第一步很常见，并导致相应的单核络合物[Pt [Ph（2）P（CH（2））（n）PPh（2）]（S（2）的混合物CH（2））]，n = 3（7），2（8），和[Pt [Ph（2）P（CH（2））（n）PPh（2）] Cl（2）]，n = 3（9），2（10）。理论计算为[Pt（2）S（2）

  DOI：

  10.1021/ic0107173
• 作为试剂：
  描述：

  邻二氯苄 在 [Pt2(dppp)2(μ-S)2] 作用下， 以 甲醇 为溶剂， 25.0 ℃ 、1499.99 MPa 条件下， 以35%的产率得到2,11-Dithia-<3,3>orthocyclophane
  参考文献：
  名称：

  Combinative use of high-pressure, metal-templating and sulfur-nucleophilicity towards dithiacyclophane synthesis and its complex intermediates

  摘要：

  Combined use of elevated pressure in the liquid phase (15 kbar), a metal template and the sulfur nucleophilicity of [Pt-2(mu-S)(2)-(P-P)(2)] (P-P = diphosphine or 2 (.) monophosphine) facilitates the one-pot synthesis of 3,8-dibenzo-1,6-dithiacyclodecane. Under r.t.p., nucleophilic addition of [Pt-2(mu-S)(2)(P-P)(2)] [P-P = 2 (.) PPh3; Ph2P(CH2)(n)PPh2, n = 2, 1,2-bis(diphenylphosphino)ethane (dppe), 3, 1, 3-bis(diphenylphosphino)propane (dppp)] with alpha-alpha'-dichloro-o-xylene would terminate as a dithiolato bridged cation viz. [PtAvSCH(2)C(6)H(4)CH(2)S)(P-P)(2)](2+). Under high pressure (15 kbar) at r.t., these stoichiometric reactions progress via a "catalytic-like" pathway to yield 3,8-dibenzo-1,6-dithiacyclodecane (up to 35%), and a series of mechanistically relevant intermediates and byproducts. The dithiolated intermediates [Pt-2(mu-SCH2C6H4CH2S)(P-P)(2)](2+) for PPh3 and dppp have been isolated as PF6 complexes and their crystal structure determined. The formation of 3,8-dibenzo-1,6-dithiacyclodecane demonstrates a convenient Synthetic strategy over the multi-step synthesis of this macrocyclic dithioether. (c) 2005 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2005.08.055

文献信息

• Stable diplatinum complexes with functional thiolato bridges from dialkylation of [Pt2(µ-S)2(P–P)2] [P–P = 2 × PPh3, Ph2P(CH2)3PPh2]
  作者：Siew Huay Chong、William Henderson、T. S. Andy Hor

  DOI：10.1039/b707526j

  日期：——

  The normally robust monoalkylated complexes [Pt2(µ-S)(µ-SR)(PPh3)4]+ can be activated towards further alkylation. Dialkylated complexes [Pt2(µ-SR)2(P–P)2]2+ (P–P = 2 × PPh3, Ph2P(CH2)3PPh2) can be stabilized and isolated by the use of electron-rich and aromatic halogenated substituents R [e.g. 3-(2-bromoethyl)indole and 2-bromo-4′-phenylacetophenone] and 1,3-bis(diphenylphosphino)propane [Ph2P(CH2)3PPh2 or dppp] which enhances the nucleophilicity of the Pt2(µ-S)2} core. This strategy led to the activation of [Pt2(µ-S)(µ-SR)(PPh3)4]+ towards R–X as well as isolation and crystallographic elucidation of [Pt2(µ-SC10H10N)2(PPh3)4](PF6)2 (2a), [Pt2(µ-SCH2C(O)C6H4C6H5)2(PPh3)4](PF6)2 (2b), and a range of functionalized-thiolato bridged complexes such as [Pt2(µ-SR)2(dppp)2](PF6)2 [R = –CH2C6H5 (8a), –CH2CHCH2 (8b) and –CH2CN (8c)]. The stepwise alkylation process is conveniently monitored by Electrospray Ionisation Mass Spectrometry, allowing for a direct qualitative comparison of the nucleophilicity of [Pt2(µ-S)2(P–P)2], thereby guiding the bench-top synthesis of some products observed spectroscopically.

  通常情况下，强健的单烷基化配合物 [Pt2(µ-S)(µ-SR)(PPh3)4]+ 可以被进一步活化进行烷基化。通过使用电富荷和芳香性卤代取代基 R（例如 3-(2-溴乙基)吲哚和 2-溴-4'-苯基乙酰苯酮）以及提高 Pt2(µ-S)2} 核的亲核性的 1,3-双(二苯基膦基)丙烷 [Ph2P(CH2)3PPh2 或 dppp]，可以稳定和分离二烷基化配合物 [Pt2(µ-SR)2(P–P)2]2+ (P–P = 2 × 磷三苯，Ph2P( )3PPh2)。这一策略不仅激活了 [Pt2(µ-S)(µ-SR)(PPh3)4]+ 对 R-X 的反应性，还成功分离和晶体结构解析了 [Pt2(µ-SC10H10N)2(PPh3)4](PF6)2 (2a)、[Pt2(µ-S C(O)C6H4C6H5)2(PPh3)4](PF6)2 (2b) 以及一系列功能化硫醇基桥联配合物，如 [Pt2(µ-SR)2(dppp)2](PF6)2 [R = - C6H5 (8a)、- CH (8b) 和 - CN (8c)]。通过电喷雾离子化质谱法可以方便地监测逐步烷基化过程，从而直接定性比较 [Pt2(µ-S)2(P–P)2] 的亲核性，指导某些光谱观察到的产品的实验台合成。
• Csp3–F bond activation by nucleophilic attack of the {Pt2S2} core assisted by non-covalent interactions
  作者：Ainara Nova、Rubén Mas-Ballesté、Gregori Ujaque、Pilar González-Duarte、Agustí Lledós

  DOI：10.1039/b801889h

  日期：——

  The high nucleophilicity of the sulfur atoms in [Pt(2)(dppp)(2)(micro-S)(2)] triggers a C-F activation process in 1,3-difluoro-2-propanol that leads to the [Pt(2)(dppp)(2)(micro-S)(micro-SCH(2)CH(OH)CH(2)F]F product through a S(N)2 mechanism, where the O-HF hydrogen bond established from the alcohol group of the organic substrate is essential for assisting the departure of the fluoride anion.

  [Pt（2）（dppp）（2）（micro-S）（2）]中硫原子的高度亲核性触发了1,3-二氟-2-丙醇中CF的活化过程，从而导致[Pt（ 2）（dppp）（2）（micro-S）（micro-SCH（2）CH（OH）CH（2）F] F产品通过S（N）2机理形成，其中O-HF氢键由有机底物的醇基对于协助氟阴离子的离去是必不可少的。
• A Novel Route to Multinuclear d ⁸ Metal−Chalcogen Compounds with Nuclearity Control
  作者：Rubén Mas‐Ballesté、William Clegg、Agustí Lledós、Pilar González‐Duarte

  DOI：10.1002/ejic.200400257

  日期：2004.8

  We have designed a new synthetic procedure to obtain multinuclear aggregates containing a Pt2S2}n core. The synthetic strategy involves the reaction of [(dppp)Pt(μ-S)2Pt(dppp)] with [PtCl2(PhCN)2] and thus the expansion of the Pt2S2} ring to a [Pt2S2}PtCl2] fragment. The lability of the chloride anions allows their replacement by bridging sulfide ligands, thus affording a new [Pt2(μ3-S)2}Pt2(μ-S)2}Pt2(μ3-S)2}]

  我们设计了一种新的合成程序来获得包含 Pt2S2}n 核的多核聚集体。合成策略涉及 [(dppp)Pt(μ-S)2Pt(dppp)] 与 [PtCl2(PhCN)2] 的反应，从而将 Pt2S2} 环扩展为 [Pt2S2}PtCl2] 片段。氯阴离子的不稳定性允许通过桥接硫化物配体来替代它们，从而提供新的 [Pt2(μ3-S)2}Pt2(μ-S)2}Pt2(μ3-S)2}] 核心。它随后演变为 [Pt2S2}3PtCl2] 为新循环奠定了基础。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)
• Aromatic C–F activation by complexes containing the {Pt2S2} core via nucleophilic substitution: a combined experimental and theoretical study
  作者：Ainara Nova、Rubén Mas-Ballesté、Gregori Ujaque、Pilar González-Duarte、Agustí Lledós

  DOI：10.1039/b901697j

  日期：——

  The C–F bond activation of perfluorobenzene and perfluoropyridine have been achieved by means of the complex [Pt2(μ-S)2(dppp)2], where dppp denotes 1,3-bis(diphenylphosphino)propane. The reaction with the first substrate requires a long time (five days) and high temperature (reflux in toluene) to yield [Pt(o-S2C6F4)(dppp)] and [Pt3(μ3-S)2(dppp)3]F2, and involves replacement of two fluorides in the

  C–F债券 激活 的 全氟苯 和 全氟吡啶已经通过复合物[PT 2（μ-S）2（DPPP）2 ]实现了反应，其中DPPP表示1,3-双（二苯基膦基）丙烷。与第一种底物的反应需要很长时间（五天）和高温（回流甲苯），得到[PT（ø -S 2 ç 6 ˚F 4）（DPPP）]和[铂3（μ 3 -S）2（DPPP）3 F的2，并涉及更换两个氟化物的邻位位置。相反，与全氟吡啶是更快（在0℃下15分钟），得到[PT 2（μ-S）μ-（p -SC 5 ˚F 4 N）}（DPPP）2 ] F，其意味着C-F活化在对位相对于吡啶 氮。已经对两个反应的机理进行了计算研究，并且过渡态的几何形状与S N Ar机理一致，其中硫基 桥接 配体替代氟阴离子。对应于第一和第二氟化物置换是131.7和137.1千焦摩尔的能量壁垒-1为全氟苯和85.9和142.7 kJ mol -1对于全氟吡啶， 分别。第一次取代的不同能
• Unusual C−H Allylic Activation in the {Pt^II(cod)} Fragment Bonded to a {Pt₂(μ-S)₂} Core
  作者：Rubén Mas-Ballesté、Paul A. Champkin、William Clegg、Pilar González-Duarte、Agustí Lledós、Gregori Ujaque

  DOI：10.1021/om034312x

  日期：2004.5.1

  Complexes [Pt-2(mu(3)-S)(2)(dppp)(2)}Pt(cod)]Cl-2 (1) and [Pt-2(mu(3)-S)(2)(cod)(2)}Pt(dppp)]Cl-2 (3), where dppp = 1,3-bis(diphenylphosphino)propane and cod = 1,5-cyclooctadiene, have been synthesized by reacting [Pt-2(mu-S)(2)(dppp)(2)] and [PtCl2(cod)] (1:1), and [Pt(SH)(2)(dppp)] and [PtCl2(cod)] (1:2), respectively. Complex I has not allowed substitution of cod by the chelating dppp ligand. Remarkably, the reaction of I with methoxide anion yields [Pt-2(mu(3)-S)(2)(dppp)(2)}Pt(C8H11)]Cl (2), which entails deprotonation of cod instead of the nucleophilic attack of CH3O- on the olefinic bond. In addition, replacement of the deprotonated cod ligand in 2 by dppp has not been achieved. A combination of experimental data and DFT calculations in 2 is consistent with the binding of C8H11- to platinum(II) by means of one eta(2)-alkene and one eta(1)-allyl bond. The structures of 1 and 2 have been confirmed by single-crystal X-ray diffraction. Analogous to 1, the reaction of 3 with sodium methoxide causes the subsequent deprotonation of the two cod ligands, yielding [Pt-2(mu(3)-S)(2)(cod)(C8H11)}Pt(dppp)] Cl (4) and [Pt-2(mu(3)-S)(2)(C8H11)(2)}Pt(dppp)] (5). In contrast to 1, replacement of cod by dppp in 3 and 4 leads to 1 and 2, respectively. Also, the substitution of one C8H11- ligand by dppp in 5 leads to 2. On the basis of DFT calculations, with inclusion of solvent effects, the factors governing the chemical behavior of the Pt(cod)}(2+) fragment bonded to a [Pt-2(mu-S)(2)L-4] (L-2 = dppp, cod, or C8H11-) metalloligand are discussed.