[Pt(SH)2(1,3-bis(diphenylphosphino)propane)] | 637032-74-7

• 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: [Pt(SH)2(1,3-bis(diphenylphosphino)propane)]
• 英文别名: Pt(SH)2(diphenyldiphosphinopropane)
• CAS: 637032-74-7
• 化学式: C₂₇H₂₈P₂PtS₂
• 分子量: 673.679
• InChiKey: KKVULSDNMWDRKX-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  32.0
• 可旋转键数：
  4.0
• 环数：
  5.0
• 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：

  1-pyridyl-2-yl-2-bromoethanone 、 [Pt(SH)2(1,3-bis(diphenylphosphino)propane)] 以 N,N-二甲基甲酰胺 为溶剂， 以81%的产率得到Pt(diphenyldiphosphinopropane)(C2S2(2-pyridine)(H))
  参考文献：
  名称：

  Low temperature emission spectra of 2-pyridyl-substituted platinum-1,2-enedithiolates

  摘要：

  The emissions from the 2-pyridyl- and 2-pyridinium-substituted platinum-1,2-enedithiolate complexes, L2Pt{S2C2(2-pyridyl(ium))(R)} where L = PPh3, PPh2Me, PPhMe2, P(propyl)3 and L-2 = dppm, dppe, and dppp were studied in DMM (DMF-CH2Cl2-MeOH, 1:1:1, v/v/v) glasses at 77 K. All of the pyridyl-substituted complexes have an emission between 18,600 and 17,900 cm(-1) with pronounced 1200 cm(-1) vibronic structure. The lifetimes of the pyridyl-substituted complexes are 216-350 mus. The pyridinium-substituted complexes have emissions in the range of 16,600-16,100 cm(-1) with less resolved vibronic structure than their pyridyl counterparts. The lifetimes of the pyridinium-substituted complexes are 158-290 mus. The emission at 77 K from both the pyridyl- and pyridinium-substituted complexes contrasts with the room temperature studies where only selected pyridinium complexes were emissive. (C) 2003 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(03)00211-1
• 作为产物：
  描述：

  [1,3-bis(diphenylphosphino)propane]dichloroplatinum(II) 、 硫化氢 、 sodium 以 乙醇 为溶剂， 以65%的产率得到[Pt(SH)2(1,3-bis(diphenylphosphino)propane)]
  参考文献：
  名称：

  Low temperature emission spectra of 2-pyridyl-substituted platinum-1,2-enedithiolates

  摘要：

  The emissions from the 2-pyridyl- and 2-pyridinium-substituted platinum-1,2-enedithiolate complexes, L2Pt{S2C2(2-pyridyl(ium))(R)} where L = PPh3, PPh2Me, PPhMe2, P(propyl)3 and L-2 = dppm, dppe, and dppp were studied in DMM (DMF-CH2Cl2-MeOH, 1:1:1, v/v/v) glasses at 77 K. All of the pyridyl-substituted complexes have an emission between 18,600 and 17,900 cm(-1) with pronounced 1200 cm(-1) vibronic structure. The lifetimes of the pyridyl-substituted complexes are 216-350 mus. The pyridinium-substituted complexes have emissions in the range of 16,600-16,100 cm(-1) with less resolved vibronic structure than their pyridyl counterparts. The lifetimes of the pyridinium-substituted complexes are 158-290 mus. The emission at 77 K from both the pyridyl- and pyridinium-substituted complexes contrasts with the room temperature studies where only selected pyridinium complexes were emissive. (C) 2003 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/s0020-1693(03)00211-1

文献信息

• 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.
• Synthesis, Structures, and Properties of Group 9− and Group 10−Group 6 Heterodinuclear Nitrosyl Complexes
  作者：Kazuya Arashiba、Hidetaka Iizuka、Shoji Matsukawa、Shigeki Kuwata、Yoshiaki Tanabe、Masakazu Iwasaki、Youichi Ishii

  DOI：10.1021/ic702309h

  日期：2008.5.19

  The reaction of the group 9 bis(hydrosulfido) complexes [Cp*M(SH)(2)(PMe3)] (M = Rh, Ir; Cp* = eta(5)-C5Me5) with the group 6 nitrosyl complexes [CP*M'Cl-2(NO)] (M' = Mo", W) in the presence of NEt3 affords a series of bis(sulfido)bridged early-late heterobimetallic (ELHB) complexes [CP*M(PMe3)(mu-S)(2)M'(NO)Cp*] (2a, M = Rh, M' = Mo; 2b, M = Rh, M' = W; 3a, M = Ir, M' = Mo; 3b, M = Ir, M' = W). Similar reactions of the group 10 bis(hydrosulfido) complexes [M(SH)(2)(dppe)] (M = Pd, Pt; dppe = Ph2P(CH2)(2)PPh2), [Pt(SH)(2)(dppp)] (dppp = Ph2P(CH2)(3)Pph(2)), and [M(SH)(2)(dpmb)] (dpmb = o-C6H4(CH2PPh2)(2)) give the group 10-group 6 ELHB complexes [(dppe)M(mu-S)(2)M'(NO)Cp*] (M = Pd, Pt; M'= Mo, W), [(dppp)Pt(mu-S)(2)M'(NO)Cp*] (6a, M'= Mo; 6b, M'= W), and [(dpmb)M(mu-S)(2)M'(NO)Cp*] (M = Pd, Pt; M' = Mo, W), respectively. Cyclic voltammetric measurements reveal that these ELHB complexes undergo reversible one-electron oxidation at the group 6 metal center, which is consistent with isolation of the single-electron oxidation products [Cp*M(PMe3)(mu-S)(2)M'(NO)Cp*][PF6] (M = Rh, Ir; M' = Mo, W). Upon treatment of 2b and 3b with ROTf (R = Me, Et; OTf = OSO(2)CFA the 0 atom of the terminal nitrosyl ligand is readily alkylated to form the alkoxyimido complexes such as [Cp*Rh(PMe3)(mu-S)(2)W(NOMe)Cp*][OTf]. In contrast, methylation of the Rh-, Ir-, and Pt-Mo complexes 2a, 3a, and 6a results in S-methylation, giving the methanethiolato complexes [Cp*M(PMe3)(mu-SMe)(mu-S)Mo(NO)Cp*][BPh4] (M = Rh, Ir) and [(dppp)Pt(mu-SMe)(mu-S)Mo(NO)Cp*][OTf], respectively. The Pt-W complex 6b undergoes either S- or O-methylation to form a mixture of [(dppp)Pt(mu-SMe)(mu-S)W(NO)Cp*][OTf] and [(dppp)Pt(mu-S)(2)W(NOMe)Cp*][OTf]. These observations indicate that O-alkylation and one-electron oxidation of the dinuclear nitrosyl complexes are facilitated by a common effect, i.e., donation of electrons from the group 9 or 10 metal center, where the group 9 metals behave as the more effective electron donor.