trans-[PtI2(dimethyl sulfide)2] | 18534-69-5

• 分子结构分类: 有机化合物 - 有机硫化合物
• 英文名称: trans-[PtI2(dimethyl sulfide)2]
• 英文别名: trans-PtI2(dimethyl sulphide)2；trans-PtI2(S(CH3)2)2；{Ptms2I2}；trans-PtI2(dimethyl sulfide)2；trans-PtI2(SMe2)2；diiodoplatinum;methylsulfanylmethane
• CAS: 18534-69-5
• 化学式: C₄H₁₂I₂PtS₂
• 分子量: 573.16
• InChiKey: KTYAVSWOQPCSLQ-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  3.73
• 重原子数：
  9.0
• 可旋转键数：
  2.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  trans-[PtI2(dimethyl sulfide)2] 以 further solvent(s) 为溶剂， 生成 {Ptms2I4}
  参考文献：
  名称：

  cis–transIsomers of PtX₄L₂(X= halogen andL= neutral ligand):trans-bis(dimethyl sulfide)tetraiodidoplatinum(IV)

  摘要：

  The octahedral title complex, [PtI4(C2H6S)(2)] or trans-PtI4(dms)(2) (dms is dimethyl sulfide), crystallizes in the monoclinic space group P2(1)/n (Z = 2), with molecular symmetry C-i, which is the most frequently occurring point group for trans-PtX4L2 {56%, 28 structures in the Cambridge Structural Database (CSD) [Allen (2002). Acta Cryst. B58, 380-388]}, followed by C-1 (22%, 11 structures). The complexes form a puckered pseudo-hexagonal layer in the (101) plane, and the layers are stacked with an interplanar distance of 7.10 angstrom. Density functional theory (DFT) calculations on an isolated complex with the observed parameters as a starting structure converged to C-2h. Constraints to Ci on the observed geometry give 3-4 kJ mol(-1) higher energy compared with C-2h. DFT calculations on [PtCl4(PzH)(2)] (PzH is pyrazole), reported in the CSD in both the cis and trans forms, show an energy difference of 21 kJ mol(-1) in favour of the trans complex. A CSD search for PtX4L2-type complexes, where X is a halogen and L is a ligand with a donor atom from group 14, 15 or 16, indicated a preferred trans geometrical arrangement, with a total fraction of 68%. The dominating crystal packing operators for the trans complexes are an inversion centre combined with a screw axis/glide plane (48%), followed by an inversion centre alone (28%).

  DOI：

  10.1107/s0108270107060799
• 作为产物：
  描述：

  {Ptms4(NO3)2} 、 potassium iodide 以 not given 为溶剂， 生成 trans-[PtI2(dimethyl sulfide)2]
  参考文献：
  名称：

  Blomstrand, C. W.; Enebrske, C., Journal fur praktische Chemie (Leipzig 1954), 1888, vol. 38, p. 358 - 365

  摘要：

  DOI：

文献信息

• Synthesis and Characterization of Group 14−Platinum(IV) Complexes
  作者：Christopher J. Levy、Jagadese J. Vittal、Richard J. Puddephatt

  DOI：10.1021/om950493u

  日期：1996.4.16

  [PtMe2(diimine)] complexes give facile trans oxidative addition of the E−X bond (E = Si, X = Br, I; E = Ge, Sn, X = Cl, Br, I). The oxidative additions occur more readily for MenEX4-n in the sequences X = I > Br > Cl and E = Sn > Ge > Si. The first stable silylplatinum(IV) complexes have been prepared in this way, and the X-ray crystal structure of [PtIMe2(Me3Si)(bpy)] shows an exceptionally long Pt−I bond length

  第14组化合物Me n EX 4- n（E = Si，Ge，Sn; X = Cl，Br，I）与富电子的[PtMe 2（diimine ）]配合物的反应可轻松实现E-的反氧化加成X键（E = Si，X = Br，I; E = Ge，Sn，X = Cl，Br，I）。对于Me n EX 4- n而言，以X = I> Br> Cl和E = Sn> Ge> Si的顺序更容易发生氧化加成。以这种方式制备了第一个稳定的甲硅烷基铂（IV）配合物，[PtIMe 2（Me 3 Si）（bpy）]的X射线晶体结构显示了异常长的Pt-I键长（2.963（1）Å ）与高反三甲基甲硅烷基的影响。1 H NMR研究表明，涉及锗和锡试剂的氧化加成反应易于逆转。几种铂（IV）-锡配合物具有掺入晶格中的第二分子锡试剂。[PtIMe 2（Me 3 Sn）（bpy- t bu 2）] 2 ·Me 3 SnI·CH 2 Cl 2的
• Mono- and Dinuclear Binding Modes of the 2,5-Bis(α-pyridyl)pyrrolate Ligand in Platinum(II) Complexes
  作者：Drew C. Newman、Michael R. Gau、Patrick J. Carroll、Karen I. Goldberg

  DOI：10.1021/acs.organomet.1c00152

  日期：2021.6.28

  A series of platinum(II) complexes with the 2,5-bis(α-pyridyl)pyrrolate (PDP) ligand were synthesized. The ligand (X) trans to the central pyrrole nitrogen of PDP was found to play a key role in whether tridentate monomeric or bidentate clamshell dimer complexes were formed. When X = CH3 or C6H5, strong σ-donor ligands, only dimeric clamshell structures were observed. In contrast, when X = Cl or I

  合成了一系列具有 2,5-双(α-吡啶基)吡咯酸酯 (PDP) 配体的铂 (II) 配合物。发现与 PDP 的中心吡咯氮反式的配体 (X) 在三齿单体或双齿蛤壳二聚体复合物的形成中起关键作用。当 X = CH 3或 C 6 H 5 时，强σ-供体配体，仅观察到二聚蛤壳结构。相反，当 X = Cl 或 I，具有 π 供体特性的配体时，可以制备二聚体和单体复合物。配体框架支持与 π 供体 X 型配体形成单体复合物的能力归因于 PDP 配体在单体构象中充当有效 π 酸的能力。
• Coordination of Alkenes at a Highly Electrophilic Site. New Dicationic Platinum(II) Complexes:  Synthesis, Structure, and Reactions with Nucleophiles
  作者：Christine Hahn、Pasquale Morvillo、Eberhardt Herdtweck、Aldo Vitagliano

  DOI：10.1021/om010833d

  日期：2002.4.29

  corresponding β-functionalized σ-alkyl complexes [Pt(PNP)(CHRCHR‘Nu)]BF4 also in the absence of auxiliary bases. In the case of the styrene derivatives an unusual decomposition pathway gives the stable alkenyl complex [Pt(PNP)(CHCHPh)]BF4. A competitive equilibrium process between substitution and addition was revealed by reacting ethylene with the isolated aniline complex [Pt(PNP)(PhNH2)](BF4)2. The nucleophilic

  二阳离子铂（II）链烯络合物[Pt（PNP）（链烯）]（BF 4）2（链烯=乙烯，丙烯，1-丁烯，Z-和E -2-丁烯，苯乙烯，降冰片烯; PNP = 2,6制备了双（二苯基膦基甲基）吡啶并通过1 H和13 C NMR光谱表征，并通过X射线衍射分析确定了乙烯配合物的分子结构。与已知的中性和单阳离子物种相比，配位双键的亲核攻击更容易发生，并且各种质子亲核试剂NuH（MeOH，H 2 O，芳族胺）给出相应的β-官能化σ-烷基络合物[Pt（PNP ）（CHRCHR'Nu）] BF 4也没有辅助基地。在苯乙烯衍生物的情况下，不寻常的分解途径给出了稳定的烯基络合物[Pt（PNP）（CH CHPh）] BF 4。通过使乙烯与分离的苯胺络合物[Pt（PNP）（PhNH 2）]（BF 4）2反应，揭示了取代与添加之间的竞争平衡过程。已发现，与类似的钯配合物相比，亲核加成产物在热力学上优于取代产物。
• Platinum and rhodium complexes of dialkenyl telluroether ligands: synthesis, dynamic nuclear magnetic resonance and crystal structure of cis-dibromo(3,3,7,7-tetramethyl-5-tellura-3,7-disilanona-1,8-diene)platinum(II)
  作者：Edward W. Abel、Julian R. Koe、Michael B. Hursthouse、K. M. Abdul Malik、Mohammed A. Mazid

  DOI：10.1039/dt9940002645

  日期：——

  data have been obtained and are discussed with reference to the chelate ring effect. The crystal structure of [PtBr2Te(CH2SiMe2-CHCH2)2}] has been determined: crystals are triclinic of space group P with a= 6.5837(9), b= 8.8594(8), c= 17.860(2)Å, α= 98.65(2), β= 97.73(1), γ= 111.26(1)° and Z= 2. The structure is monomeric with the platinum atom exhibiting square-planar geometry. The two bromine atoms

  已经合成了许多二烯基碲醚醚配体。与铂（II）和铑（I）的金属中心在非水介质中在低温下反应，生成的络合物中的配体分别是二齿的（通过碲原子和一个烯烃官能团结合）和三齿的。二齿铂络合物是流动性的，表现出烯烃部分的交换，已经对其能垒进行了评估。已获得碲125 NMR数据，并已参考螯合环效应进行了讨论。已确定[PtBr 2 Te（CH 2 SiMe 2 -CH CH 2）2 }]的晶体结构：晶体为空间群P的三斜晶，具有a = 6.5837（9），b = 8.8594（8），c = 17.860（2）Å，α= 98.65（2），β= 97.73（1），γ= 111.26（1）°和Z =2。结构铂原子是单体，铂原子表现出正方形平面的几何形状。两个溴原子是顺式，二（硅烯基）碲醚醚配体通过碲原子和一个烯烃部分与金属螯合。
• Klason, P., 1903, vol. 28, # 6, p. 3 - 42
  作者：Klason, P.

  DOI：——

  日期：——