trans-[PtMeCl(dmso)₂] | 70424-04-3

• 分子结构分类: 有机化合物 - 有机硫化合物
• 英文名称: trans-[PtMeCl(dmso)₂]
• 英文别名: trans-[Pt(DMSO)₂MeCl]；carbanide;chloroplatinum(1+);methylsulfinylmethane
• CAS: 70424-04-3
• 化学式: C₅H₁₅ClO₂PtS₂
• 分子量: 401.838
• InChiKey: XNTNPYTZOLPEIR-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  trans-[PtMeCl(dmso)₂] 在 bis(dimethylamino)acridine 作用下， 以 二氯甲烷 为溶剂， 以99%的产率得到trans(C,N)-chloromethyl(dimethyl sulfoxide)(bis(dimethylamino)acridine)platinum(II)
  参考文献：
  名称：

  trans-Chloromethylbis(dimethyl sulfoxide)platinum(II):  X-ray Structure, Mechanism of Isomerization, and Its Use as a Precursor to Organoamine Complexes of Variable Geometrical Configurations

  摘要：

  An unusual 2:1 aggregate between the complex trans-[PtCl(CH3)(DMSO)(2)] (1; DMSO = dimethyl sulfoxide) and the organotin compound bis(mu(3)-oxo)bis(mu-chloro)bis(mu-dimethyltin(IV))bis(chlorodimethyltin(IV)) [Cl(CH3)(2)-SnOSn(CH3)(2)Cl](2) has been isolated and characterized by X-ray analysis. The crystals belong to the triclinic space group with lattic constants a = 9.373(2) Angstrom, b = 9.576(1) Angstrom, c = 14.087(3) Angstrom, alpha = 70.29(1), beta = 75.50(1)degrees, gamma = 72.21(2)degrees, and Z = 2. Least-squares refinement of the structure led to an R factor of 2.37%. H-1, C-13, and (195)PtNMR measurements revealed that in chloroform solution complex 1 gives a mixture of four different species, which have been unambigously identified as the starting complex 1 in equilbrium with cis-[PtCl(CH3)-(DMSO)(2)] and the two corresponding isomeric aqua-species cis and trans-[PtCl(CH3)(DMSO)(2)](OH2)]. The Pt-195 NMR magnetization transfer technique allowed determination of the rate of interconversion among the various complexes, showing that the direct trans-cis isomerism between the [PtCl(CH3)DMSO)(2)] species is negligible and that the geometrical interconversion occurs through a water-catalyzed pathway. The exchange between free and coordinated DMSO in cis- and trans-[PtCl(CH3)(DMSO)(2)] has been measured by H-1 NMR magnetization transfer experiments. The molecule of DMSO in the position trans to a methyl group was found to be 10-fold more labile than that trans to another sulfur bonded dimethyl sulfoxide. The reactivity of complex 1 in chloroform with a series of monodentate nitrogen ligands having widely different electronic and steric properties has been investigated by H-1 NMR spectorscopy. The utility of this system as precursor for the synthesis of cis and trans-[PtCl(CH3)(DMSO)(am)] is discussed together with the evidence for the factors promoting the prevalence of a geometrical configuration.

  DOI：

  10.1021/ic960428s
• 作为产物：
  描述：

  cis-[PtMe₂(dmso)₂] 、 cis-dichlorobis(dimethylsulfoxide)platinum(II) 以 二氯甲烷 为溶剂， 反应 24.0h， 以65%的产率得到trans-[PtMeCl(dmso)₂]
  参考文献：
  名称：

  再次探讨反式-[Pt（dmso）2 ClMe]和顺式-[Pt（dmso）2 Me 2 ]的合成：实验和DFT研究

  摘要：

  的制备反式- [PT（DMSO）2的ClMe]（2）和顺式- [PT（DMSO）2我2 ]（3）从顺式- [PT（DMSO）2氯2 ]（1）和SnMe 4具有重新检查（dmso =二甲基亚砜）。从实验和DFT研究中获得的信息已允许改进先前报道的在反应时间，反应产率和原子经济性方面合成两种配合物的方法。这些研究表明，配合物1与第一当量的SnMe 4反应形成反式-[PT（DMSO）2的ClMe]（2）作为中间体迅速与SnMe的第二当量进行反应4，得到顺式- [PT（DMSO）2我2 ]（3）。当仅添加1当量的有机锡烷试剂时，3与过量的未反应1的混合使反应回到反式[Pt（dmso）2 ClMe]的形成（2）。已经使用DFT计算研究了这种成比例的机理。

  DOI：

  10.1016/j.jorganchem.2019.06.002

文献信息

• Mechanistic Insight into the Protonolysis of the Pt−C Bond as a Model for C−H Bond Activation by Platinum(II) Complexes
  作者：Raffaello Romeo、Giuseppina D'Amico

  DOI：10.1021/om060217n

  日期：2006.7.1

  The kinetic and NMR features of the protonolysis reactions on platinum(II) alkyl complexes of the types cis-[PtMe2L2], [PtMe2(L-L)], cis-[PtMeClL2], and [PtMeCl(L-L)] (L = PEt3, P(Pri)3, PCy3, P(4-MePh)3, L-L = dppm, dppe, dppp, dppb) in methanol suggest a rate-determining proton attack at the Pt−C bond. In contrast, a multistep oxidative-addition−reductive-elimination mechanism characterizes the methane

  顺式-[PtMe 2 L 2 ]，[PtMe 2（LL）]，顺式-[PtMeClL 2 ]和[PtMeCl（LL）]的铂（II）烷基络合物的质子分解反应的动力学和NMR特征。（L = PEt 3，P（Pr i）3，PCy 3，P（4-MePh）3，LL = dppm，dppe，dppp，dppb）在甲醇中显示出决定Pt-C键质子进攻的速率。相比之下，多步氧化加减还原机理表征了相应反式-[PtMeClL 2的质子化过程中的甲烷损失] 物种。在暗示这两个系统的不同反应途径方面具有特殊诊断性的工具是（i）动力学氘同位素实验的结果不同（ii）低温1 H NMR检测或不检测Pt（IV）氢化烷基中间产物实验，以及（iii）检测或不存在同位素加扰以及将氘掺入Pt-CH 3中，并损失一定范围的CH n D n - 4异构体。对于所有系统，质子分解的速度受配体空间拥塞的阻碍，受配体电子的贡献而加速，并且几乎
• Mono‐ and Trinuclear Tripodal Platinum(II) Chelated Complexes Containing a Pyridine/Sulfoxide Based Anchoring Framework
  作者：Anna Barattucci、M. Rosaria Plutino、Cristina Faggi、Paola Bonaccorsi、Luigi Monsù Scolaro、Maria Chiara Aversa

  DOI：10.1002/ejic.201300042

  日期：2013.7

  species 6a to a CD3CN solution of a platinum(II) complex of the type cis-[PtMe2(Me2SO)2] (Pt1) or trans-[PtMeCl(Me2SO)2] (Pt2), platinum(II) coordination and chelation occurred, as definitively indicated by a sharp change in the 1H NMR spectrum towards the final corresponding chelated platinum(II) species and free dimethyl sulfoxide. The prepared platinum(II) species contain one or three fragments of the

  新的三足配体 2,4,6-triethyl-1,3,5-tris[1-(2-pyridinyl)ethenyl]sulfinylmethyl}benzos 6，其特征在于三个侧链，每个都含有亚砜和吡啶部分，合成自相应的次磺酸和2-乙炔基吡啶。获得并分离了两种非对映体混合物，一种外消旋混合物6a，具有C3对称轴，而另一种6b没有对称性。为了研究这些螯合-κN,κS型配体的配位能力，还合成了单支化外消旋[1-(2-吡啶基)乙烯基]亚磺酰基苯9。将等量的单螯合配体 9 或三足类物质 6a 添加到顺式-[PtMe2(Me2SO)2] (Pt1) 或反式-[PtMeCl(Me2SO) 类型的铂 (II) 络合物的 CD3CN 溶液中2] (Pt2), 铂 (II) 发生配位和螯合，正如 1H NMR 谱向最终相应的螯合铂 (II) 物质和游离二甲基亚砜的急剧变化所明确表明的那样。制备的铂 (II)
• Synthesis of platinum(II) alkyl and aryl complexes from K2[PtCl4] and tetraorganotin compounds in dimethyl sulphoxide
  作者：Colin Eaborn、Kalipada Kundu、Alan Pidcock

  DOI：10.1039/dt9810000933

  日期：——

  Complexes cis-[PtR2(dmso)2] and cis-[PtRCl(dmso)2](dmso = dimethyl sulphoxide) are readily obtained from K2[PtCl4] and SnMe3R (R = aryl or Me) in dmso at 70–90 °C. Hydrogen-1 n.m.r. spectra show that the dmso ligands are bound through sulphur in solution and that the dmso ligand trans to R in cis-[PtRCl(dmso)2] undergoes dissociation and exchange at ambient temperature. With anionic reagents X–(X =

  络合物顺- [PTR 2（DMSO）2 ]和顺- [PTRCl（DMSO）2 ]（DMSO =二甲亚砜）可容易地选自K得到2 [氯铂酸4 ]和SnMe 3 R（R =芳基或Me）在DMSO在70–90°C下。氢-1 NMR谱表明，该DMSO配体在溶液中，通过硫结合的配体DMSO反式中至R顺- [PTRCl（DMSO）2 ]经历解离和交换在室温下。与阴离子试剂X –（X = Br，I或SCN）形成复杂的顺式-[PTPhCl（DMSO）2]形成桥接复合物[PT 2 Ph 2（µ-X）2（DMSO）2 ]。除二芳基络合物外，SnMe 3（C 6 H 4 OMe-2）形成环金属化的络合物[H 2 -2）（DMSO）2。所有配合物的DMSO配体都容易被磷供体AsPh 3，SbPh 3或2,2'-联吡啶取代；报道了含磷络合物的31 P- 1 H} nmr参数。
• Water-Soluble Mono- and Dimethyl N-Heterocyclic Carbene Platinum(II) Complexes: Synthesis and Reactivity
  作者：Edwin A. Baquero、Juan C. Flores、Josefina Perles、Pilar Gómez-Sal、Ernesto de Jesús

  DOI：10.1021/om500753v

  日期：2014.10.13

  formula cis-[PtMe2(dmso)(NHC·Na)] (2), in which NHC is an anionic N-heterocyclic carbene bearing a sulfonatopropyl chain on one of the nitrogen atoms and a sulfonatopropyl (a), methyl (b), mesityl (c), or 2,6-diisopropylphenyl group (d) on the other, have been prepared. The hydrolytic stability of the Pt–C bonds in these complexes under different neutral, alkaline, and acidic aqueous conditions has also

  分子式为顺式-[PtMe 2（dmso）（NHC·Na）]（2）的水溶性二甲基配合物家族，其中NHC是在氮原子之一上带有磺酰磺丙基链的阴离子N杂环卡宾， sulfonatopropyl（一），甲基（b），三甲苯基（ç），或2,6-二异丙基（d上的除外），已经制备。还研究了在不同的中性，碱性和酸性水溶液条件下，这些络合物中Pt–C键的水解稳定性。发现络合物2在室温下在水中在中性或碱性条件下非常稳定。降解在较高温度下发生，但涉及C sp除Pt-Me键水解外，还具有3 -H活化和C-C还原消除过程。良好的亲核试剂有利于铂-甲基键的水解裂解。因此，向2的水溶液中添加KCN导致形成了单甲基络合物K [PtMe（CN）2（NHC·Na）]（9），而二甲基络合物K [PtMe 2（CNR）（NHC· Na）]（10）用异氰化物CNCH 2 COOK形成。在2的水溶液中添加化学计量的质子酸可导致一个或两个
• Platinum(<scp>ii</scp>) complexes bearing 1,1′-bis(diphenylphosphino)ferrocene as building blocks for functionalized redox active porphyrins
  作者：Luigi Monsù Scolaro、Maria Rosaria Plutino、Andrea Romeo、Raffaello Romeo、Giampaolo Ricciardi、Sandra Belviso、Alberto Albinati

  DOI：10.1039/b516391a

  日期：——

  dppf (1,1′-bis(diphenylphosphino)ferrocene) and dppe (1,2-bis(diphenylphosphino)ethane)) with 5,10,15,20-tetrakis(4-pyridyl)-21H,23H-porphyrin (TpyP) led to the formation of the symmetrical tetraplatinated porphyrin complexes, [PtMe(PP)]4TpyP·X4 (PP = dppf, X = CF3SO3−, 3, and PP = dppe, X = BF4−, 5) containing the organometallic fragment PtMe(PP)}. The precursor sulfoxide platinum complexes [PtM

  阳离子络离子[PTMe（Me 2 SO）（PP）] +（PP = DPPF（1,1'-双（二苯基膦基）二茂铁）和DPPE （1,2-双（二苯基膦基）乙烷）） 和 5,10,15,20-四（4-吡啶）-21 H，23 H-卟啉 （TpyP）导致形成对称的四铂 卟啉络合物，[PTME（PP）] 4 TpyP·X 4（PP = DPPF，X = CF 3 SO 3 - ，3，和PP =DPPE，X = BF 4 - ，5）含有有机金属片段PTME（PP）}。前体亚砜铂配合物[PTME（ME 2 SO）（DPPF）] CF 3 SO 3，2和[PTME（ME 2 SO）（DPPE）] BF 4，4，通过制备卤化物分别从[PTMeCl（DPPF）]，1中提取和通过[PTMe 2（DPPE）]的受控质子分解，在少量二甲基亚砜。所有这些起始铂（II）化合物以及卟啉导数3和5可以通过以下方式充分表征元素分析，