trans-chlorohydridobis(triphenylphosphine)platinum(II) | 16902-93-5

• 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: trans-chlorohydridobis(triphenylphosphine)platinum(II)
• 英文别名: trans-Pt(H)(Cl)(PPh3)2；Chloro(hydrido)platinum;triphenylphosphane
• CAS: 16902-93-5
• 化学式: C₃₆H₃₁ClP₂Pt
• 分子量: 756.123
• InChiKey: UAFUWNADULFYLQ-UHFFFAOYSA-M

物化性质

• 熔点：
  215 °C

计算性质

• 辛醇/水分配系数(LogP)：
  7.31
• 重原子数：
  40
• 可旋转键数：
  6
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  trans-chlorohydridobis(triphenylphosphine)platinum(II) 在 triphenyl phosphine 、 CO 、 dppe 、 CHCl₃ 、 H₂ 作用下， 以 乙醇 、 二氯甲烷 、 氯仿 、 甲苯 为溶剂， 生成 [platinum(II)dichloride(1,2-bis(diphenylphosphino)ethane)]
  参考文献：
  名称：

  铂-锡体系在烯烃加氢甲酰化反应中的化学计量模型反应

  摘要：

  The three independent steps involved in the hydroformylation process, insertion of the olefin, insertion of carbon monoxide, and hydrogenolysis, have been investigated with use of platinum-tin catalysts and 1-pentene as olefin at low pressure and temperature in CH2Cl2. In the temperature range 198-308 K, the three reactions can be studied consecutively. All the intermediates observed were prepared and characterized separately. The complex trans-[PtH(SnCl3)(PPh3)2] was used as the initial compound for this sequence. The hydrido complex crystallized in the monoclinic space group C2/c, with a = 31.345 (5) angstrom, b = 12.716 (3) angstrom, c = 18.135 (3) angstrom, beta = 96.5 (2)-degrees, Z = 8, and R (R(w)) = 0.056 (0.060) for 3235 independent reflections having I > 2.56-sigma(I). The large Pt-Sn bond (2.601 (1) angstrom) distance correlates satisfactorily with the low 1J(Pt-Sn) value. The Pt-Sn bond is necessary for the insertion of 1-pentene in the hydrido-platinum complex and for the hydrogenolysis of the acyl compounds under these mild conditions. The insertion of 1-pentene was observed at 198 K, giving the cis-alkyl complex; CO insertion took place after isomerization to the trans-alkyl complex. The instability of Pt-Sn and Pt-C bonds in the trans-acyl complex favors easy decarbonylation or loss of SnCl2, so any other platinum complex without tin accepts SnCl2 from the acyl complex. The hydrogenolysis of trans-[Pt(SnCl3)(COC5H11)(PPh3)2] under 1.5 bar of H2-CO (1:1) did not yield n-hexanal quantitatively; only 12% of n-hexanal was formed. Thus, decarbonylation was the main process observed. From the reactions studied, it is possible to propose the following order of Pt-Sn bond stability: trans-[Pt(SnCl3)(COC5H11)(PPh3)2] < [Pt(SnCl3)(C5H11)(PPh3)2] < trans-[PtH-(SnCl3)(PPh3)2] < [PtH(SnCl3)(CO)(PPh3)2] < [Pt(mu-Cl)(SnCl3)(PPh3)]2 < [PtCl(SnCl3)(PPh3)]- < [PtCl2(SnCl3)2]2-. The insertion reactions studied with cis-[PtCl2(olefin)(PR3)] as an olefin carrier and the hydrido-platinum complexes trans-[PtHCl(PPh3)2], trans-[PtH(SnCl3)(PPh3)2], and [PtH(SnCl3)-(CO)(PPh3)2] as hydrogen carriers exclude the participation of intermolecular steps by reaction of two different platinum complexes under the experimental conditions described.

  DOI：

  10.1021/om00058a019
• 作为产物：
  描述：

  cis-dichlorobis(triphenylphosphine)platinum(II) 在 氢气 、 四甲基氯化铵 、 tin(ll) chloride 作用下， 以 氯仿 为溶剂， 生成 trans-chlorohydridobis(triphenylphosphine)platinum(II)
  参考文献：
  名称：

  A simple preparative route to the complexes trans-[PtHCl(P)p-XC6H4)3)2] involving tin(II) chloride and hydrogen

  摘要：

  DOI：

  10.1016/s0020-1693(00)95384-2

文献信息

• Metals in orgranic syntheses
  作者：R. Bardi、A.M. Piazzesi、G. Cavinato、P. Cavoli、L. Toniolo

  DOI：10.1016/s0022-328x(00)93181-4

  日期：1982.1

  aldehyde from the acyl derivative, but it is not necessary for the formation of intermediate I, since this can be isolated in good yield even in the absence of the tin compound. The higher regioselectivity observed using intermediate I or II, compared with that when the precursor is used is discussed in terms of steric effects of the ligands competing for coordination to the platinum atom. The catalytic

  反式- [氯铂酸（COPR-n）的（PPH 3）2 ]（I）已经从通过处理丙烯的混合物得到的混合物良好的产率分离，顺式- [氯铂酸2（PPH 3）2 ]和的SnCl 2 ·在醇中存在或不存在氢的情况下，用一氧化碳在H 2 O中进行反应，实际上并没有发生明显的加氢甲酰化或羟基羰基化。所述顺式- [PECL 2（PPH 3 2 ] -SnCl 2 ·2小时2 O系统是在甲基异丁基酮的催化加氢甲酰化高活性，并从反应混合物在该培养基中已分离出反式-[Pt（SnCl 3）（COPr-n）（PPh 3）2 ]（II）（产率33％）。II型络合物中PtSn键的存在在促进由酰基衍生物形成醛的过程中起着关键作用，但是中间体I的形成不是必需的，因为可以高收率分离出中间体I。即使没有锡化合物也是如此。与使用前体时相比，使用中间体I或II观察到的更高的区域选择性是根据配体竞争与铂原子配位的空间效应来讨论的。还将
• Isoprene platinum(<scp>II</scp>) complexes from cis-dichlorobis(triphenylphosphine) platinum(<scp>II</scp>) and isopropenylacetylene. Crystal and molecular structures of trans-chloro(1-isopropenylvinyl)bis(triphenylphosphine)-platinum(<scp>II</scp>)–benzene (1/1) and trans-(isopropenylethynyl)(1-isopropenylvinyl)bis(triphenylphosphine)platinum(<scp>II</scp>)
  作者：Anita Furlani、Maria Vittoria Russo、Angiola Chiesi Villa、Amelia Gaetani Manfredotti、Carlo Guastini

  DOI：10.1039/dt9770002154

  日期：——

  reaction time and reagent concentrations. For comparison, the behaviour of phenylacetylene under similar conditions has been examined and trans-[Pt(CCPh)(CH2CPh)(PPh3)2] has also been obtained. The structures of (1) and (2) have been determined by single-crystal X-ray drffractometry: (1), monoclinic, a= 15.521 (3), b= 18.738(8), c= 16.872(5)Å, β= 125.07(2)°, Z= 4, space group Cc, R= 0.056: (2), orthorhombic

  当在异丙烯基乙炔的存在下，将顺式-[PtCl 2（PPh 3）2 ]与水合肼在乙醇中加热时，可获得三种主要产物：反式-[PtCl（CH 2 C–CMe CH 2）（PPh 3）2 ]（ 1），反式- [铂（CH 2 C-CME CH 2）（C C-CME CH 2）（PPH 3）2 ]（2），和[PT（CH C-CME CH 2）（PPH 3）2]（3）。（1），（2）或（3）的形成取决于反应时间和试剂浓度。为了比较，已经研究了在相似条件下苯乙炔的行为，并且还获得了反式-[Pt（C CPh）（CH 2 CPh）（PPh 3）2 ]。（1）和（2）的结构已通过单晶X射线衍射法确定：（1），单斜晶，a = 15.521（3），b = 18.738（8），c = 16.872（5）Å， β= 125.07（2）°，Z = 4，空间群Cc，R = 0.056：（2），正交，a = 18.94（1），b
• Heterometallic complexes with borole ligands †‡
  作者：Pierre Braunstein、Ulli Englert、Gerhard E. Herberich、Mark Neuschütz、Martin U. Schmidt

  DOI：10.1039/a903846i

  日期：——

  The borole-containing carbonylmetalates [(η-C4H4BPh)Re(CO)3]– ([Re]–) and [(η-C4H4BPh)Fe(CO)2H]– ([Fe]–) were used for the synthesis of heterometallic complexes with Re–Hg, Re–Cu, Re–Ag, Re–Au or Fe–Pt metal–metal bonds, respectively. The complex [Re]–Hg–[Re] 1 was characterized by X-ray diffraction and contains a linear metal chain. In the presence of HgCl2, redistribution reactions were observed, leading to [Re]–Hg–Cl 2 which was independently prepared from [Re]– and an excess of HgCl2. The reaction of [Fe]– with trans-[PtBr2(4-Mepy)2] (4-Mepy = 4-methylpyridine) afforded the trinuclear complex trans-[Pt[Fe]2(4-Mepy)2] 6 which was characterized by X-ray diffraction and contains two hydrido ligands which bridge the Fe–Pt bonds.

  含硼烷的羰基金属酸盐[(η-C4H4BPh)Re(CO)3]⁻（[Re]⁻）和[(η-C4H4BPh)Fe(CO)2H]⁻（[Fe]⁻）分别用于合成了含有Re-Hg、Re-Cu、Re-Ag、Re-Au或Fe-Pt金属-金属键的异金属配合物。配合物[Re]⁻Hg⁻[Re] 1通过X射线衍射进行了表征，并含有一个线性金属链。在存在HgCl2的情况下，观察到了重分布反应，生成了[Re]⁻Hg⁻Cl 2，该化合物也可以从[Re]⁻和过量的HgCl2独立制备。[Fe]⁻与trans-[PtBr2(4-Mepy)2]（4-Mepy = 4-甲基吡啶）的反应生成三核配合物trans-[Pt[Fe]2(4-Mepy)2] 6，该配合物通过X射线衍射进行了表征，并含有两个通过Fe-Pt键桥接的氢化物配体。
• Stability of (chloromethyl)platinum(II) complexes
  作者：Robert McCrindle、Gilles J. Arsenault、Anuradha Gupta、Mark J. Hampden-Smith、Richard E. Rice、Alan J. McAlees

  DOI：10.1039/dt9910000949

  日期：——

  The stabilities of [Pt(CH2Cl)2(cod)], [Pt(CH2Cl)Cl(cod)](cod = cycloocta-1,5-diene) and a range of phosphine-containing mono- and cis-bis-(chloromethyl)platinum(II) complexes have been investigated in deuteriochloroform at room temperature. Some of the bis(chloromethyl) derivatives appear to be indefinitely stable (cod and chelating arylphosphines), others suffer very slow decomposition to the dichlorides

  [Pt（CH 2 Cl）2（cod）]，[Pt（CH 2 Cl）Cl（cod）]（cod =环辛-1,5-二烯）和一定范围的含膦单和顺式的稳定性-双-（氯甲基）铂（II在室温下，在氘代氯仿中研究了复合物。一些双（氯甲基）衍生物似乎是无限稳定的（鳕鱼和螯合的芳基膦），其他的则分解成非常缓慢的二氯化物（非螯合的芳基膦），其余的则相对迅速，干净地分解为二氯化物加乙烯。 （烷基膦，非螯合比螯合更快）。通过将六氟异丙醇加入到氘代氯仿溶液中，可以诱导芳基膦配合物的快速分解。尝试通过添加P（C 6 H 11）生成[Pt（CH 2 Cl）2 P（C 6 H 11）3 } 2 ]3至[Pt（CH 2 Cl） 2（cod）]形成顺式-[Pt – CH 2 CH 2 P +（C 6 H 11） 3 } Cl 2 P（C 6 H 11） 3 }]; 提出了一种机制。研究的所有顺式-单（氯甲基）衍生物似乎都是
• Oxidative addition of triorganotin halides to platinum(0) complexes
  作者：Colin Eaborn、Alan Pidcock、Barry R. Steele

  DOI：10.1039/dt9760000767

  日期：——

  Triorganotin chlorides react with complexes of Pt0 to give products of insertion into the Sn–C rather than the Sn–Cl bond as reported previously. Products of the type cis-[PtR(PPh3)2(SnR′2X)](R = Ph, R′2X = Ph2Cl, MePhCl, Me2Cl, BrPh2, Ph2I, Ph2(OH), Ph2(ONO2), or Ph3) have been obtained from [Pt(C2H4)(PPh3)2] and SnPhR′2X, cis-[PtMe(PPh3)2(SnMe2Cl)] from [Pt(C2H4)(PPh3)2] and SnMe3Cl, and cis-[PtMe(PEt3)2(SnMe3)]

  三有机锡氯化物与Pt 0的配合物反应，生成插入到Sn–C中的产物，而不是先前报道的Sn–Cl键。类型的产品顺- [PTR（PPH 3）2（SNR' 2 X）]（R =苯基，R' 2 X =苯基2氯，MePhCl中，Me 2氯，BrPh 2中，Ph 2我中，Ph 2（ OH）中，Ph 2（ONO 2），或PH 3）已经从[PT（C获得的2 ħ 4）（PPH 3）2 ]和SnPhR' 2 X，顺-[ Pt（C 2 H 4）（PPh 3）2 ]和SnMe 3 Cl的-[PtMe（PPh 3）2（SnMe 2 Cl）]]和顺式-[PtMe（PEt 3）2（SnMe 3）] [Pt（PEt 3）4 ]和SnMe 4。已经重新研究了报道的给出具有Cl和SnR 3配体的配合物的各种反应，并显示了给出具有R和SnR 2的Cl配体的配合物或衍生自它们的配合物。已报道SnPh 3配体转变为Ph配体和Snph2