Cl2Pt((PPh2)2C=CH2) | 103237-84-9

• 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: Cl2Pt((PPh2)2C=CH2)
• 英文别名: [platinum(II)dichloride(PPh2)CCH2]；dichloroplatinum;1-diphenylphosphanylethenyl(diphenyl)phosphane
• CAS: 103237-84-9
• 化学式: C₂₆H₂₂Cl₂P₂Pt
• 分子量: 662.394
• InChiKey: GVGBFDFTHHKXJZ-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  7.1
• 重原子数：
  31.0
• 可旋转键数：
  4.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.0
• 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：

  Cl2Pt((PPh2)2C=CH2) 在 C₂H₅OH 、 catalyst: N(CH₂CH₃)3 作用下， 以 二氯甲烷 为溶剂， 以90%的产率得到
  参考文献：
  名称：

  Use of Michael additions to (Ph₂P)₂CCH₂complexes to prepare thiophene- and pyrrole-functionalised metal–phosphine complexes

  摘要：

  The complex [Pd(O2CMe)2(vdpp)] la [vdpp = (Ph2P)2C=CH2] undergoes nucleophilic addition at the double bond with primary alcohols to afford [Pd(O2CMe)2{(Ph2P)2CHCH2OR}] 2 [R = Me, Et, CH2CH2C4H3S-3 or CH2C6H3(OMe)2-3,4]. These were not isolated pure, but metathesis with NaI gave the corresponding diiodides 3, which were isolated, and have been fully characterised by microanalysis and infrared and NMR (H-1 and P-31-{H-1}) spectroscopies. By using 2- (3-thienyl)ethanol as the nucleophile, the complex [PdI2{(Ph2P)2CHCH2OCH2CH2C4H3S-3)] 3c was obtained, and its electrochemistry examined. The reactivity of the double bond in 1a towards other potential weak nucleophiles has been examined. In particular, pyrrole underwent electrophilic addition with la to give, after work-up with NaI, [PdI2{(Ph2P)2CHCH2C4H3NH}]4b. Proton NMR spectroscopy established that 4b was a mixture of 2- and 3-pyrrole isomers (ca. 3: 1). The complexes [MCl2(vdpp)] (M = Pd 1c or Pt 1d) were less reactive, but underwent addition with alcohols in the presence of NEt3 as catalyst to afford [MCl2{(Ph2P)2CHCH2OR}] (M = Pd 5 or Pt 6, R = Et or CH2CH2C4H3S-3). The complex [Pt(vdpp)2][PF6]2 7 has been prepared from [PtCl2(PhCN)2], vdpp and AgPF6 in dichloromethane-acetonitrile. Details of the reaction of 7 with 2- (3-thienyl)ethanol are given. The crystal structure of 3c has been determined.

  DOI：

  10.1039/dt9920003403
• 作为产物：
  描述：

  dichlorobis(trimethylacetonitrile)platinum(II) 、 1,1-双(二苯基膦)乙烯 以 二氯甲烷 为溶剂， 以93%的产率得到Cl2Pt((PPh2)2C=CH2)
  参考文献：
  名称：

  与二氯化铂（II）或二碘化物螯合时（Ph 2 P）2 CCH 2的亲核性（Michael）加成

  摘要：

  用（Ph 2 P）2 C CH 2（vdpp）在二氯甲烷中处理[PtCl 2（NCBu t）2 ]，得到[PtCl 2（vdpp- PP '）]（1a）。用多种胺或NN-二甲基肼在二氯甲烷中处理（1a），可快速获得迈克尔加成产物，收率很高，即。[PtCl 2 {（Ph 2 P）2 -CHCH 2 NHR}] [R = NMe 2（2a），CH 2 CH CH 2（3），D -CHMePh（4）或CH 2 C 6 H 4 OMe-4（5a）]。与[PtMe 2（vdpp- PP '）]相比，复合物（1a）对迈克尔加成的反应性更高；因此它与H 2 NC 6 H 4 Me-4或H 2 NCH 2 CO 2 Et形成加合物，即。[PtCl 2 {（Ph 2 P）6 CHCH 2 NHC 6 H 4 Me-4}]（7）或[PtCl 2 {（Ph 2 P）2 CHCH 2 NHCH 2 CO 2 Et

  DOI：

  10.1039/dt9890001527

文献信息

• Induced Acceleration of Phosphine Exchange in Metal Carbonyls by Pendant Groups of Coordinated Polyphosphines. Two Dangling Phosphine Arms Are Much Better Than One¹
  作者：Richard L. Keiter、John William Benson、Ellen A. Keiter、Weiying Lin、Zhongjiang Jia、Donna M. Olson、Douglas E. Brandt、Jeremy L. Wheeler

  DOI：10.1021/om980289h

  日期：1998.9.1

  dangling phosphines is faster than chelation for each of the four complexes, but chelation of 1 or 2 is much faster than chelation of 3 or 4. It appears that the second dangling phosphine arm present in 1 and 2 accelerates the exchange of all metal-attached ligands. Also observed is long-range phosphorus−carbon coupling, possibly enhanced by a “through-space” interaction, between the short-armed dangling

  动力学和联动异构体的异构化的热力学（OC）5 W [η 1 -PPh 2 CH 2 CH（PPH 2）2 ]（1）和（OC）5 W [η 1 -PPh 2 CH（PPH 2）通过31 P 1 H} NMR在10-55°C的温度范围内研究了氯仿中的CH 2 PPh 2 ]（2）。1到2的转化是放热的（ΔH = -12.25±0.1 kJ mol - 1），并伴随着熵的大幅降低（ΔS = -28.2±0.3 J mol - 1 K - 1）。该反应比预期的要快得多[ ķ =（1.18±0.01）×10 - 5个小号- 1 ]在25℃，并且其小活化焓（Δ ħ ⧧ = 92.6±1.9千焦耳摩尔- 1）和大的负激活熵（Δ小号⧧ = -28.2±6.2Ĵ摩尔- 1 ķ - 1）建议缔合机理。该反应是大小的4个数量比的异构化更快（OC）5 W [η 1 -PPh 2 CH 2 CH 2 P（p -Tol）2
• Nucleophilic (Michael) additions to (Ph₂P)₂CCH₂when chelated to dimethylplatinum(<scp>II</scp>), di(o-tolyl)platinum(<scp>II</scp>), or iodo(trimethyl)platinum(<scp>IV</scp>). Crystal structure of [PtMe₃I{(PPh₂)CH(PPh₂)CH₂NHCH₂Ph}]
  作者：Fatma S. M. Hassan、Simon J. Higgins、Grant B. Jacobsen、Bernard L. Shaw、Mark Thornton-Pett

  DOI：10.1039/dt9880003011

  日期：——

  and NHCH2CH2NH2(12), or of the type [Pt(C6H4Me-o)2(PPh2)2CHCH2R}] with R = NHNHMe (3b) or NHCH2CHCH2(6b). Some of the additions were reversible and the adducts of (1b) were not isolated pure. The platinum(II) complex (1a) reacted with Mel to give fac-[PtMe3I(vdpp-PP′)](13) which reacted with PhCH2NH2 to give [PtMe3I(PPh2)2CHCH2NHCH2Ph}](14) which isomerised in solution to give a mixture of [[graphic

  用（Ph 2 P）2 C CH 2（vdpp）处理[PtMe 2（cod）]（cod =环辛-1,5-二烯），得到[PtMe 2（vdpp- PP '）]（1a）。用vdpp处理[Pt（C 6 H 4 Me- o）2（cod）]，或用邻甲苯基溴化镁处理更好的[PtCl 2（vdpp- PP '）]，得到[Pt（C 6 H 4 Me- o））2（vdpp- PP '）]（1b）。（1a）或（1b）被多种胺和肼高度活化，趋向亲核攻击（迈克尔加成反应），生成[PtMe 2 （（PPh 2）2 CHCH 2 R}]类型的加合物，其中R = NHNH 2（2），NHNHMe（3a），NHCH 2 C CH（4），NMeCH 2 C CH（5），NHCH 2 CH CH 2（6a），NMeCH 2 CH CH 2（7），L -NHCHMePh（8a），D-NHCHMePh（8b），NHCH 2 Ph（9），NHCH
• Intramolecular exchange of coordinated and dangling phosphines in pentacarbonyl group 6 complexes of 1,1,2-tris(diphenylphosphino)ethane
  作者：Richard L. Keiter、Ping Ye、Ellen A. Keiter、John William Benson、Weiying Lin、Douglas E. Brandt、Joel S. Southern、Arnold L. Rheingold、Ilia Guzei、Kraig A. Wheeler、Lew W. Cary

  DOI：10.1016/j.ica.2010.08.039

  日期：2010.12

  activation for 1Cr ⇌ 2Cr and 1W ⇌ 2W are 119.0 and 92.6 kJ mol −1 , respectively, and entropies of activation are 1.4 and −28.2 J K −1 mol −1 , respectively. Isomerization is 10 4 times faster for these complexes than for (OC) 5 M[κ 1 -PPh 2 CH 2 CH 2 P( p -tolyl) 2 ]. A novel mechanism is proposed to account for the rate differences. The X-ray crystal structure of 2W shows that the phosphorus atom of the

  连接异构体（OC）5 M [κ1 -PPh 2 CH 2 CH（PPh 2）2] 1和（OC）5 M [κ1 -PPh 2 CH（PPh 2）CH 2 PPh 2] 2（M = Cr，Mo和W在室温下平衡存在。CDCl 3中在25°C下1Cr Cr 2Cr，1Mo⇌2Mo和1W⇌2W的平衡常数分别为2.61、5.0和4.74。焓有利于正向反应（分别为ΔH = -13.5，−12和-12.2 kJ mol -1），而熵有利于逆反应（分别为ΔS = −37.6，−28和-28.2 JK -1 mol -1）。 ）。异构化比螯合1Mo≫ 2Mo≫ 1W lation 2W> 1Cr⇌2Cr快得多。1Cr⇌2Cr和1W⇌2W的活化焓分别为119.0和92.6 kJ mol -1，活化熵分别为1.4和-28.2 J K -1 mol -1。这些配合物的异构化速度比（OC）5 M [κ1 -PPh 2
• The very high activity of (Ph₂P)₂CCH₂to Michael additions when complexed to platinum(<scp>II</scp>) or platinum(<scp>IV</scp>)
  作者：Xavier L. R. Fonmtaine、Fatma S. M. Hassan、Simon J. Higgins、Grant B. Jacobsen、Bernard L. Shaw、Mark Thornton-Pett

  DOI：10.1039/c39850001635

  日期：——