[Pt(4-MeC₆H₄)2{2-ClC₆H₄CH=NCH₂CH₂NMe₂}] | 1379673-85-4

• 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(4-MeC₆H₄)2{2-ClC₆H₄CH=NCH₂CH₂NMe₂}]
• CAS: 1379673-85-4
• 化学式: C₂₅H₂₉ClN₂Pt
• 分子量: 588.052
• InChiKey: VHCCMEXHKRTAAH-UHFFFAOYSA-N

反应信息

• 作为反应物：
  描述：

  [Pt(4-MeC₆H₄)2{2-ClC₆H₄CH=NCH₂CH₂NMe₂}] 以 甲苯 为溶剂， 生成 [PtCl(4-MeC₆H₄)₂{C₆H₄CH=NCH₂CH₂NMe₂}]
  参考文献：
  名称：

  Kinetico-Mechanistic Studies on Intramolecular C–X Bond Activation (X = Br, Cl) of Amino-Imino Ligands on Pt(II) Compounds. Prevalence of a Concerted Mechanism in Nonpolar, Polar, and Ionic Liquid Media

  摘要：

  C-Br and C-Cl oxidative addition reactions of molecules containing a set of {N-amino,N-imino} chelating donor groups (2-X,6-YC6H4CHNCH2CH2NMe2, X = Br, Cl; Y = Cl, H) attached to a {Pt-II(Ar)(2)} (Ar = Ph, 4-MeC6H4) have been studied. The Pt(IV) complexes formed, [PtAr2X{2-YCC5H3CH=NCH2CH2NMe2}], containing a metalated tridentate [C,N,N'] ligand have been fully characterized by the usual techniques, and the X-ray crystal structure of the complex with Ar = 4-MeC6H4 and X =Y = Cl has been determined. Monitoring of the reactions at varying temperatures and pressures and in different solvents agrees with a mechanism that involves the preliminary decoordination of the N-amino donor from the ligand to produce a three-coordinated intermediate. This evolves, via a concerted C-X bond activation, to form a second pentacoordinated intermediate species that, on coordination of the N-amino donor, produces the final complex. The kinetico-mechanistic parameters measured indicate that the concerted character of the process is maintained from nonpolar (xylene and toluene) to polar (acetone) and ionic liquid ((Bmin(NTf2)) media. Furthermore, the Delta V-double dagger values measured indicate that, for the (2,6-Cl)C6H3CH=NCH2CH2NMe2 ligand, the existence of hydrogen bonding within the metalating molecule is a determinant for the acceleration observed.

  DOI：

  10.1021/om300374f

文献信息

• New Insights in the Formation of Five- Versus Seven-Membered Platinacycles: A Kinetico-Mechanistic Study
  作者：Paul V. Bernhardt、Teresa Calvet、Margarita Crespo、Mercè Font-Bardía、Susanna Jansat、Manuel Martínez

  DOI：10.1021/ic3023584

  日期：2013.1.7

  actuation of an unexpected equilibrium between its cis-(X,NMe2) and trans-(X,NMe2) isomers. While the cis-(X,NMe2) isomer produces the 7-membered metallacycle, the trans-(X,NMe2) form leads exclusively to the 5-membered analogue. The isomerization process is dominated by the steric hindrance existing between the Ar–Pt and Ar–Ar′CHN-Pt moieties in the cis-(X,NMe2) isomer that forces a Z conformation of

  PT组成的反应（IV）式的有机金属配合物环金属[PTXAr 2（中，Ar' CH Ñ CH 2 CH 2 Ñ我2）]从制备和动力学机理的角度研究了通过正式的C–C还原消除/ C–H氧化加成/ Ar–H还原消除顺序生产5和7元PT（II）金属环的过程。关键中间体的检测和表征还可以通过仔细选择反应条件（包括时间）来实现，这些条件包括从动力学研究中提取的时间。从收集到的数据，很明显的是，反应性的微调是可能的相对于形成所述备选的5-和7-元环金属化配合物（即，[PTX（AR-中，Ar' CH = Ñ CH 2 CH 2 ñ我2）]和[PTX（氩-Ar ' CH = ñCH 2 CH 2 N Me 2）]）。在所有情况下出现的共同还原消除反应以形成非环金属[PTX（AR）（AR-氩型的中间体化合物' CH = Ñ CH 2 CH 2 Ñ我2）]，这导致上述的选择性形成通过激活其顺式（X，N Me 2）和反式（X，N