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首页> 外文期刊>Organometallics >Platinum-Catalyzed Ethylene Hydroamination with Aniline: Synthesis, Characterization, and Studies of Intermediates
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Platinum-Catalyzed Ethylene Hydroamination with Aniline: Synthesis, Characterization, and Studies of Intermediates

机译：苯胺铂催化乙烯加氢胺化反应：中间体的合成，表征与研究

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摘要

Starting from either K2PtCl4 or K[PtCl3(C2H4)] center dot H2O (Zeise's salt), complexes (nBu(4)P)(2)[PtBr4] (1), nBu(4)P[PtBr3(C2H4)] (2), nBu(4)P[PtBr3(PhNH2)] (3), trans-[PtBr2(C2H4)(PhNH2)] (4), cis-[PtBr2-(C2H4)(PhNH2)] (5), and cis-[PtBr2(PhNH2)21 (6) have been obtained by efficient one-pot procedures. All have been fully characterized by microanalysis (C, H, N), multinuclear NMR spectrometry (H-1, C-13, Pt-195), UV-visible spectroscopy, and single-crystal X-ray diffraction. Compound I slowly loses Br- in solution to yield (nBu(4)P)(2)[Pt2Br6] (1'), which has also been characterized crystallographically. The relative stability of the various compounds has been probed experimentally by NMR studies in several solvents and computationally by gas-phase geometry optimizations followed by C-PCM calculations of the solvation effects in dichloromethane and aniline. The calculations also included the bis(ethylene) complexes [PtBr2(C2H4)(2)] in the trans (two different conformations 7 and 7') and cis (8) configurations. The solution experiments gave no evidence fora nucleophilic attack of aniline onto coordinated ethylene under mild conditions (T up to 68 degrees C), setting a lower limit of 29 kcal mol(-1) for the activation barrier of this process. Therefore, the relative energies computed for the other compounds suggest that all ethylene-containing complexes (2, 4, 5, 7, and 8) are viable candidates for the nucleophilic addition step of the PtBr2-catalyzed ethylene hydroamination by aniline. Use of the isolated complex 2, 4, or 5 in combination with nBu(4)Br as precatalysts for the ethylene hydroamination by aniline yields similar catalytic activities.
机译：从K2PtCl4或K [PtCl3（C2H4）]中心点H2O（蔡司盐）开始，络合物（nBu（4）P）（2）[PtBr4]（1），nBu（4）P [PtBr3（C2H4）]]（ 2），nBu（4）P [PtBr3（PhNH2）]（3），反式-[PtBr2（C2H4）（PhNH2）]（4），顺式[PtBr2-（C2H4）（PhNH2）]（5）和顺式[PtBr2（PhNH2）21（6）已通过有效的一锅法获得。通过微分析（C，H，N），多核NMR光谱（H-1，C-13，Pt-195），紫外可见光谱和单晶X射线衍射已对所有特征进行了全面表征。化合物I在溶液中缓慢失去Br-生成（nBu（4）P）（2）[Pt2Br6]（1'），该晶体也已进行了结晶表征。各种化合物的相对稳定性已通过在几种溶剂中进行的NMR研究进行了实验，并通过气相几何优化进行了计算，然后通过C-PCM计算了二氯甲烷和苯胺中的溶剂化效果。计算还包括反式（两个不同的构型7和7'）和顺式（8）构型的双（乙烯）配合物[PtBr2（C2H4）（2）]。溶液实验没有证据表明在温和的条件下（T高达68摄氏度）苯胺对配位乙烯的亲核攻击，为此过程的活化势垒设定了29 kcal mol（-1）的下限。因此，计算出的其他化合物的相对能量表明，所有含乙烯的配合物（2、4、5、7和8）都是苯胺在PtBr2催化的乙烯加氢氨基化亲核加成步骤中可行的候选物。分离的配合物2、4或5与nBu（4）Br的组合用作苯胺进行乙烯加氢胺化的预催化剂可产生相似的催化活性。

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