Twists and Turns of Platinum-Allene Complexes: NMR Techniques for the Study of the Dynamic Behavior in Solution
Twists and Turns of Platinum-Allene Complexes: NMR Techniques for the Study of the Dynamic Behavior in Solution
复制标题
铂-丙二烯配合物的曲折：用于研究溶液中动态行为的核磁共振技术
DOI：
10.1021/acs.organomet.6b00778
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发表时间：
2016
期刊：
影响因子：
2.8
通讯作者：
Quirós M
中科院分区：
文献类型：
--
作者：
Quirós M
本文应用经典的（动态交换线形分析）和新的（SSTD NMR）NMR技术，研究了四配位和五配位的含氮铂联烯配合物在溶液中流动行为的三个主要过程的动力学和热力学参数。我们的研究结果表明，分子内的螺旋和旋转运动密切相关，确认η1-交错结构作为可能的中间体。这些配合物中的配体交换似乎是通过配体独立的解离机制发生的，其中配位溶剂可能参与中间体的稳定。在联烯与其他金属的相互作用中观察到的差异可能是解释铂催化过程中观察到的不同反应性的基础。
Classic (dynamic exchange line-shape analysis) and novel (SSTD NMR) NMR techniques have been applied in order to obtain the kinetic and thermodynamic parameters of the three main processes occurring in the fluxional behavior of Pt-allene complexes withN-containing ligands, in four and five coordination mode, in solution. Our results show intramolecular helical and rotational movements closely related to each other, confirming η1-staggered structures as possible intermediates. The ligand exchange in these complexes seems to occur via a ligand-independent dissociative mechanism, where coordinating solvents might be involved in the stabilization of the intermediates. The differences observed in the interaction of allenes with other metals could be the basis to explain the divergent reactivity observed in platinum-catalyzed processes.