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非无辜的菲咯啉单元:调节氢胺化反应中催化活性的电子巢。

The non-innocent phenalenyl unit: an electronic nest to modulate the catalytic activity in hydroamination reaction.

机构信息

Department of Chemical Sciences, Indian Institute of Science Education and Research-Kolkata, Mohanpur-741252, India.

出版信息

Sci Rep. 2013 Oct 2;3:2821. doi: 10.1038/srep02821.

Abstract

The phenalenyl unit has played intriguing role in different fields of research spanning from chemistry, material chemistry to device physics acting as key electronic reservoir which has not only led to the best organic single component conductor but also created the spin memory device of next generation. Now we show the non-innocent behaviour of phenalenyl unit in modulating the catalytic behaviour in a homogeneous organic transformation. The present study establishes that the cationic state of phenalenyl unit can act as an organic Lewis acceptor unit to influence the catalytic outcome of intermolecular hydroamination reaction of carbodiimides. For the present study, we utilized organoaluminum complexes of phenalenyl ligands in which the phenalenyl unit maintains the closed shell electronic state. The DFT calculation reveals that the energy of LUMO of the catalyst is mainly controlled by phenalenyl ligands which in turn determines the outcome of the catalysis.

摘要

菲咯啉单元在化学、材料化学到器件物理等多个研究领域发挥了引人入胜的作用,作为关键的电子储存库,它不仅导致了最佳的有机单组分导体的出现,还创造了下一代的自旋记忆器件。现在,我们展示了菲咯啉单元在调节均相有机转化中的催化行为方面的非定域行为。本研究表明,菲咯啉单元的阳离子态可以作为一种有机路易斯受体单元,影响碳二亚胺的分子间氢胺化反应的催化结果。在本研究中,我们利用了菲咯啉配体的有机铝配合物,其中菲咯啉单元保持闭壳电子态。DFT 计算表明,催化剂的最低未占轨道(LUMO)能量主要由菲咯啉配体控制,这反过来又决定了催化的结果。

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