Density functional insights on the role of iron tricarbonyl in manipulating the ring opening of 4π-hetero cyclobutane analogues – a shift from pseudopericyclic to pericyclic

IF 1.7 4区化学 Q3 CHEMISTRY, MULTIDISCIPLINARY

Journal of Chemical Sciences Pub Date : 2024-06-18 DOI:10.1007/s12039-024-02278-2

Chandrasekaran Prathipa, Lakshminarayanan Akilandeswari, Veejendra K. Yadav, Padmanaban Kalpana

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Abstract

The π-binding of iron tricarbonyl, Fe(CO)₃, tripod is known to effectively alter the stereoselectivity and torquoselectivity of electrocyclic ring opening (ERO) of cyclobutene and its derivatives by changing the mechanism. Representative examples of pseudopericyclic and also borderline pericyclic ERO reactions were chosen for the present study to establish the role of Fe(CO)₃ in manipulating the reactions. The parameters like nucleus-independent chemical shift (NICS), natural bond orbital (NBO) analysis, and topological parameters like ∇²ρ(r) (Laplacian) and ε (ellipticity) have revealed marked drifting of the reaction lying on the pseudopericyclic end to the borderline pericyclic end, which is due to Fe(CO)₃ binding.

Graphical abstract

Iron tricarbonyl alters the nature of pseudopericyclic reaction by making it borderline pericyclic. Activation barrier increases for pseudopericyclic case which is very low in the absence of Fe(CO)_3. No disconnection of orbitals is observed for pseudopericyclic system when complexed with Fe(CO)₃.

Abstract Image

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关于三羰基铁在操纵 4π-hetero 环丁烷类似物开环过程中的作用的密度泛函深入研究--从假周环到周环的转变

众所周知，三羰基铁（Fe(CO)3）的π结合可以通过改变机理，有效地改变环丁烯及其衍生物的电环开环（ERO）的立体选择性和扭矩选择性。本研究选取了具有代表性的假环和边缘环ERO 反应实例，以确定 Fe(CO)3 在操纵反应中的作用。核无关化学位移 (NICS)、天然键轨道 (NBO) 分析等参数，以及∇2ρ(r) （拉普拉奇）和 ε （椭圆度）等拓扑参数显示，由于 Fe(CO)3 的结合，位于假周环末端的反应明显漂移到了边缘周环末端。与 Fe(CO)3 化合时，在假周环体系中没有观察到轨道断开。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Journal of Chemical Sciences CHEMISTRY, MULTIDISCIPLINARY-

CiteScore

3.10

自引率

5.90%

发文量

107

审稿时长

1 months

期刊介绍： Journal of Chemical Sciences is a monthly journal published by the Indian Academy of Sciences. It formed part of the original Proceedings of the Indian Academy of Sciences – Part A, started by the Nobel Laureate Prof C V Raman in 1934, that was split in 1978 into three separate journals. It was renamed as Journal of Chemical Sciences in 2004. The journal publishes original research articles and rapid communications, covering all areas of chemical sciences. A significant feature of the journal is its special issues, brought out from time to time, devoted to conference symposia/proceedings in frontier areas of the subject, held not only in India but also in other countries.