Rotational Characterization of an n → π* Interaction in a Pyridine–Formaldehyde Adduct,The Journal of Physical Chemistry Letters

当前位置： X-MOL 学术 › J. Phys. Chem. Lett. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Rotational Characterization of an n → π* Interaction in a Pyridine–Formaldehyde Adduct
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2018-07-30 00:00:00 , DOI: 10.1021/acs.jpclett.8b01719
Susana Blanco ₁ , Juan Carlos López ₁

Affiliation

The rotational spectrum of the pyridine–formaldehyde adduct generated in a supersonic expansion has been analyzed using Fourier transform microwave spectroscopy. The spectrum shows a quadrupole coupling hyperfine structure due to the presence of ¹⁴N. The spectra of the parent species, ¹³C and ¹⁵N isotopologues, have been observed to investigate its structure. The complex shows C_s symmetry with the plane of pyridine bisecting the ∠HCH angle of formaldehyde and the N atom located along the Bürgi–Dunitz trajectory of nucleophile addition to a carbonyl group (r(N–C) = 2.855(4) Å, ∠NC═O = 102.8(6)°). From this structure and with the help of ab initio computations and natural bond orbital analysis, it is shown unambiguously that pyridine links to formaldehyde, the smallest molecule bearing a carbonyl group, through an n → π* interaction together with a weak C–H···O bond.

中文翻译：

吡啶-甲醛加合物中n→π*相互作用的旋转表征

超音速膨胀中生成的吡啶-甲醛加合物的旋转光谱已使用傅立叶变换微波光谱法进行了分析。由于存在¹⁴ N，该光谱显示出四极偶合超精细结构。已观察到母体物质¹³ C和¹⁵ N同位素同位素的光谱以研究其结构。该络合物显示出C _s对称性，吡啶平面将甲醛的∠HCH角平分，并且沿着羰基的亲核试剂的Bürgi-Dunitz轨迹位于N原子上（r（NC）= 2.855（4）Å，∠NC= O = 102.8（6）°）。通过这种结构并借助从头算和自然键轨道分析，可以清楚地表明，吡啶通过n→π*相互作用以及弱的C–H·链接到甲醛，甲醛是带有羰基的最小分子。 ··O键。

更新日期：2018-07-30

点击分享查看原文

点击收藏

阅读更多本刊新发论文本刊介绍/投稿指南