Cooperativity between H-bonds and tetrel bonds. Transformation of a noncovalent C⋯N tetrel bond to a covalent bond†

IF 2.9 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics Pub Date : 2023-10-20 DOI:10.1039/D3CP04430K

Xin Wang, Qingzhong Li and Steve Scheiner

引用次数: 0

Abstract

The dimers and trimers formed by imidazole (IM) and F₂TO (T = C, Si, Ge) are studied by ab initio calculations. IM can engage in either a NH⋯O H-bond with F₂TO or a T⋯N tetrel bond (TB) with the π-hole above the T atom. The latter is a true noncovalent TB for T = C but is a much shorter and stronger covalent bond with F₂SiO or F₂GeO. When a second IM is added, the cooperativity emerging from its H-bond with the first IM makes it a stronger nucleophile, leading to two minima with F₂CO. The first structure contains a long noncovalent C⋯O TB and there is a much shorter covalent bond in the other, with a small energy barrier separating them. The same sort of double minimum occurs when the two IM units are situated parallel to one another in a stacked geometry.

Abstract Image

查看原文本刊更多论文

氢键和四价键之间的协同作用。一个非共价的C·N四重键转变为共价键。

用从头算方法研究了咪唑（IM）和F2TO（T=C，Si，Ge）形成的二聚体和三聚体。IM可以与F2TO形成NH·O氢键，也可以与T原子上方的π-空穴形成T·N四面体键（TB）。对于T=C，后者是真正的非共价TB，但与F2SiO或F2GeO是更短更强的共价键。当加入第二个IM时，其氢键与第一个IM的协同作用使其成为更强的亲核试剂，导致F2CO的两个极小值。第一个结构包含一个长的非共价C·O TB，另一个结构中有一个短得多的共价键，它们之间有一个小的能垒。当两个IM单元在堆叠几何结构中彼此平行时，会出现相同类型的双最小值。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

Physical Chemistry Chemical Physics 化学-物理：原子、分子和化学物理

CiteScore

5.50

自引率

9.10%

发文量

2675

审稿时长

2.0 months

期刊介绍： Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.