{"title":"Participation of Transition Metal Atoms in Noncovalent Bonds","authors":"Steve Scheiner","doi":"10.1039/d4cp03716b","DOIUrl":null,"url":null,"abstract":"The existence of halogen, chalcogen, pnicogen, and tetrel bonds as variants of noncovalent σ and π-hole bonds is now widely accepted, and their properties have been elucidated. The ability of the d-block transition metals to potentially act as Lewis acids in a similar capacity is examined systematically by DFT calculations. Metals examined span the entire range of the d-block from Group 3 to 12, and are selected from several rows of the periodic table. These atoms are placed in a variety of neutral MXn molecules, with X = Cl and O, and paired with a NH3 nucleophile. The resulting M··N bonds tend to be stronger than their p-block analogues, many of them with a substantial degree of covalency. The way in which the properties of these bonds is affected by the row and column of the periodic table from which the M atom is drawn, and the number and nature of ligands, is elucidated.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":2.9000,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Physical Chemistry Chemical Physics","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4cp03716b","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
The existence of halogen, chalcogen, pnicogen, and tetrel bonds as variants of noncovalent σ and π-hole bonds is now widely accepted, and their properties have been elucidated. The ability of the d-block transition metals to potentially act as Lewis acids in a similar capacity is examined systematically by DFT calculations. Metals examined span the entire range of the d-block from Group 3 to 12, and are selected from several rows of the periodic table. These atoms are placed in a variety of neutral MXn molecules, with X = Cl and O, and paired with a NH3 nucleophile. The resulting M··N bonds tend to be stronger than their p-block analogues, many of them with a substantial degree of covalency. The way in which the properties of these bonds is affected by the row and column of the periodic table from which the M atom is drawn, and the number and nature of ligands, is elucidated.
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.
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