{"title":"Influence of the Nature of Group 15 Element on [AuI]–C≡E/Azide 1,3-Dipolar Cycloaddition Reaction","authors":"Daniel González-Pinardo, and , Israel Fernández*, ","doi":"10.1021/acs.inorgchem.5c0011010.1021/acs.inorgchem.5c00110","DOIUrl":null,"url":null,"abstract":"<p >The impact of the nature of the Group 15 element on both the bonding situation and the reactivity of gold(I)-C ≡ E (E = N to Bi) complexes has been studied quantum chemically within the density theory functional framework. For this purpose, the 1,3-dipolar cycloaddition reaction involving <i>t</i>BuN<sub>3</sub> as dipole has been selected and its main features, including the regioselectivity of the transformation and the in-plane aromaticity of the corresponding transition structures, have been investigated. It is found that the reactivity of the complexes is increased as one moves down Group 15 (N ≪ <i>P</i> < As < Sb < Bi). This reactivity trend has been rationalized by using the combined activation strain model and energy decomposition analysis methods, which indicate that the process is mainly dominated by the strain energy required by the reactants to reach the corresponding transition state geometries.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"64 11","pages":"5628–5636 5628–5636"},"PeriodicalIF":4.7000,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.inorgchem.5c00110","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
The impact of the nature of the Group 15 element on both the bonding situation and the reactivity of gold(I)-C ≡ E (E = N to Bi) complexes has been studied quantum chemically within the density theory functional framework. For this purpose, the 1,3-dipolar cycloaddition reaction involving tBuN3 as dipole has been selected and its main features, including the regioselectivity of the transformation and the in-plane aromaticity of the corresponding transition structures, have been investigated. It is found that the reactivity of the complexes is increased as one moves down Group 15 (N ≪ P < As < Sb < Bi). This reactivity trend has been rationalized by using the combined activation strain model and energy decomposition analysis methods, which indicate that the process is mainly dominated by the strain energy required by the reactants to reach the corresponding transition state geometries.
第15族元素的性质对金(I)-C≡E （E = N to Bi）配合物的成键情况和反应性的影响已经在密度理论泛函框架下进行了量子化学研究。为此，选择了以tBuN3为偶极子的1,3-偶极环加成反应，并对其主要特征，包括转化的区域选择性和相应过渡结构的面内芳构性进行了研究。研究发现，配合物的反应性随着第15组(N≪P <；& lt;某人& lt;Bi)。结合激活应变模型和能量分解分析方法对这种反应性趋势进行了合理化分析，表明反应过程主要由反应物达到相应过渡态几何形状所需的应变能主导。
期刊介绍：
Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.
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