Occurrence of Double Bond in <i>π</i>-Aromatic Rings: An Easy Way to Design Doubly Aromatic Carbon-Metal Structures
A chemical bonding of several metallabenzenes and metallabenzynes was studied via an adaptive natural density partitioning (AdNDP) algorithm and the induced magnetic field analysis. A unique chemical bonding pattern was discovered where the M=C (M: Os, Re) double bond coexists with the delocalized 6...
| Main Authors: | , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2021-11-01
|
| Series: | Molecules |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1420-3049/26/23/7232 |
| _version_ | 1827674776643043328 |
|---|---|
| author | Nikolay V. Tkachenko Alvaro Muñoz-Castro Alexander I. Boldyrev |
| author_facet | Nikolay V. Tkachenko Alvaro Muñoz-Castro Alexander I. Boldyrev |
| author_sort | Nikolay V. Tkachenko |
| collection | DOAJ |
| description | A chemical bonding of several metallabenzenes and metallabenzynes was studied via an adaptive natural density partitioning (AdNDP) algorithm and the induced magnetic field analysis. A unique chemical bonding pattern was discovered where the M=C (M: Os, Re) double bond coexists with the delocalized 6c-2e π-bonding elements responsible for aromatic properties of the investigated complexes. In opposition to the previous description where 8 delocalized π-electrons were reported in metallabenzenes and metallabenzynes, we showed that only six delocalized π-electrons are present in those molecules. Thus, there is no deviation from Hückel’s aromaticity rule for metallabenzynes/metallabenzenes complexes. Based on the discovered bonding pattern, we propose two thermodynamically stable novel molecules that possess not only π-delocalization but also retain six σ-delocalized electrons, rendering them as doubly aromatic species. As a result, our investigation gives a new direction for the search for carbon-metal doubly aromatic molecules. |
| first_indexed | 2024-03-10T04:47:01Z |
| format | Article |
| id | doaj.art-0cc48e2f8810445e86f78e972caf66c4 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T04:47:01Z |
| publishDate | 2021-11-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-0cc48e2f8810445e86f78e972caf66c42023-11-23T02:49:21ZengMDPI AGMolecules1420-30492021-11-012623723210.3390/molecules26237232Occurrence of Double Bond in <i>π</i>-Aromatic Rings: An Easy Way to Design Doubly Aromatic Carbon-Metal StructuresNikolay V. Tkachenko0Alvaro Muñoz-Castro1Alexander I. Boldyrev2Department of Chemistry and Biochemistry, Utah State University, 0300 Old Main Hill, Logan, UT 84322-0300, USAGrupo de Química Inorgánica y Materiales Moleculares, Facultad de Ingeniería, Universidad Autonoma de Chile, El Llano Subercaseaux, Santiago 2801, ChileDepartment of Chemistry and Biochemistry, Utah State University, 0300 Old Main Hill, Logan, UT 84322-0300, USAA chemical bonding of several metallabenzenes and metallabenzynes was studied via an adaptive natural density partitioning (AdNDP) algorithm and the induced magnetic field analysis. A unique chemical bonding pattern was discovered where the M=C (M: Os, Re) double bond coexists with the delocalized 6c-2e π-bonding elements responsible for aromatic properties of the investigated complexes. In opposition to the previous description where 8 delocalized π-electrons were reported in metallabenzenes and metallabenzynes, we showed that only six delocalized π-electrons are present in those molecules. Thus, there is no deviation from Hückel’s aromaticity rule for metallabenzynes/metallabenzenes complexes. Based on the discovered bonding pattern, we propose two thermodynamically stable novel molecules that possess not only π-delocalization but also retain six σ-delocalized electrons, rendering them as doubly aromatic species. As a result, our investigation gives a new direction for the search for carbon-metal doubly aromatic molecules.https://www.mdpi.com/1420-3049/26/23/7232aromaticitydouble-aromaticitymetallabenzynesHückel’s aromaticity rule |
| spellingShingle | Nikolay V. Tkachenko Alvaro Muñoz-Castro Alexander I. Boldyrev Occurrence of Double Bond in <i>π</i>-Aromatic Rings: An Easy Way to Design Doubly Aromatic Carbon-Metal Structures Molecules aromaticity double-aromaticity metallabenzynes Hückel’s aromaticity rule |
| title | Occurrence of Double Bond in <i>π</i>-Aromatic Rings: An Easy Way to Design Doubly Aromatic Carbon-Metal Structures |
| title_full | Occurrence of Double Bond in <i>π</i>-Aromatic Rings: An Easy Way to Design Doubly Aromatic Carbon-Metal Structures |
| title_fullStr | Occurrence of Double Bond in <i>π</i>-Aromatic Rings: An Easy Way to Design Doubly Aromatic Carbon-Metal Structures |
| title_full_unstemmed | Occurrence of Double Bond in <i>π</i>-Aromatic Rings: An Easy Way to Design Doubly Aromatic Carbon-Metal Structures |
| title_short | Occurrence of Double Bond in <i>π</i>-Aromatic Rings: An Easy Way to Design Doubly Aromatic Carbon-Metal Structures |
| title_sort | occurrence of double bond in i π i aromatic rings an easy way to design doubly aromatic carbon metal structures |
| topic | aromaticity double-aromaticity metallabenzynes Hückel’s aromaticity rule |
| url | https://www.mdpi.com/1420-3049/26/23/7232 |
| work_keys_str_mv | AT nikolayvtkachenko occurrenceofdoublebondinipiaromaticringsaneasywaytodesigndoublyaromaticcarbonmetalstructures AT alvaromunozcastro occurrenceofdoublebondinipiaromaticringsaneasywaytodesigndoublyaromaticcarbonmetalstructures AT alexanderiboldyrev occurrenceofdoublebondinipiaromaticringsaneasywaytodesigndoublyaromaticcarbonmetalstructures |