| Full text | |
| Author(s): |
Nagurniak, Glaucio Regis
[1]
;
Teixeira Peraca, Carina de Souza
[1]
;
Orenha, Renato Pereira
[2]
;
Tame Parreira, Renato Luis
[2]
;
Piotrowski, Mauricio Jeomar
[1]
Total Authors: 5
|
| Affiliation: | [1] Univ Fed Pelotas, Dept Phys, POB 354, BR-96010900 Pelotas, RS - Brazil
[2] Univ Franca, Nucleo Pesquisas Ciencias Exatas & Tecnol, Franca, SP - Brazil
Total Affiliations: 2
|
| Document type: | Journal article |
| Source: | NEW JOURNAL OF CHEMISTRY; v. 43, n. 39, p. 15681-15690, OCT 21 2019. |
| Web of Science Citations: | 0 |
| Abstract | |
Multiple-bonded heteronuclear combinations have recently received great attention because of the first experimental arsagermene (>Ge \& xe001;As-) synthesis, which is a relevant topic in organometallic chemistry. However, a systematic elucidation of the Ge \& xe001;As bond still remains necessary. Here, we report a computational investigation, based on second order Moller-Plesset perturbation theory and density functional theory calculations, of arsagermene with a tricoordinate germanium center, to understand the >Ge \& xe001;As- double bond and the influence of the substituents on the stabilization process. We considered a diversified set of R2GeAsR compounds to understand the nature and magnitude of the arsagermene bond. Geometrically we have obtained an excellent agreement with experimental results, where the Ge \& xe001;As bond is confirmed to be a double bond, with a theoretical underestimation of 0.05 angstrom in the bond length. After a complete characterization of the substituents, we obtain that they influence the Ge \& xe001;As formation, mainly through a push-and-pull effect, which comes mainly from the R groups bonded to the Ge species. From the studied topological parameters, a large strength is obtained for the Ge \& xe001;As bond with electron density accumulation, considering electronegative R groups (e.g., halogens), as well as lone pair groups (hydroxy, methoxy, and amine groups). Finally, from the energy decomposition analysis, we obtained a type of interaction-model and the nature of the Ge \& xe001;As bond for all compounds, especially for (H3Si)(2)GeAsPh, which is our model of the synthesized arsagermene compound. The >Ge \& xe001;As- bond was characterized with 52.86% orbital contribution, 44.19% electrostatic interaction, and 2.95% dispersive contribution. The other compounds followed the same trend, helping to complete the picture for the double-bond elucidation for arsagermene. (AU) | |
| FAPESP's process: | 11/07623-8 - The use of quantum-mechanical methods to study the bonds and chemical interactions in self-organizing systems with applications in catalysis, medicinal chemistry, electrochromism, energy storage and conversion |
| Grantee: | Renato Luis Tame Parreira |
| Support Opportunities: | Research Grants - Young Investigators Grants |
| FAPESP's process: | 17/04138-8 - Attainment of chemical, analytical, biological, pharmacological and technological studies to fill the gaps on the development of Brazilian propolis sector |
| Grantee: | Jairo Kenupp Bastos |
| Support Opportunities: | Research Projects - Thematic Grants |