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Systematic DFT Studies on Binary Pseudo‐tetrahedral Zintl Anions: Relative Stabilities and Reactivities towards Protons, Trimethylsilyl Groups, and Iron Complex Fragments

Binary pseudo‐tetrahedral Zintl anions composed of (semi)metal atoms of the p‐block elements have proven to be excellent starting materials for the synthesis of a variety of heterometallic and intermetalloid transition metal–main group metal cluster anions. However, only ten of the theoretically pos...

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Autores principales: Guggolz, Lukas, Dehnen, Stefanie
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2020
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7540718/
https://www.ncbi.nlm.nih.gov/pubmed/32285972
http://dx.doi.org/10.1002/chem.202001379
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author Guggolz, Lukas
Dehnen, Stefanie
author_facet Guggolz, Lukas
Dehnen, Stefanie
author_sort Guggolz, Lukas
collection PubMed
description Binary pseudo‐tetrahedral Zintl anions composed of (semi)metal atoms of the p‐block elements have proven to be excellent starting materials for the synthesis of a variety of heterometallic and intermetalloid transition metal–main group metal cluster anions. However, only ten of the theoretically possible 48 anions have been experimentally accessed to date as isolable salts. This brings up the question whether the other species are generally not achievable, or whether synthetic chemists just have not succeeded in their preparation so far. To contribute to a possible answer to this question, global minimum structures were calculated for all anions of the type (TrTt(3))(5−), (TrPn(3))(2−), and (Tt(2)Pn(2))(2−), comprising elements of periods 3 to 6 (Tr: triel, Al⋅⋅⋅Tl; Tt: tetrel, Si⋅⋅⋅Pb; Pn: pnictogen, P⋅⋅⋅Bi). By analyzing the computational results, a concept was developed to predict which of the yet missing anions should be synthesizable and why. Additionally, the results of an electrophilic attack by protons or trimethylsilyl groups or a nucleophilic attack by transition metal complex fragments are described. The latter yields butterfly‐like structures that can be viewed as a new form of adaptable tridentate chelating ligands.
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spelling pubmed-75407182020-10-15 Systematic DFT Studies on Binary Pseudo‐tetrahedral Zintl Anions: Relative Stabilities and Reactivities towards Protons, Trimethylsilyl Groups, and Iron Complex Fragments Guggolz, Lukas Dehnen, Stefanie Chemistry Full Papers Binary pseudo‐tetrahedral Zintl anions composed of (semi)metal atoms of the p‐block elements have proven to be excellent starting materials for the synthesis of a variety of heterometallic and intermetalloid transition metal–main group metal cluster anions. However, only ten of the theoretically possible 48 anions have been experimentally accessed to date as isolable salts. This brings up the question whether the other species are generally not achievable, or whether synthetic chemists just have not succeeded in their preparation so far. To contribute to a possible answer to this question, global minimum structures were calculated for all anions of the type (TrTt(3))(5−), (TrPn(3))(2−), and (Tt(2)Pn(2))(2−), comprising elements of periods 3 to 6 (Tr: triel, Al⋅⋅⋅Tl; Tt: tetrel, Si⋅⋅⋅Pb; Pn: pnictogen, P⋅⋅⋅Bi). By analyzing the computational results, a concept was developed to predict which of the yet missing anions should be synthesizable and why. Additionally, the results of an electrophilic attack by protons or trimethylsilyl groups or a nucleophilic attack by transition metal complex fragments are described. The latter yields butterfly‐like structures that can be viewed as a new form of adaptable tridentate chelating ligands. John Wiley and Sons Inc. 2020-08-17 2020-09-10 /pmc/articles/PMC7540718/ /pubmed/32285972 http://dx.doi.org/10.1002/chem.202001379 Text en © 2020 The Authors. Published by Wiley-VCH GmbH This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
spellingShingle Full Papers
Guggolz, Lukas
Dehnen, Stefanie
Systematic DFT Studies on Binary Pseudo‐tetrahedral Zintl Anions: Relative Stabilities and Reactivities towards Protons, Trimethylsilyl Groups, and Iron Complex Fragments
title Systematic DFT Studies on Binary Pseudo‐tetrahedral Zintl Anions: Relative Stabilities and Reactivities towards Protons, Trimethylsilyl Groups, and Iron Complex Fragments
title_full Systematic DFT Studies on Binary Pseudo‐tetrahedral Zintl Anions: Relative Stabilities and Reactivities towards Protons, Trimethylsilyl Groups, and Iron Complex Fragments
title_fullStr Systematic DFT Studies on Binary Pseudo‐tetrahedral Zintl Anions: Relative Stabilities and Reactivities towards Protons, Trimethylsilyl Groups, and Iron Complex Fragments
title_full_unstemmed Systematic DFT Studies on Binary Pseudo‐tetrahedral Zintl Anions: Relative Stabilities and Reactivities towards Protons, Trimethylsilyl Groups, and Iron Complex Fragments
title_short Systematic DFT Studies on Binary Pseudo‐tetrahedral Zintl Anions: Relative Stabilities and Reactivities towards Protons, Trimethylsilyl Groups, and Iron Complex Fragments
title_sort systematic dft studies on binary pseudo‐tetrahedral zintl anions: relative stabilities and reactivities towards protons, trimethylsilyl groups, and iron complex fragments
topic Full Papers
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7540718/
https://www.ncbi.nlm.nih.gov/pubmed/32285972
http://dx.doi.org/10.1002/chem.202001379
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