KIT | KIT-Bibliothek | Impressum | Datenschutz

Assembly of One to Four As$_4$ Analogues, (Ge$_2$As$_2$)$^{2-}$ or (Ge$_3$As)$^{3-}$, in the Coordination Sphere of [PhM]$^+$, [MesM]$^+$, or M$^{2+}$ (M = Zn, Cd, Hg)

Wei, Shangxin 1; Peerless, Benjamin 1; Guggolz, Lukas 1; Mitzinger, Stefan 1; Dehnen, Stefanie 1
1 Institut für Nanotechnologie (INT), Karlsruher Institut für Technologie (KIT)

Abstract:

Pseudo-tetrahedral units of p-block atoms proved to be excellent building blocks for novel molecular architectures and for introducing new elemental combinations which are not otherwise accessible. In this work, we present a series of clusters obtained by reactions of binary Ge/As anions with [MPh2] (M=Zn, Cd, Hg; Ph=phenyl). The study is grounded on the fact that the binary reactant gained by extracting the solid ‘K2GeAs’ with ethane-1,2-diamine (en) co-exists as (Ge2As2)2− and (Ge3As)3− in solution. This allows for a larger variety of products by ‘selecting’ the most suitable species for the final ternary complex to crystallize. The reactions afforded the unprecedented first step of the corresponding interaction, thus attachment of (MPh)+ to a pseudo-tetrahedral unit in [PhZn(Ge3As)]2− (1) and [PhHg(Ge3As)]2− (2), and complex anions with two, three, or four units, [(Ge3As)Zn(Ge2As2)]3− (3), [Cd3(Ge3As)3]3− (4), and [Zn3(Ge3As)4]6− (5). Quantum chemistry confirmed the compositions and the positions of the Ge or As atoms, beside explaining structural peculiarities. The subtle impact of different [MR2] reactants was additionally studied by corresponding reactions using [ZnMes2] (Mes=mesityl), which showed success in selectively crystallizing [MesZn(Ge3As)]2− (6). ... mehr


Verlagsausgabe §
DOI: 10.5445/IR/1000157793
Veröffentlicht am 29.06.2023
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Nanotechnologie (INT)
Publikationstyp Zeitschriftenaufsatz
Publikationsjahr 2023
Sprache Englisch
Identifikator ISSN: 1433-7851, 1521-3773
KITopen-ID: 1000157793
HGF-Programm 43.31.01 (POF IV, LK 01) Multifunctionality Molecular Design & Material Architecture
Erschienen in Angewandte Chemie International Edition
Verlag John Wiley and Sons
Band 62
Heft 23
Seiten Art.-Nr.: e202303037
Vorab online veröffentlicht am 11.04.2023
Nachgewiesen in Web of Science
Scopus
Dimensions
KIT – Die Forschungsuniversität in der Helmholtz-Gemeinschaft
KITopen Landing Page