Improving solubility and versatility of compounds containing binary and ternary Zintl anions through derivatization, cation exchange, mechanistic, and reactivity studies

• Applicant: Professorin Dr. Stefanie Dehnen
• Subject Area: Inorganic Molecular Chemistry - Synthesis and Characterisation ; Solid State and Surface Chemistry, Material Synthesis
• Term: from 2017 to 2023
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 338584285

• Final Report Year: 2025

Final Report Abstract

This Project was a continuation of the preceding project that investigated the reactivity of intermetallic solids and binary pseudo-tetrahedral anions of p-block elements. This project worked to expand on these foundational studies by expanding the scope of transition metal complexes as reagents used in conjunction with the intermetallic solids and Zintl anions. Over the course of this project several new compounds were isolated and investigated by experimental and extensive quantum chemical methods. The primary tool of characterization remains as single crystal X-ray diffraction, however, mass spectrometry and other spectroscopic methods, such as NMR spectroscopy and UV-vis spectroscopy have been started. By comparing the reactivity of intermetallic solids and pseudo-tetrahedral anions, it has been possible to discern the deciding factors that influence the reactivity of these fascinating compounds. New solvents have opened a wide range of new reagents that were previously unfeasible to use and is the start of several new projects. Appreciation of the influence of the ligand sphere has led to an increased control of reactions, namely leading to the formation of new cluster compounds. Detailed investigations, and variation of reaction conditions, have led to new insights into the formation of cluster compounds. All this work has provided a firmer understanding into Zintl cluster synthesis, and has given a stronger blueprint for future endeavors in Zintl chemistry.

Publications

• Stabilizing a metalloid {Zn12} unit within a polymetallide environment in [K2Zn20Bi16]6−. Nature Communications, 11(1).
  Eulenstein, Armin R.; Franzke, Yannick J.; Bügel, Patrick; Massa, Werner; Weigend, Florian & Dehnen, Stefanie
  
• Substantial π-aromaticity in the anionic heavy-metal cluster [Th@Bi12]4−. Nature Chemistry, 13(2), 149-155.
  Eulenstein, Armin R.; Franzke, Yannick J.; Lichtenberger, Niels; Wilson, Robert J.; Deubner, H. Lars; Kraus, Florian; Clérac, Rodolphe; Weigend, Florian & Dehnen, Stefanie
  
• Insights into Formation and Relationship of Multimetallic Clusters: On the Way toward Bi-Rich Nanostructures. Journal of the American Chemical Society, 143(18), 7176-7188.
  Pan, Fuxing; Wei, Shangxin; Guggolz, Lukas; Eulenstein, Armin R.; Tambornino, Frank & Dehnen, Stefanie
  
• Tetrahedral [Sb(AuMe)4]3− Occurring in Multimetallic Cluster Syntheses: About the Structure‐Directing Role of Methyl Groups. Angewandte Chemie, 133(47), 25246-25251.
  Pan, Fuxing; Lukanowski, Marcel; Weigend, Florian & Dehnen, Stefanie
  
• Capture the missing: formation of (PbBi3)− and {[AuPb5Bi3]2}4− via atom exchange or reorganization of the pseudo‐tetrahedral Zintl anion (Pb2Bi2)2−. Natural Sciences, 2(3).
  Pan, Fuxing; Guggolz, Lukas & Dehnen, Stefanie
  
• Cluster Chemistry with ( Pseudo -)Tetrahedra Involving Group 13–15 (Semi-)Metal Atoms. CCS Chemistry, 4(3), 809-824.
  Pan, Fuxing; Guggolz, Lukas & Dehnen, Stefanie
  
• Electronic structure and bonding in endohedral Zintl clusters. Chemical Society Reviews, 51(2), 628-649.
  McGrady, John E.; Weigend, Florian & Dehnen, Stefanie
  
• Reactive Solubilization of Heterometallic Clusters by Treatment of (TrBi3)2− Anions (Tr=Ga, In, Tl) with [Mn{N(SiMe3)2}2]. Angewandte Chemie International Edition, 61(42).
  Rienmüller, Julia; Schmidt, Andreas; Yutronkie, Nathan J.; Clérac, Rodolphe; Werncke, C. Gunnar; Weigend, Florian & Dehnen, Stefanie
  
• Titelbild: Between Elemental Match and Mismatch: From K12Ge3.5Sb6 to Salts of (Ge2Sb2)2−, (Ge4Sb12)4−, and (Ge4Sb14)4− (Angew. Chem. 41/2022). Angewandte Chemie, 134(41).
  Beuthert, Katrin; Pan, Fuxing; Guggolz, Lukas; Wilson, Robert J.; Hempelmann, Jan; Dronskowski, Richard & Dehnen, Stefanie
  
• φ-Aromaticity in prismatic {Bi6}-based clusters. Nature Chemistry, 15(3), 347-356.
  Peerless, Benjamin; Schmidt, Andreas; Franzke, Yannick J. & Dehnen, Stefanie
  
• Assembly of One to Four As4 Analogues, (Ge2As2)2− or (Ge3As)3−, in the Coordination Sphere of [PhM]+, [MesM]+, or M2+ (M=Zn, Cd, Hg). Angewandte Chemie, 135(23).
  Wei, Shangxin; Peerless, Benjamin; Guggolz, Lukas; Mitzinger, Stefan & Dehnen, Stefanie
  
• Bismuth-Based Metal Clusters─From Molecular Aesthetics to Contemporary Materials Science. Accounts of Chemical Research, 56(9), 1018-1030.
  Pan, Fuxing; Peerless, Benjamin & Dehnen, Stefanie
  
• Formation of [K(18‐crown‐6)]2Bi2 and the influence of 18‐crown‐6 on the crystallization of bismuth‐based Zintl clusters obtained from Bi22−. Zeitschrift für anorganische und allgemeine Chemie, 649(17).
  Schmidt, Andreas; Peerless, Benjamin & Dehnen, Stefanie
  
• Insight into the formation of bismuth-tungsten carbonyl clusters. Communications Chemistry, 6(1).
  Beuthert, Katrin; Peerless, Benjamin & Dehnen, Stefanie
  
• Synthesis of the (Sn4Bi4)2− Anion by Mild Oxidation of (Sn2Bi2)2−. Zeitschrift für anorganische und allgemeine Chemie, 650(4).
  Lohse, Yannick R.; Weinert, Bastian; Peerless, Benjamin & Dehnen, Stefanie