WCA-Cluster: Synthesis and characterization of polyatomic elemental clusters of groups 15 to 18 and their simple metal complexes as salts of weakly coordinating anions
Final Report Abstract
With this project we sought A) for the development of new reagents to deelectronate (remove an electron) from neutral precursors and to B) prepare new late main group cage- and cluster-cations, to C) prepare synthons for ‘naked‘ metal salts partnered with weakly coordinating anions (WCAs), to use the latter in D) to prepare coordination compounds of such M+ (Cu, Au) or M2+ (Cd, Hg, Sn, Pb) ‘naked‘ metal cations and E) to functionalize the coordinated P4-cluster in the salts (P4)Fe(Cp)(CO)2[WCA]. A) led to five papers, three on new reagents shifting the positive potential limits for deelectronation in the employed non-basic reaction environment of 1,2,3,4-tetrafluorobenzene up to 2.0 V vs. Fc+/Fc and two on novel WCAs necessary to stabilize the target cations. B) led to two papers on the phosphorus-based cations P5+ (as an intermediate), P9+ and the first account of a tetrahedral cluster cation P3E+ (E = S, Se, Te). C) led for the desired metal M = Hg to very surprising result, as – despite the use of the strongly deelectronating reagents from A) – the expected Hg2+ was only prepared as a highly reactive intermediate that did immediately undergo further reactions, including bond activation reactions of the solvent and formation of organo-Mercurycation salts. Yet, the reactions could be steered to systematically obtain (solvated) mercury cluster cations [(arene)Hgn(arene)]2+ with n = 2, 3, 4. In two further papers we found access to a naked Au+ and Cu+ synthon. D) The naked Au+ and Cu+ synthons from C) were used to prepare the highly unusual Cu(N 2)-complex with the highest hitherto reported NN stretching frequency at 2314 cm^–1 (one publication; in addition, a theoretical publication on the bonding in such systems and as opposed to ‘normal’ N2-complexes) and Au(P4)- as well as Au(P4S3)-complexes (one publication). E) The functionalization of the coordinated P4-cluster was successful with several reagents and will lead to two publications by the end of 2024: One demonstrating that protic reagents like water or alcohols do react with the cage (by contrast to free P4 which is inert) and another paper in which the polarization of the attacking nucleophile was inverted, i.e. by using silanes R3Si-H. These reactions have coordinated P4-, P3- and P2-fragments as intermediates and finally led to useful P1-compounds. Quite a bit of mechanistic work was done here. Yet, the reaction only did work stoichiometrically, but not catalytically. Still, a very relevant result.
Publications
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First experimental evidence for the elusive tetrahedral cations [EP3]+ (E = S, Se, Te) in the condensed phase. Chemical Science, 10(46), 10779-10788.
Weis, Philippe; Röhner, David Christopher; Prediger, Richard; Butschke, Burkhard; Scherer, Harald; Weber, Stefan & Krossing, Ingo
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Synthesis and Application of a Perfluorinated Ammoniumyl Radical Cation as a Very Strong Deelectronator. Angewandte Chemie International Edition, 59(24), 9453-9459.
Schorpp, Marcel; Heizmann, Tim; Schmucker, Maximillian; Rein, Stephan; Weber, Stefan & Krossing, Ingo
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Homoatomic cations: From [P5]+to [P9]+. Science Advances, 8(36).
Frötschel-Rittmeyer, Julia; Holthausen, Michael; Friedmann, Christian; Röhner, David; Krossing, Ingo & Weigand, Jan J.
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Terminal end‐on coordination of dinitrogen versus isoelectronic CO: A comparison using the charge displacement analysis. Journal of Computational Chemistry, 44(3), 149-158.
Schmitt, Manuel & Krossing, Ingo
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Chemistry with weakly coordinating aluminates [Al(ORF)4]− and borates [B(ORF)4]−: From fundamentals to application. Comprehensive Inorganic Chemistry III, 378-438.
Barthélemy, Antoine; Dabringhaus, Philipp; Jacob, Eike; Koger, Hendrik; Röhner, David; Schmitt, Manuel; Sellin, Malte & Ingo, Krossing
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The perfluoroadamantoxy aluminate as an ideal weakly coordinating anion? – synthesis and first applications. Dalton Transactions, 52(14), 4355-4370.
Billion, Andreas; Schorpp, Marcel; Feser, Rebecca; Schmitt, Manuel; Eisele, Lea; Scherer, Harald; Sonoda, Takaaki; Kawa, Hajimu; Butschke, Burkhard & Krossing, Ingo
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Gold carbonyl cations and beyond: homoleptic gold(i) complexes with P4 and P4S3 and the half-sandwich cation [Au(C6H6)(CO)]+. Chemical Communications, 60(41), 5403-5406.
Schmitt, Manuel; Nestle, Sarah; Radtke, Valentin & Krossing, Ingo
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Pushing redox potentials to highly positive values using inert fluorobenzenes and weakly coordinating anions. Nature Communications, 15(1).
Armbruster, Christian; Sellin, Malte; Seiler, Matthis; Würz, Tanja; Oesten, Friederike; Schmucker, Maximilian; Sterbak, Tabea; Fischer, Julia; Radtke, Valentin; Hunger, Johannes & Krossing, Ingo
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Synthesis and Characterization of a Copper Dinitrogen Complex Supported by a Weakly Coordinating Anion. Angewandte Chemie International Edition, 63(38).
Willrett, Julie; Schmitt, Manuel; Zhuravlev, Vadim; Sellin, Malte; Malinowski, Przemysław J. & Krossing, Ingo
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Utilizing the Perfluoronaphthalene Radical Cation as a Selective Deelectronator to Access a Variety of Strongly Oxidizing Reactive Cations. Angewandte Chemie International Edition, 63(34).
Sellin, Malte; Willrett, Julie; Röhner, David; Heizmann, Tim; Fischer, Julia; Seiler, Matthis; Holzmann, Celia; Engesser, Tobias A.; Radtke, Valentin & Krossing, Ingo
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Video Documented Upscaled Synthesis of Salts of the Parent Carbaborate Ion [CB11H12]−, its Undecafluorinated Form [CHB11F11]− and Useful Starting Materials for its Introduction. Chemistry–Methods, 4(11).
Kulenkampff, Jan; Armbruster, Christian; Drolshagen, Johanna; Regnat, Celine; Wienold, Tina; Spari, Luisa; Fix, Jana; Sterbak, Tabea; Scherer, Harald & Krossing, Ingo
