Tris(3,5‐dimethylpyrazolyl)methane‐Based Heterobimetallic Complexes that Contain Zn and CdTransition‐Metal Bonds: Synthesis,Structures, and Quantum Chemical Calculations |
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| Authors: | Dr. Jens Meyer Dr. Sandra González‐Gallardo Silvia Hohnstein Delphine Garnier Dr. Markus K. Armbruster Dr. Karin Fink Prof. Dr. Wim Klopper Prof. Dr. Frank Breher |
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| Affiliation: | 1. Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT), Engesserstrasse 15, 76131 Karlsruhe (Germany);2. Institute of Physical Chemistry, Karlsruhe Institute of Technology (KIT), Fritz‐Haber‐Weg 2, 76131 Karlsruhe (Germany);3. Institute of Nanotechnology, Karlsruhe Institute of Technology (KIT), Postfach 3630, 76021 Karlsruhe (Germany) |
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| Abstract: | Reactions of the tris(3,5‐dimethylpyrazolyl)methanide amido complexes [M′{C(3,5‐Me2pz)3}{N(SiMe3)2}] (M′=Mg ( 1 a ), Zn ( 1 b ), Cd ( 1 c ); 3,5‐Me2pz=3,5‐dimethylpyrazolyl) with two equivalents of the acidic Group 6 cyclopentadienyl (Cp) tricarbonyl hydrides [MCp(CO)3H] (M=Cr ( 2 a ), Mo ( 2 b )) gave different types of heterobimetallic complex. In each case, two reactions took place, namely the conversion of the tris(3,5‐dimethylpyrazolyl)methanide ligand (Tpmd*) into the ‐methane derivative (Tpm*) and the reaction of the acidic hydride M?H bond with the M′?N(SiMe3)2 moiety. The latter produces HN(SiMe3)2 as a byproduct. The Group 2 representatives [Mg(Tpm*){MCp(CO)3}2(thf)] ( 3 a / b ) form isocarbonyl bridges between the magnesium and chromium/molybdenum centres, whereas direct metal–metal bonds are formed in the case of the ions [Zn(Tpm*){MCp(CO)3}]+ ( 4 a / b ; [MCp(CO)3]? as the counteranion) and [Cd(Tpm*){MCp(CO)3}(thf)]+ ( 5 a / b ; [Cd{MCp(CO)3}3]? as the counteranion). Complexes 4 a and 5 a / b are the first complexes that contain Zn?Cr, Cd?Cr, and Cd?Mo bonds (bond lengths 251.6, 269.8, and 278.9 pm, respectively). Quantum chemical calculations on 4 a / b* (and also on 5 a / b* ) provide evidence for an interaction between the metal atoms. |
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| Keywords: | bimetallic complexes energy‐decomposition analysis metal– metal interactions tripodal ligands xenophilic bonds |
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