The reactivity of TiCp2Cl2 (d(0)) towards Zintl clusters was studied in liquid ammonia (Cp = cyclopentadienyl). Reduction of Ti(IV)Cp2Cl2 and ligand exchange led to the formation of [Ti(III)Cp2(NH3)2](+), also obtainable by recrystallization of [CpTi(III)Cl]2. Upon reaction with [K4Sn9], ligand exchange leads to [TiCp2(η(1)-Sn9)(NH3)](3-). A small variation of the stoichiometry led to the formation of [Ti(η(4)-Sn8)Cp](3-), which cocrystallizes with [TiCp2(NH3)2](+) and [TiCp2(η(1)-Sn9)(NH3)](3-). Finally, the large intermetalloid cluster anion [Ti4Sn15Cp5](n-) (n = 4 or 5) was obtained from the reaction of K12Sn17 and TiCp2Cl2 in liquid ammonia. The isolation of three side products, [K([18]crown-6)]Cp, [K([18]crown-6)]Cp(NH3), and [K([2.2]crypt)]Cp, suggests a stepwise elimination of the Cl(-) and Cp(-) ligands from TiCp2Cl2 and thus gives a hint to the mechanism of the product formation in which [Ti(η(4+2)-Sn8)Cp](3-) has a key role.
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http://dx.doi.org/10.1002/anie.201407855 | DOI Listing |
Nanoscale
January 2025
Technical University of Darmstadt, Eduard-Zintl-Institute, Peter-Grünberg-Straße 8, 64287 Darmstadt, Germany.
The magnetic behavior of endohedrally transition-metal-doped tetrel clusters SnTM (TM = Cr, Mn, Fe) was investigated using a combined experimental and theoretical approach. Based on an improved experimental setup, the magnetic deflection was measured over a wide temperature range of = 16-240 K. From a Curie analysis of the experimentally observed single-sided shift at high nozzle temperatures, the spin multiplicities and -factors were determined.
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December 2024
Department of Chemistry, TUM School of Natural Sciences, Technical University of Munich (TUM), Lichtenbergstraße 4, D-85748, Garching, Germany.
Silicon is by far the most important semiconducting material. However, solution-based synthetic approaches for unsaturated silicon-rich molecules require less efficient multi-step syntheses. We report on a straightforward access to soluble, polyhedral Si clusters from the binary phase KSi, which contains both [Si] and [Si] clusters.
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November 2024
Department of Chemistry, University of Oxford, 12 Mansfield Road, Oxford, OX1 3QR, UK.
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November 2024
Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716, United States.
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View Article and Find Full Text PDFInorg Chem
October 2024
Department of Chemistry, Michigan State University, 578 South Shaw Lane, East Lansing, Michigan 48824, United States.
An organometallic erbium bismuth cluster complex, [K(THF)][Cp*ErBi] (), featuring a heterometallocubane core was isolated. The cube emerges from the rare Bi Zintl ion, bridging two erbium centers for the first time. SQUID magnetometry and calculations uncovered dominant antiferromagnetic coupling enabled through the chair-like hexabismuth anion.
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