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Bielec, Philipp; Nelson, Ryky; Stoffel, Ralf P.; Eisenburger, Lucien; Guenther, Daniel; Henss, Ann-Kathrin; Wright, Jonathan P.; Oeckler, Oliver; Dronskowski, Richard; Schnick, Wolfgang (2019): Cationic Pb-2 Dumbbells Stabilized in the Highly Covalent Lead Nitridosilicate Pb2Si5N8. In: Angewandte Chemie-International Edition, Vol. 58, No. 5: pp. 1432-1436
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Due to the weak oxidative force of N-2, nitrides are only typically formed with the less electronegative metals. Meeting this challenge, we here present Pb2Si5N8, the first nitridosilicate containing highly electron-affine cations of a metal from the right side of the Zintl border. By using advanced synchrotron X-ray diffraction, the crystal structure was determined from a tiny single crystal of 1 x 3 x 3 mu m(3) in size, revealing a significantly different bonding situation compared to all other nitridosilicates known so far. Indeed, DFT calculations confirm distinct amounts of covalency not only between Pb and N but also between formal Pb2+ cations. Thus, unprecedented cationic Pb-2 dumbbells with a stretching vibration at 117 cm(-1) were found in Pb2Si5N8, the first representative of a crystallographically elucidated lead nitride, stabilized by high amounts of covalency.