A New Family of High Oxidation State Antiperovskite Nitrides: La3MN5 (M = Cr, Mn and Mo)

Angew Chem Int Ed Engl. 2024 Apr 23:e202405498. doi: 10.1002/anie.202405498. Online ahead of print.ABSTRACTThree new nitrides La3MN5 (M = Cr, Mn, and Mo) have been synthesized using a high pressure azide route. These are the first examples of ternary Cs3CoCl5-type nitrides, and show that this (MN4)NLa3 antiperovskite structure type may be used to stabilise high oxidation-state transition metals in tetrahedral molecular [MN4]n- nitridometallate anions. Magnetic measurements confirm that Cr and Mo are in the M6+ state, but the M = Mn phase has an anomalously small paramagnetic moment and large cell volume. Neutron powder diffraction data are fitted using an anion-excess La3MnN5.30 model (space group I4/mcm, a = 6.81587(9) Å and c = 11.22664(18) Å at 200 K) in which Mn is close to the +7 state. Excess-anion incorporation into Cs3CoCl5-type materials has not been previously reported, and this or other substitution mechanisms may enable many other high oxidation state transition metal nitrides to be prepared.PMID:38651652 | DOI:10.1002/anie.202405498

Source: Angewandte Chemie - April 23, 2024 Category: Chemistry Authors: Yao Yuan Minghui Yang Simon D Klo ß John Paul Attfield Source Type: research