New nitridocobaltates(I): Crystal structures and physical properties

[CoN2]/[CN2]‐Substitution in a Crystalline Phase with Composition Close to Sr6[CoN2]2[CN2]

“…The refinement of the occupation factors resulted in a site occupancy for cobalt of 0.71(1) ( x = 0.29(1) in the formula Sr 2 [CoN 2 ] 1– x [CN 2 ] x ), which is significantly higher than the value of 0.67 as expected from the structure formula for a charge‐balanced Co I compound (Sr 2+ 6 [Co I N 2 ] 5– 2 [CN 2 ] 2– ); for comparison the results of both refinements are given in Tables 1, 2, and 3. Taking into account the established counting rules (Sr 2+ , [CN 2 ] 2– ), the magnetic susceptibility data, and the XANES measurements, which all indicate a Co I state 15, the chemical composition Sr 6 [CoN 2 ] 2 [CN 2 ] seems nonetheless to be valid. To achieve electroneutrality in Sr 2 [CoN 2 ] 1– x [CN 2 ] x ( x = 0.29(1)), the significantly larger refined value for cobalt would lead to an oxidation state of Co +1.2 , which is not consistent with the physical properties measurements.…”

Ba2[(NC)NiN]: Ein Cyano‐Nitrido‐Nickelat(0)

“…A. niedrige Oxidationsstufen £ 1 auf 1. Bei Anwesenheit von Kohlenstoff im System bilden sich unter oxidierenden Bedingungen Nitridometallat‐Carbodiimide 2 sowie unter inerten Bedingungen Cyanoverbindungen 3. Als erstes reduziertes Cyano‐Nitrido‐Nickelat mit Barium konnte das zu Sr 2 [(NC)NiN] 4 isotype Ba 2 [(NC)Ni 0 N] durch Reaktion von Mischungen fein gepulverter Ausgangsstoffe (Ba 2 N, Ni und NaCN) in Tantalampullen bei 1023 K erhalten werden.…”

“…A. niedrige Oxidationsstufen £ 1 auf [1]. Bei Anwesenheit von Kohlenstoff im System bilden sich unter oxidierenden Bedingungen Nitridometallat-Carbodiimide [2] sowie unter inerten Bedingungen Cyanoverbindungen [3].…”