Metall‐Pseudohalogenide. 27. Zur Struktur der Dicyanamide zweiwertiger 3d‐Metalle M(N(CN)₂)₂

Abstract

Auf der Grundlage von IR‐Untersuchungen im Bereich von 200–2 400 cm−1, von Elektronenspektren und Röntgenuntersuchungen werden die Strukturen von 3d‐Metall‐dicyanamiden M(N(CN)2)2 (M = Mn, Fe, Co, Ni, Cu, Zn) beschrieben. Die Verbindungen lassen sich zwei verschiedenen Strukturtypen zuordnen, in denen die Anionen entweder als dreizählige oder zweizählige Brückenliganden auftreten. Kobalt‐ und Mangan‐dicyanamid bilden Struktur‐Isomere mit pseudo‐oktaedrischer (α‐Formen) bzw. ‐tetraedrischer Mikrosymmetrie (β‐Formen). Der polymertetraedrische Verbindungstyp, dem auch Zinkdicyanamid zuzuordnen ist, scheint eine bisher nicht beschriebene Bindungsart verbrückender Dicyanamid‐Gruppen zu enthalten.

Synthesis, structure and magnetic characterization of dinuclear copper(ii) complexes bridged by bicompartmental phenolate

“…region corresponding to n s (C^N) and two weak to medium absorption bands in the 2220-2290 cm À1 region corresponding to n as (C^N), and n s + n as (C^N) 38 and these were in agreement with those observed in other monodentate dicyanamido complexes. 39 The frequencies of these peaks were shied to higher values compared to the corresponding peaks observed in the free dca in its sodium salt (2129, 2232 and 2286 cm À1 )…”

Syntheses, structures and magnetic properties of μ1,5-dicyanamide bridged di- and polynuclear manganese(II) complexes containing neutral N-donor Schiff bases: Control of coordination number and nuclearity by varying denticity

“…However, 3 and 4 exhibit low conductivity values ($55 ohm À1 cm 2 mol À1 ) in MeCN reflecting association of the counter ions with the metallated cationic organic frameworks in solid state and in solution. In IR spectra, the stretching vibrations of dca in 1 and 2 are seen as strong m s (C"N) absorptions in the region 2170-2190 cm À1 and two weak to medium m as + m s (C"N) and m as (C"N) absorptions in the range 2240-2310 cm À1 (vide Section 2); the shift towards higher frequency values as compared to those of free dca (2179 cm À1 , 2232 and 2286 cm À1 ) [39] is presumably due to bibridging l 1,5 coordination mode of the pseudohalide [19,25]. However, in 3/4, corresponding dca stretches are shifted towards lower values [22,23] …”

Low-dimensional Compounds Containing Cyano Groups. XI. Preparation, Crystal Structure and Properties of Two Copper(II) Dicyanamide Complexes with PF 6 − Anions

“…For this purpose the m as (CBN) and m s (CBN) vibrations are of basic importance. The spectrum of the free ion in the sodium salt shows strong bands at 2232 and 2179 cm )1 for m as (CBN) and m s (CBN), respectively [25]. In the case of monodentate coordination of dca through a cyano N atom as a rule two m(CBN) bands appear in the 2235-2220 range cm )1 (for m as (CBN)) and 2175-2160 cm )1 (for m s (CBN)), respectively.…”