Über Dicyanamide : Synthese, Struktur und Charakterisierung

  • On dicyanamides : synthesis, structure and characterisation

Mann, Markus; Dronskowski, Richard (Thesis advisor); Oppel, Iris Marga (Thesis advisor)

Aachen (2019)
Dissertation / PhD Thesis

Dissertation, RWTH Aachen University, 2019

Abstract

In this thesis three different synthesis strategies for dicyanamides and the successfully synthesized compounds Hg2[N(CN)2]2, Tl[N(CN)2], LiCs2[N(CN)2]3 , M(NH3)2[N(CN)2]2 with M = Ni, Co and their structures are presented and discussed. The synthesis of Hg2[N(CN)2]2 from Na[N(CN)2] and Hg2(NO3)2 was already described in 1922, and here the crystal structure was determined for the first time. Tl[N(CN)2] and LiCs2[N(CN)2]3 were produced by metathesis of the respective metal halides and Ag[dca] monocrystalline. Using the high solubility of NaCl compared to M(NH3)2[N(CN)2]2 with M = Ni, Co in an ammoniacal aqueous solution of Na[N(CN)2] and MCl2, single crystals of the diammine-metal(II)-bisdicyanamide compounds could be isolated. For these structures, it could be shown that the ammonia molecules involved form hydrogen bridges to the dicyanamide, resulting in cross-linking of the two-dimensional M[N(CN)2]2 planes. By SQUID measurements both compounds were characterized as paramagnetic. UV/VIS spectroscopy was also used to characterize the dicyanamide as a medium-field ligand and its incremental volume was calculated from the determined structures. In addition, experiments on the low-temperature synthesis of iron(III)carbodiimide are presented.

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