Universität zu Köln

Rennebaum, Tobias ORCID: 0000-0003-0241-4680 (2024). Studies on Nitrogenous Sulfates. PhD thesis, Universität zu Köln.

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Abstract

This dissertation deals with the chemical compound class of nitrogen-containing derivatives of sulfuric acid. The formal substitution of a hydroxyl group (-OH) by nitrogen or an amino group ( NH2) yields a structural entity that represents a large number of known and conceivable compounds. In total four sub-areas were synthetically and analytically elaborated in this work. By reactions of the nitrogen sources P3N3Cl6 and (S3N2Cl)Cl with metal salts in liquid sulfur trioxide, various compounds with cyclic nitridosulfate anions were obtained. These are both complex compounds and classic ionic structures. Structural elucidation was mainly carried out by single crystal X-ray diffraction. The yielded anions [S3NO8]−, [S4N2O10]2−, [S4NO11]−, [S4N3O9]3− and [S4N3O8Cl]2− exhibit a similar structure motif. Additionally, it was possible to isolate a phosphorus-containing compound with the constitution of S6N4O13H2∙P2O3Cl4 from the reaction system SO3/P3N3Cl6. The second part of this thesis covers the systematic studies on the sulfonates of hydrazine. The sulfonates have been known for a long time but lack completely of analytical data. The zwitterionic hydrazine monosulfonic acid and its barium salt were characterized in detail as monosulfonated compounds. Furthermore, the hydrazine disulfonate, [(SO3)HNNH(SO3)]2−, and isomeric hydrazine iso-disulfonate, [H2NN(SO3)2]2−, in various salts were analyzed and compared structurally. Finally, the elusive hydrazine tetrasulfonate anion was synthesized and investigated in two compounds. The structure determination off all hydrazine sulfonates was carried out by single crystal X-ray diffraction. This was followed by a phase analysis of the crystalline compounds using the Rietveld method. In addition, the thermal decomposition behavior was examined and the vibrational spectroscopic properties were worked out with the aid of quantum mechanical calculations. Thirdly, the azidosulfate anion, [SO3N3]–, was focused on, which is also a known but not thoroughly analyzed anion in the literature. Using different approaches, the compounds (TBA)3(N3)3[SO3N3], (TBA)[SO3N3], K[SO3N3] and Na3[SO3N3]3(CH3CN) were synthesized and elucidated using single crystal XRD. K[SO3N3] was obtained in larger quantities, which enabled a comprehensive study by spectroscopic and thermal methods. In the last chapter, three new mixed cationic highly symmetric compounds of the nitrido-tris-sulfate [N(SO3)3]3– were prepared from K3[N(SO3)3](H2O)2 in alkaline medium. K3[N(SO3)3](H2O)2 was analyzed by X-ray methods and the thermal behavior was investigated. The sensitivity towards hydrolysis of the [N(SO3)3]3– anion was also confirmed in salt metathesis.

Item Type:	Thesis (PhD thesis)
Translated title:	Title Language Studien zu stickstoffhaltigen Sulfaten German
Creators:	Creators Email ORCID ORCID Put Code Rennebaum, Tobias tobiasrennebaum@outlook.de orcid.org/0000-0003-0241-4680 UNSPECIFIED
URN:	urn:nbn:de:hbz:38-744980
Date:	29 November 2024
Language:	English
Faculty:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Inorganic Chemistry
Subjects:	Chemistry and allied sciences
Uncontrolled Keywords:	Keywords Language Nitrogenous Sulfates English Sulfur Trioxide English Solvothermal Synthesis English
Date of oral exam:	10 September 2024
Referee:	Name Academic Title Wickleder, Mathias S. Prof. Dr.
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/74498