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Preparation of Acyclic and Heterocyclic Tellurathianitrogen Compounds: Contributions to a Better Understanding of Complex Reaction Pathways
Author(s) -
Boese Roland,
Haas Alois,
Hoppmann Eike,
Merz Klaus,
Olteanu Alexandra
Publication year - 2002
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/1521-3749(200203)628:3<673::aid-zaac673>3.0.co;2-p
Subject(s) - chemistry , decomposition , tetrahydrofuran , medicinal chemistry , lewis acids and bases , nitrogen , molecule , crystal structure , stereochemistry , organic chemistry , catalysis , solvent
Reactions between Cl 3 S 3 N 3 and TeCl 4 provide [S 4 N 3 + ][Te 2 Cl 9 ‐ ] and [ $\overline{SSNNN}^+$ ][TeCl 5 ‐ ], the latter molecule, for the first time in SN‐chemistry, contains a five membered ring with three nitrogen atoms linked to each other. The course of this unusual reaction is discussed and both structures are proved by X‐ray structure determinations. New routes to the known cages (XTeNSN) 3 N (X = F, Cl) result from the decomposition of X 2 Te(NSN) 2 TeX 2 in tetrahydrofuran. In the presence of MCl 3 (M = Ga, Al, Fe) besides (ClTeNSN) 3 N2THF also [MCl 2 (THF) 4 + ][TeCl 5 THF ‐ ] could be isolated proving that TeCl 4 is an additional product in this decomposition process. The crystal structures for (ClTeNSN) 3 N2THF and [Cl 2 Al(THF) 4 + ]‐[TeCl 5 THF ‐ ] are determined. The reaction steps for this complicated unforeseen decomposition, based on known reactions and substances, are discussed. Strong Lewis‐acids such as AlF 3 or AsF 5 form with F 2 Te(NSN) 2 TeF 2 mono‐ and tetrafold positively charged cations respectively. Metathetical reactions between F 2 Te(NSN) 2‐ TeF 2 and (CH 3 ) 3 SiR provide R(F)Te(NSN) 2 Te(F)R [R = CF 3 C(O)O‐ and CF 3 SO 2 O‐]. When R 2 Te(NSO) 2 is treated with TeF 4 the already mentioned compounds and F 3 TeR are formed. The reaction of TeCl 4 with R 2 Te(NSO) 2 gives Cl 3 TeR and unsubstituted Cl 6 Te 2 N 2 S ( 1 ). The condensation of TeX 4 with [(CH 3 ) 3 SiNSN] 2 S provides the corresponding tellurium containing eight membered rings X 2 Te(NSN) 2 S (X = F, Cl).