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Open AccessArticle

Mono- and Hexanuclear Zinc Halide Complexes with Soft Thiopyridazine Based Scorpionate Ligands

Institute of Chemistry, Inorganic Chemistry, University of Graz, Schubertstrasse 1, 8010 Graz, Austria
Institute of Chemistry, Organic and Bioorganic Chemistry, University of Graz, Heinrichstrasse 28, 8010 Graz, Austria
Author to whom correspondence should be addressed.
Inorganics 2019, 7(2), 24;
Received: 20 December 2018 / Revised: 4 February 2019 / Accepted: 5 February 2019 / Published: 19 February 2019
(This article belongs to the Special Issue Metal Complexes Containing Boron Based Ligands)
Scorpionate ligands with three soft sulfur donor sites have become very important in coordination chemistry. Despite its ability to form highly electrophilic species, electron-deficient thiopyridazines have rarely been used, whereas the chemistry of electron-rich thioheterocycles has been explored rather intensively. Here, the unusual chemical behavior of a thiopyridazine (6-tert-butylpyridazine-3-thione, HtBuPn) based scorpionate ligand towards zinc is reported. Thus, the reaction of zinc halides with tris(6-tert-butyl-3-thiopyridazinyl)borate Na[TntBu] leads to the formation of discrete torus-shaped hexameric zinc complexes [TntBuZnX]6 (X = Br, I) with uncommonly long zinc halide bonds. In contrast, reaction of the sterically more demanding ligand K[TnMe,tBu] leads to decomposition, forming Zn(HPnMe,tBu)2X2 (X = Br, I). The latter can be prepared independently by reaction of the respective zinc halides and two equiv of HPnMe,tBu. The bromide compound was used as precursor which further reacts with K[TnMe,tBu] forming the mononuclear complex [TnMe,tBu]ZnBr(HPnMe,tBu). The molecular structures of all compounds were elucidated by single-crystal X-ray diffraction analysis. Characterization in solution was performed by means of 1H, 13C and DOSY NMR spectroscopy which revealed the hexameric constitution of [TntBuZnBr]6 to be predominant. In contrast, [TnMe,tBu]ZnBr(HPnMe,tBu) was found to be dynamic in solution. View Full-Text
Keywords: soft scorpionate; zinc; hexanuclear compounds soft scorpionate; zinc; hexanuclear compounds
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MDPI and ACS Style

Tüchler, M.; Ramböck, M.; Glanzer, S.; Zangger, K.; Belaj, F.; Mösch-Zanetti, N.C. Mono- and Hexanuclear Zinc Halide Complexes with Soft Thiopyridazine Based Scorpionate Ligands. Inorganics 2019, 7, 24.

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