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  Heteroleptic Complexes of the Tridentate Pyridine-2,6-di-tetrazolate Ligand

Krest, A., Sandleben, A., Valldor, M., Werker, M., Ruschewitz, U., & Klein, A. (2017). Heteroleptic Complexes of the Tridentate Pyridine-2,6-di-tetrazolate Ligand. ChemistrySelect, 2(21), 5849-5859. doi:10.1002/slct.201701124.

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Item Permalink: http://hdl.handle.net/11858/00-001M-0000-002D-CA82-8 Version Permalink: http://hdl.handle.net/11858/00-001M-0000-002D-CA85-2
Genre: Journal Article

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 Creators:
Krest, Alexander1, Author
Sandleben, Aaron1, Author
Valldor, Martin2, Author              
Werker, Melanie1, Author
Ruschewitz, Uwe1, Author
Klein, Axel1, Author
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1External Organizations, ou_persistent22              
2Martin Valldor, Physics of Correlated Matter, Max Planck Institute for Chemical Physics of Solids, Max Planck Society, ou_1863454              

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 Abstract: The synthesis and spectroscopic characterisation of a series of heteroleptic complexes of the tridentate pyridine-2,6-di-(5-tetrazolate) (pydtz(2-)) with Co(II), Ni(II), Cu(II) and Zn(II) and pyridine (Py) and H2O as coligands is reported. Single crystal XRD data reveals the formation of octahedrally configured complexes [Co(pydtz)(H2O)(Py)(2)], [Co(pydtz)(H2O)(2)(Py)]2H(2)O, [Ni(pydtz)(Py)(3)]2Py, and [Zn(pydtz)(H2O)(Py)(2)]Py, and a markedly Jahn-Teller distorted octahedral structure for [Cu(pydtz)(H2O)(2)(Py)]. Magnetic measurements reveal a S = 3/2 high-spin configuration for the Co(II) complex [Co(pydtz)(H2O)(Py)(2)], an S = 1 ground state for the Ni(II) derivative and S = 1/2 Cu(II) ions for [Cu(pydtz)(H2O)(2)(Py)], the latter is supported by electron-paramagnetic-resonance spectroscopy. The crystalline materials are subject to severe corrosion as revealed by powder XRD and DSC-TG experiments. H2O and pyridine co-crystallisates and coligands are easily cleaved. At the same time DSC-TG reveal very high stability of the [M(pydtz)] fragments with exothermic decomposition at T > 300 degrees C. As a consequence, in pyridine solution in all cases the species [M(pydtz)(Py)(3)] are observed. Ultraviolet-visible light absorption spectroscopy reveals a strong ligand field procured by the pydtz(2-) ligand and electrochemical measurements suggest very strong sigma-donation but only weak -accepting abilities of pydtz(2-) compared to the isostructural terpy (2,2';6',2''-terpyridine) ligand.

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Language(s): eng - English
 Dates: 2017-07-042017-07-04
 Publication Status: Published in print
 Pages: -
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 Table of Contents: -
 Rev. Method: -
 Identifiers: ISI: 000406682000009
DOI: 10.1002/slct.201701124
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Title: ChemistrySelect
Source Genre: Journal
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Publ. Info: Weinheim : Wiley-VCH
Pages: - Volume / Issue: 2 (21) Sequence Number: - Start / End Page: 5849 - 5859 Identifier: Other: 2365-6549
CoNE: https://pure.mpg.de/cone/journals/resource/2365-6549