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Experimental and Theoretical Investigations of Tellurium(IV) Diimides and Imidotelluroxanes: X-ray Structures of B(C6F5)3 Adducts of OTe(μ-NtBu)2TeNtBu, [OTe(μ-NtBu)2Te(μ-O)]2 and tBuNH2

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Schatte, G., Chivers, T., Tuononen, H., Suontamo, R., Laitinen, R., & Valkonen, J. (2005). Experimental and Theoretical Investigations of Tellurium(IV) Diimides and Imidotelluroxanes: X-ray Structures of B(C6F5)3 Adducts of OTe(μ-NtBu)2TeNtBu, [OTe(μ-NtBu)2Te(μ-O)]2 and tBuNH2. Inorganic Chemistry, 44(2), 443-451. https://doi.org/10.1021/ic048565+
Published in
Inorganic Chemistry
Authors
Schatte, Gabriele |
Chivers, Tristram |
Tuononen, Heikki |
Suontamo, Reijo |
Laitinen, Risto |
Valkonen, Jussi
Date
2005
Discipline
Epäorgaaninen ja analyyttinen kemiaInorganic and Analytical Chemistry
Copyright
© 2005 American Chemical Society. This is a final draft version of an article whose final and definitive form has been published by ACS. Published in this repository with the kind permission of the publisher.

 
The hydrolysis of tBuNTe(μ-NtBu)2TeNtBu (1) with 1 or 2 equiv of (C6F5)3B·H2O results in the successive replacement of terminal imido groups by oxo ligands to give the telluroxane-Lewis acid adducts (C6F5)3B·OTe(μ-NtBu)2TeNtBu (2) and [(C6F5)3B·OTe(μ-NtBu)2Te(μ-O)]2 (3), which were characterized by multinuclear NMR spectroscopy and X-ray crystallography. The TeO distance in 2 is 1.870(2) Å. The di-adduct 3 involves the association of four tBuNTeO monomers to give a tetramer in which both terminal TeO groups [d(TeO) = 1.866(3) Å] are coordinated to B(C6F5)3. The central Te2O2 ring in 3 is distinctly unsymmetrical [d(TeO) = 1.912(3) and 2.088(2) Å]. The X-ray structure of (C6F5)3B·NH2tBu (4), the byproduct of these hydrolysis reactions, is also reported. The geometries and energies of tellurium(IV) diimides and imido telluroxanes were determined using quantum chemical calculations. The calculated energies for the reactions E(NR)2 + Te(NR)2 (E = S, Se, Te; R = H, Me, tBu, SiMe3) confirm that cyclodimerization of tellurium(IV) diimides is strongly exothermic. In the mixed-chalcogen systems, the cycloaddition is energetically favorable for the Se/Te combination. The calculated energies for the further oligomerization of the dimers XE(μ-NMe)2EX (E = Se, Te; X = NMe, O) indicate that the formation of tetramers is strongly exothermic for the tellurium systems but endothermic (X = NMe) or thermoneutral (X = O) for the selenium systems, consistent with experimental observations. ...
Publisher
ACS
ISSN Search the Publication Forum
0020-1669
Keywords
telluuri(IV) diimidit imidotelluroksaanit tellurium(IV) diimides imidotelluroxanes
DOI
https://doi.org/10.1021/ic048565+
URI

http://urn.fi/URN:NBN:fi:jyu-201511183702

Publication in research information system

https://converis.jyu.fi/converis/portal/detail/Publication/14759283

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