University of Oulu

Laasonen, H., Ikäheimonen, J., Suomela, M., Rautiainen, J., Laitinen, R. (2019) Titanocene Selenide Sulfides Revisited: Formation, Stabilities, and NMR Spectroscopic Properties. Molecules, 24 (2), 319. doi:10.3390/molecules24020319

Titanocene selenide sulfides revisited : formation, stabilities, and NMR spectroscopic properties

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Author: Laasonen, Heli1,2; Ikäheimonen, Johanna1,3; Suomela, Mikko1,4;
Organizations: 1Laboratory of Inorganic Chemistry, Environmental and Chemical Engineering, University of Oulu, P.O. Box 3000, 90014 Oulu, Finland
2Department of Health, Legal Rights and Technologies, National Supervisory Authority for Welfare and Health (Valvira), P.O. Box 210, 00281 Helsinki, Finland
3Outokumpu Stainless Oy, Terästie 1, 95490 Tornio, Finland
4Eurofins Nab Labs Oy, Industry Services, Nuottasaarentie 17, 90400 Oulu, Finland
5Department of Chemistry, Nanoscience Centre, University of Jyväskylä, P.O. Box 35, 40014 Jyväskylä, Finland
Format: article
Version: published version
Access: open
Online Access: PDF Full Text (PDF, 2.6 MB)
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Language: English
Published: Multidisciplinary Digital Publishing Institute, 2019
Publish Date: 2019-10-08


[TiCp2S5] (phase A), [TiCp2Se5] (phase F), and five solid solutions of mixed titanocene selenide sulfides [TiCp2SexS5−x] (Cp = C5H5) with the initial Se:S ranging from 1:4 to 4:1 (phases B–E) were prepared by reduction of elemental sulfur or selenium or their mixtures by lithium triethylhydridoborate in thf followed by the treatment with titanocene dichloride [TiCp2Cl2]. Their 77Se and 13C NMR spectra were recorded from the CS2 solution. The definite assignment of the 77Se NMR spectra was based on the PBE0/def2-TZVPP calculations of the 77Se chemical shifts and is supported by 13C NMR spectra of the samples. The following complexes in varying ratios were identified in the CS2 solutions of the phases B–E: [TiCp2Se5] (51), [TiCp2Se4S] (41), [TiCp2Se3S2] (31), [TiCp2SSe3S] (36), [TiCp2SSe2S2] (25), [TiCp2SSeS3] (12), and [TiCp2S5] (01). The disorder scheme in the chalcogen atom positions of the phases B–E observed upon crystal structure determinations is consistent with the spectral assignment. The enthalpies of formation calculated for all twenty [TiCp2SexS5−x] (x = 0–5) at DLPNO-CCSD(T)/CBS level including corrections for core-valence correlation and scalar relativistic, as well as spin-orbit coupling contributions indicated that within a given chemical composition, the isomers of most favourable enthalpy of formation were those, which were observed by 77Se and 13C NMR spectroscopy.

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Series: Molecules
ISSN: 1420-3049
ISSN-E: 1420-3049
ISSN-L: 1420-3049
Volume: 24
Issue: 2
Article number: 319
DOI: 10.3390/molecules24020319
Type of Publication: A1 Journal article – refereed
Field of Science: 116 Chemical sciences
Funding: This research was funded by Academy of Finland, University of Jyväskylä (J.M.R.), and Neste Oy Foundation (H.L.).
Copyright information: © 2019 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (