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Open AccessFeature PaperArticle

Titanocene Selenide Sulfides Revisited: Formation, Stabilities, and NMR Spectroscopic Properties

1
Laboratory of Inorganic Chemistry, Environmental and Chemical Engineering, University of Oulu, P.O. Box 3000, 90014 Oulu, Finland
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Department of Health, Legal Rights and Technologies, National Supervisory Authority for Welfare and Health (Valvira), P.O. Box 210, 00281 Helsinki, Finland
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Outokumpu Stainless Oy, Terästie 1, 95490 Tornio, Finland
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Eurofins Nab Labs Oy, Industry Services, Nuottasaarentie 17, 90400 Oulu, Finland
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Department of Chemistry, Nanoscience Centre, University of Jyväskylä, P.O. Box 35, 40014 Jyväskylä, Finland
*
Author to whom correspondence should be addressed.
Molecules 2019, 24(2), 319; https://doi.org/10.3390/molecules24020319
Received: 31 December 2018 / Revised: 10 January 2019 / Accepted: 11 January 2019 / Published: 16 January 2019
(This article belongs to the Special Issue Main Group Elements in Synthesis)
[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 BE) 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 BE: [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 BE 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. View Full-Text
Keywords: titanocene selenide sulfides; 77Se-NMR spectroscopy; 13C-NMR spectroscopy; crystal structures; DLPNO-CCSD(T) calculations titanocene selenide sulfides; 77Se-NMR spectroscopy; 13C-NMR spectroscopy; crystal structures; DLPNO-CCSD(T) calculations
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MDPI and ACS Style

Laasonen, H.; Ikäheimonen, J.; Suomela, M.; Rautiainen, J.M.; Laitinen, R.S. Titanocene Selenide Sulfides Revisited: Formation, Stabilities, and NMR Spectroscopic Properties. Molecules 2019, 24, 319.

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