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

6533b7dcfe1ef96bd1273588

RESEARCH PRODUCT

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

Mikko Suomela Heli Laasonen Risto S. Laitinen Johanna Ikäheimonen J. Mikko Rautiainen

subject

sulfidit 77Se-NMR spectroscopy Pharmaceutical Science Crystal structure Sulfides organometalliyhdisteet 010402 general chemistry 01 natural sciences Article Analytical Chemistry lcsh:QD241-441 Selenium crystal structures chemistry.chemical_compound Chalcogen lcsh:Organic chemistry titanocene selenide sulfides Selenide 0103 physical sciences Drug Discovery Organometallic Compounds Carbon-13 Magnetic Resonance Spectroscopy NMR-spektroskopia Physical and Theoretical Chemistry ta116 DLPNO-CCSD(T) calculations 13C-NMR spectroscopy Crystallography Molecular Structure 010304 chemical physics <sup>13</sup>C-NMR spectroscopy Chemistry Chemical shift Organic Chemistry Titanocene dichloride Carbon-13 NMR kiteet Standard enthalpy of formation 0104 chemical sciences NMR spectra database titaani <sup>77</sup>Se-NMR spectroscopy Chemistry (miscellaneous)Carbon Disulfide seleeni Quantum Theory Molecular Medicine Physical chemistry

description

[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.

year	journal	country	edition	language
2019-01-16	Molecules

https://doi.org/10.3390/molecules24020319