{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,9]],"date-time":"2026-10-09T19:52:11Z","timestamp":1791575531454,"version":"4.3.4"},"reference-count":69,"publisher":"MDPI AG","issue":"2","license":[{"start":{"date-parts":[[2019,1,16]],"date-time":"2019-01-16T00:00:00Z","timestamp":1547596800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"Finnish Grid and Cloud","award":["urn:nbn:fi:research-infras-2016072533"],"award-info":[{"award-number":["urn:nbn:fi:research-infras-2016072533"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>[TiCp2S5] (phase A), [TiCp2Se5] (phase F), and five solid solutions of mixed titanocene selenide sulfides [TiCp2SexS5\u2212x] (Cp = C5H5\u2212) with the initial Se:S ranging from 1:4 to 4:1 (phases B\u2013E) 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\u2013E: [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\u2013E observed upon crystal structure determinations is consistent with the spectral assignment. The enthalpies of formation calculated for all twenty [TiCp2SexS5\u2212x] (x = 0\u20135) 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.<\/jats:p>","DOI":"10.3390\/molecules24020319","type":"journal-article","created":{"date-parts":[[2019,1,17]],"date-time":"2019-01-17T03:02:03Z","timestamp":1547694123000},"page":"319","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Titanocene Selenide Sulfides Revisited: Formation, Stabilities, and NMR Spectroscopic Properties"],"prefix":"10.3390","volume":"24","author":[{"given":"Heli","family":"Laasonen","sequence":"first","affiliation":[{"name":"Laboratory of Inorganic Chemistry, Environmental and Chemical Engineering, University of Oulu, P.O. Box 3000, 90014 Oulu, Finland"},{"name":"Department of Health, Legal Rights and Technologies, National Supervisory Authority for Welfare and Health (Valvira), P.O. Box 210, 00281 Helsinki, Finland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Johanna","family":"Ik\u00e4heimonen","sequence":"additional","affiliation":[{"name":"Laboratory of Inorganic Chemistry, Environmental and Chemical Engineering, University of Oulu, P.O. Box 3000, 90014 Oulu, Finland"},{"name":"Outokumpu Stainless Oy, Ter\u00e4stie 1, 95490 Tornio, Finland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mikko","family":"Suomela","sequence":"additional","affiliation":[{"name":"Laboratory of Inorganic Chemistry, Environmental and Chemical Engineering, University of Oulu, P.O. Box 3000, 90014 Oulu, Finland"},{"name":"Eurofins Nab Labs Oy, Industry Services, Nuottasaarentie 17, 90400 Oulu, Finland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3695-4151","authenticated-orcid":false,"given":"J. Mikko","family":"Rautiainen","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Nanoscience Centre, University of Jyv\u00e4skyl\u00e4, P.O. Box 35, 40014 Jyv\u00e4skyl\u00e4, Finland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7070-8707","authenticated-orcid":false,"given":"Risto S.","family":"Laitinen","sequence":"additional","affiliation":[{"name":"Laboratory of Inorganic Chemistry, Environmental and Chemical Engineering, University of Oulu, P.O. 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