Show simple item record
dc.contributor.author |
Křižan, Martin |
|
dc.contributor.author |
Honzíček, Jan |
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dc.contributor.author |
Vinklárek, Jaromír |
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dc.contributor.author |
Růžičková, Zdeňka |
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dc.contributor.author |
Erben, Milan |
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dc.date.accessioned |
2014-12-16T15:34:41Z |
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dc.date.available |
2014-12-16T15:34:41Z |
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dc.date.issued |
2014 |
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dc.identifier.issn |
1144-0546 |
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dc.identifier.issn |
1369-9261 |
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dc.identifier.uri |
http://hdl.handle.net/10195/58487 |
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dc.description.abstract |
A series of complexes of the type [Ti(′Cp)2Y] {′Cp = η5-C5H5 (Cp), η5-C5H4SiMe3 (SiCp), η5-1,3-C5H3(Me3Si)2 (Si2Cp); Y = Cl−, CN−, NCS−, NCSe−, dicyanamide (dca), tricyanomethanide (tcm) and 1,2,3,4-thiatriazol-5-thiolate (ttt)} were prepared and studied by ESR spectroscopy. Ring-substituted compounds [Ti(SiCp)2Cl], [Ti(Si2Cp)2Cl], [Ti(SiCp)2CN] and [Ti(Si2Cp)2CN] dissolved in coordinating solvents exist in an equilibrium with solvated species. The thiatriazolthiolate ligand in complexes [Ti(′Cp)2(ttt)] behaves as a S,N-chelator to yield a thermally unstable 4-membered chelate ring having the ESR signal with significant splitting due to coupling with one 14N nucleus. Solutions of [Ti(′Cp)2Y] (Y = NCS−, NCSe−, dca and tcm) readily dissolve the additional pseudohalide salt giving anionic species [Ti(′Cp)2Y2]− with a characteristic ESR pattern caused by super-hyperfine splitting by two 14N nuclei. Cyanide complexes dissolve additional KCN as well, but no coupling to ligand nuclei (neither 14N nor 13C) was observed. The frozen-solution ESR spectra of [Ti(Si2Cp)2Cl], [Ti(Si2Cp)2CN] and [Ti(′Cp)2Y] (Y = NCS−, NCSe− and ttt) are typical for monomeric species of rhombic symmetry. The remaining complexes form dimeric {[Ti(Cp)2Cl]2, [Ti(SiCp)2Cl]2, [Ti(′Cp)2dca]2, and [Ti(′Cp)2tcm]2} or trimeric {[Ti(SiCp)2CN]3} adducts under these conditions. The nuclearity of [Ti(Cp)2CN] cannot be accurately determined by ESR spectroscopy due to its poor solubility but the presence of species with a higher spin ground state was confirmed (similar to the case of the above-mentioned dimers and trimer) by the observation of formally forbidden half-field transition. The reported results of the crystal structure analysis of [Ti(SiCp)2Cl], [Ti(Cp)2tcm], [Ti(SiCp)2tcm], [Ti(SiCp)2dca], [Ti(SiCp)2CN], and [TiCp2(NCS)]2O corroborate the findings based on spectroscopic measurements. |
eng |
dc.language.iso |
eng |
|
dc.publisher |
Royal Society of Chemistry |
cze |
dc.relation.ispartof |
New Journal of Chemistry. 2014 |
eng |
dc.rights |
open access |
eng |
dc.title |
Titanocene(III) pseudohalides: an ESR and structural study |
eng |
dc.type |
Article |
cze |
dc.peerreviewed |
yes |
eng |
dc.publicationstatus |
published |
eng |
dc.identifier.doi |
10.1039/C4NJ01404A |
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dc.relation.publisherversion |
http://pubs.rsc.org/en/Content/ArticleLanding/2015/NJ/C4NJ01404A#!divAbstract |
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dc.rights.licence |
This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence http://creativecommons.org/licenses/by-nc/3.0/ |
eng |
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