Titanocene(III) pseudohalides: an ESR and structural study
作者： Martin Křižan , Jan Honzíček , Jaromír Vinklárek , Zdeňka Růžičková , Milan Erben
DOI: 10.1039/C4NJ01404A
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摘要: A series of complexes 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 studied by ESR spectroscopy. Ring-substituted compounds [Ti(SiCp)2Cl], [Ti(Si2Cp)2Cl], [Ti(SiCp)2CN] [Ti(Si2Cp)2CN] dissolved in coordinating solvents exist an equilibrium with solvated species. The thiatriazolthiolate ligand [Ti(′Cp)2(ttt)] behaves as a S,N-chelator to yield thermally unstable 4-membered chelate ring having signal significant splitting due coupling one 14N nucleus. Solutions (Y dca tcm) readily dissolve additional pseudohalide salt giving anionic species [Ti(′Cp)2Y2]− characteristic pattern caused super-hyperfine two nuclei. Cyanide KCN well, but no nuclei (neither nor 13C) was observed. frozen-solution spectra NCSe− ttt) are typical for monomeric rhombic symmetry. remaining form dimeric {[Ti(Cp)2Cl]2, [Ti(SiCp)2Cl]2, [Ti(′Cp)2dca]2, [Ti(′Cp)2tcm]2} or trimeric {[Ti(SiCp)2CN]3} adducts under these conditions. nuclearity [Ti(Cp)2CN] cannot be accurately determined spectroscopy its poor solubility presence higher spin ground state confirmed (similar case above-mentioned dimers trimer) observation formally forbidden half-field transition. reported results crystal structure analysis [Ti(Cp)2tcm], [Ti(SiCp)2tcm], [Ti(SiCp)2dca], [Ti(SiCp)2CN], [TiCp2(NCS)]2O corroborate findings based on spectroscopic measurements.
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