Unprecedented Spectroscopic and Computational Evidence for Allenyl and Propargyl Titanocene(IV) Complexes: Electrophilic Quenching of Their Metallotropic Equilibrium

TitleUnprecedented Spectroscopic and Computational Evidence for Allenyl and Propargyl Titanocene(IV) Complexes: Electrophilic Quenching of Their Metallotropic Equilibrium
Publication TypeJournal Article
Year of Publication2016
AuthorsRuiz-Muelle ABelén, Oña-Burgos P, Ortuño MA, J. Oltra E, Rodríguez-García I, Fernandez I
JournalChemistry – A European Journal
Volume22
Pagination2427–2439
ISSN1521-3765
Keywordsdensity functional calculations, DOSY, metallotropic equilibrium, NMR spectroscopy, titanocenes
Abstract

The synthesis and structural characterization of allenyl titanocene(IV) [TiClCp2(CH=C=CH2)] 3 and propargyl titanocene(IV) [TiClCp2(CH2−C≡C−(CH2)4CH3)] 9 have been described for the first time. Advanced NMR methods including diffusion NMR methods (diffusion pulsed field gradient stimulated spin echo (PFG-STE) and DOSY) have been applied and established that these organometallics are monomers in THF solution with hydrodynamic radii (from the Stokes–Einstein equation) of 3.5 and 4.1 Å for 3 and 9, respectively. Full 1H, 13C, Δ1H, and Δ13C NMR data are given, and through the analysis of the Ramsey equation, the first electronic insights into these derivatives are provided. In solution, they are involved in their respective metallotropic allenyl–propargyl equilibria that, after quenching experiments with aromatic and aliphatic aldehydes, ketones, and protonating agents, always give the propargyl products P (when carbonyls are employed), or allenyl products A (when a proton source is added) as the major isomers. In all the cases assayed, the ratio of products suggests that the metallotropic equilibrium should be faster than the reactions of 3 and 9 with electrophiles. Indeed, DFT calculations predict lower Gibbs energy barriers for the metallotropic equilibrium, thus confirming dynamic kinetic resolution.

URLhttp://dx.doi.org/10.1002/chem.201504281
DOI10.1002/chem.201504281
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