TY - JOUR
T1 - Unprecedented Spectroscopic and Computational Evidence for Allenyl and Propargyl Titanocene(IV) Complexes
T2 - Electrophilic Quenching of Their Metallotropic Equilibrium
AU - Ruiz-Muelle, Ana Belén
AU - Oña-Burgos, Pascual
AU - Ortuño, Manuel A.
AU - Oltra, J. Enrique
AU - Rodríguez-García, Ignacio
AU - Fernández, Ignacio
N1 - Publisher Copyright:
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
PY - 2016/2/12
Y1 - 2016/2/12
N2 - 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 4.1Å for 3 and 9, respectively. Full 1H, 13C, Δ1H, and Δ13CNMR 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.
AB - 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 4.1Å for 3 and 9, respectively. Full 1H, 13C, Δ1H, and Δ13CNMR 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.
KW - density functional calculations
KW - DOSY
KW - metallotropic equilibrium
KW - NMR spectroscopy
KW - titanocenes
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U2 - 10.1002/chem.201504281
DO - 10.1002/chem.201504281
M3 - Article
C2 - 26786999
AN - SCOPUS:84961285674
SN - 0947-6539
VL - 22
SP - 2427
EP - 2439
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 7
ER -