RT info:eu-repo/semantics/article
T1 Reactivity of Tuck-over Titanium Oxo Complexes with Isocyanides
A1 Gómez-Pantoja Güemes, María
A1 González Pérez, Juan Ignacio
A1 Martín Alonso, Avelino
A1 Mena Montoro, Miguel
A1 Santamaría Angulo, Cristina
A1 Temprado Morena, Manuel
K1 Química
K1 Chemistry
AB The reactivity of the "tuck-over" species [Ti2(η5-C5Me5)(CH2Ph)3(μ-η5-C5Me4CH2-κC)(μ-O)] (1) and [Ti2(η5-C5Me5)(CH2CMe3)(μ-η5-C5Me4CH2-κC)(μ-CH2CMe2CH2)(μ-O)] (2) toward isocyanides has been examined both synthetically and theoretically. Treatment of 1with the isocyanides RNC, R = Me3SiCH2, 2,6-Me2C6H3, tBu,iPr, leads to a series of η2-iminoacyl species (3−6) where the molecule of isocyanide inserts into one of the terminal metal−alkyl bonds. The analogous reaction of the "tuck-over" metallacycle species 2 with 2,6-Me2C6H3NC andtBuNC results inthe initial insertion of one isocyanide into the terminal Ti−alkyl bondto form the iminoacyl complexes 7 and 8, followed by a secondinsertion into the metallacycle moiety to generate 9, in the case of tertbutylisocyanide. DFT calculations support the selective reactivity observed experimentally with a kinetic and thermodynamicpreference for RNC insertion on the terminal alkyl groups bound to both metallic centers over the alternative insertion on the "tuck-over"ligand.
SN 0276-7333
YR 2018
FD 2018-06-22
LK http://hdl.handle.net/10017/38900
UL http://hdl.handle.net/10017/38900
LA eng
NO Ministerio de Economía y CompetitividadUniversidad de Alcalá
DS MINDS@UW
RD 24-abr-2024