TY - JOUR
T1 - Mixed Imidazolin-2-iminato-Cp∗ Thorium(IV) Complexes
T2 - Synthesis and Reactivity Toward Oxygen-Containing Substrates
AU - Karmel, Isabell S.R.
AU - Fridman, Natalia
AU - Tamm, Matthias
AU - Eisen, Moris S.
N1 - Publisher Copyright:
© 2015 American Chemical Society.
PY - 2015/6/22
Y1 - 2015/6/22
N2 - The mixed pentamethylcyclopentadienyl thorium(IV) imidazolin-2-iminato complexes Cp∗2Th(ImDippN)(Me) (2) and Cp∗2Th(ImMesN)(Me) (3) were synthesized in quantitative yields via rapid protonolysis of Cp∗2Th(Me)2 (1) with the respective neutral imidazolin-2-iminato ligand ImRNH. Cp∗2Th(ImDippN)(Me) (2) and Cp∗2Th(ImMesN)(Me) (3) display short Th-N bond lengths and large Th-N-C angles. The reactivity of complex 2 and 3 toward oxygen-containing substrates was studied, and the catalytic activity of 2 was compared to the dimethyl (bispentamethyl-cyclopentadienyl) thorium complex 1. Complex 2 was applied in the catalytic Tishchenko reaction with aromatic, heteroaromatic, and branched aliphatic aldehydes, displaying a higher catalytic activity than Cp∗2Th(Me)2 and Cp∗2Th(ImMesN)(Me). Furthermore, 2 was applied as a catalyst in the crossed Tishchenko reaction and in the oligomerization of bis(aldehydes), as well as in the ring-opening polymerization of ε-caprolactone. In all reactions, the activity of Cp∗2Th(ImDippN)(Me) (2) and Cp∗2Th(ImMesN)(Me) (3) was higher than that observed for Cp∗2Th(Me)2 (1), which can be attributed to the increased electron density introduced by the coordination of the imidazolin-2-iminato ligand. (Chemical Equation Presented).
AB - The mixed pentamethylcyclopentadienyl thorium(IV) imidazolin-2-iminato complexes Cp∗2Th(ImDippN)(Me) (2) and Cp∗2Th(ImMesN)(Me) (3) were synthesized in quantitative yields via rapid protonolysis of Cp∗2Th(Me)2 (1) with the respective neutral imidazolin-2-iminato ligand ImRNH. Cp∗2Th(ImDippN)(Me) (2) and Cp∗2Th(ImMesN)(Me) (3) display short Th-N bond lengths and large Th-N-C angles. The reactivity of complex 2 and 3 toward oxygen-containing substrates was studied, and the catalytic activity of 2 was compared to the dimethyl (bispentamethyl-cyclopentadienyl) thorium complex 1. Complex 2 was applied in the catalytic Tishchenko reaction with aromatic, heteroaromatic, and branched aliphatic aldehydes, displaying a higher catalytic activity than Cp∗2Th(Me)2 and Cp∗2Th(ImMesN)(Me). Furthermore, 2 was applied as a catalyst in the crossed Tishchenko reaction and in the oligomerization of bis(aldehydes), as well as in the ring-opening polymerization of ε-caprolactone. In all reactions, the activity of Cp∗2Th(ImDippN)(Me) (2) and Cp∗2Th(ImMesN)(Me) (3) was higher than that observed for Cp∗2Th(Me)2 (1), which can be attributed to the increased electron density introduced by the coordination of the imidazolin-2-iminato ligand. (Chemical Equation Presented).
UR - http://www.scopus.com/inward/record.url?scp=84935023224&partnerID=8YFLogxK
U2 - 10.1021/acs.organomet.5b00273
DO - 10.1021/acs.organomet.5b00273
M3 - 文章
AN - SCOPUS:84935023224
SN - 0276-7333
VL - 34
SP - 2933
EP - 2942
JO - Organometallics
JF - Organometallics
IS - 12
ER -