Mixed Imidazolin-2-iminato-Cp∗ Thorium(IV) Complexes: Synthesis and Reactivity Toward Oxygen-Containing Substrates

Isabell S.R. Karmel, Natalia Fridman, Matthias Tamm*, Moris S. Eisen

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

29 Scopus citations

Abstract

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).

Original languageEnglish
Pages (from-to)2933-2942
Number of pages10
JournalOrganometallics
Volume34
Issue number12
DOIs
StatePublished - 22 Jun 2015
Externally publishedYes

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