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Mono(imidazolin-2-iminato) Actinide Complexes: Synthesis and Application in the Catalytic Dimerization of Aldehydes.
- Source :
-
Journal of the American Chemical Society . 12/10/2014, Vol. 136 Issue 49, p17180-17192. 13p. - Publication Year :
- 2014
-
Abstract
- The synthesis of the rnono(imidazolin-2-iminato) actinide(IV) complexes [(ImRN)An(N{SiMe3)2}3] (3-8) was accomplished by the protonolysis reaction between the respective imidazolin-2-imine (ImRNH, R = tBu, Mes, Dipp) and the actinide metallacycles [{(Me3Si)N}2An{κ²C,N-CH2SiMe2N(SiMe3)}] (1, An = U; 2, M = Th). The thorium and uranium complexes were obtained in high yields, and their structures were established by single-crystal X-ray diffraction analysis. The mono(imidazolin-2-iminato) actinide complexes 3-8 display short An-N bonds together with large An-N-C angles, indicating strong electron donation from the imidazolin-2-iminato moiety to the metal, corroborating a substantial π-character to the An-N bond. The reactivity of complexes 3-8 toward benzaldehyde was studied in the catalytic dimerization of aldehydes (Tishchenko reaction), displaying low to moderate catalytic activities for the uranium complexes 3-5 and moderate to high catalytic activities for the thorium analogues 6-8, among which 8 exhibited the highest catalytic activity. In addition, actinide coordination compounds showed unprecedented reactivity toward cyclic and branched aliphatic aldehydes in the catalytic Tishchenko reaction mediated by the thorium complex [(ImDippN)Th{N(SiMe3)2}3] (8), exhibiting high activity even at room temperature. Moreover, complex 8 was successfully applied in the crossed Tishchenko reaction between an aromatic or polyaromatic and an aliphatic cyclic and branched aldehyde, yielding selectively the asymmetrically substituted ester in high yields (80-100%). [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 00027863
- Volume :
- 136
- Issue :
- 49
- Database :
- Academic Search Index
- Journal :
- Journal of the American Chemical Society
- Publication Type :
- Academic Journal
- Accession number :
- 100326555
- Full Text :
- https://doi.org/10.1021/ja5091436