Synthesis, characterization and catalytic performances of benzimidazolin-2-iminato actinide (IV) complexes in the Tishchenko reactions for symmetrical and unsymmetrical esters

TY - JOUR

T1 - Synthesis, characterization and catalytic performances of benzimidazolin-2-iminato actinide (IV) complexes in the Tishchenko reactions for symmetrical and unsymmetrical esters

AU - Liu, Heng

AU - Khononov, Maxim

AU - Fridman, Natalia

AU - Tamm, Matthias

AU - Eisen, Moris S.

N1 - Publisher Copyright: © 2017 Elsevier B.V.

PY - 2018/2/15

Y1 - 2018/2/15

N2 - A new family of benzimdazolin-2-iminato actinide−(IV) complexes [(Bim7-MeDipp/MeN)An(N(SiMe3)2)3] (An = U (3), Th (4)) and [(Bim4-MeDipp/MeN)An(N(SiMe3)2)3] (An = U (5), Th (6)) were synthesized and their solid state structures were established by single-crystal X-ray diffraction analysis. The catalytic performances of complexes 3–6 towards the homo- and cross-coupling of aldehydes (Tishchenko reaction) were studied and the thorium complexes 4 and 6 displayed moderate to high activities for the production of the corresponding symmetric and unsymmetrical esters. Coupling of aldehyde and alcohols, known as the tandem proton-transfer esterification, and the intermolecular coupling reaction between aldehyde and trifluoromethylketones were also investigated by these thorium complexes, indicating a complementary method to obtain unsymmetrical esters selectively. Plausible mechanisms for these reactions are proposed based on stoichiometric studies.

AB - A new family of benzimdazolin-2-iminato actinide−(IV) complexes [(Bim7-MeDipp/MeN)An(N(SiMe3)2)3] (An = U (3), Th (4)) and [(Bim4-MeDipp/MeN)An(N(SiMe3)2)3] (An = U (5), Th (6)) were synthesized and their solid state structures were established by single-crystal X-ray diffraction analysis. The catalytic performances of complexes 3–6 towards the homo- and cross-coupling of aldehydes (Tishchenko reaction) were studied and the thorium complexes 4 and 6 displayed moderate to high activities for the production of the corresponding symmetric and unsymmetrical esters. Coupling of aldehyde and alcohols, known as the tandem proton-transfer esterification, and the intermolecular coupling reaction between aldehyde and trifluoromethylketones were also investigated by these thorium complexes, indicating a complementary method to obtain unsymmetrical esters selectively. Plausible mechanisms for these reactions are proposed based on stoichiometric studies.

KW - Actinide catalysts

KW - Benzimidazolin-2-iminato

KW - Coupling reaction

KW - Ester

KW - Tishchenko reaction

UR - http://www.scopus.com/inward/record.url?scp=85031736717&partnerID=8YFLogxK

U2 - 10.1016/j.jorganchem.2017.09.020

DO - 10.1016/j.jorganchem.2017.09.020

M3 - 文章

AN - SCOPUS:85031736717

SN - 0022-328X

VL - 857

SP - 123

EP - 137

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

ER -