TY - JOUR
T1 - Actinide-Mediated Catalytic Addition of E-H Bonds (E=N, P, S) to Carbodiimides, Isocyanates, and Isothiocyanates
AU - Karmel, Isabell S.R.
AU - Tamm, Matthias
AU - Eisen, Moris S.
N1 - Publisher Copyright:
© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
PY - 2015/10/1
Y1 - 2015/10/1
N2 - Unprecedented catalytic reactivity of actinide coordination complexes toward heterocumulenes, such as carbodiimides, isocyanates, and isothiocyanates is reported. The mono(imidazolin-2-iminato) thorium(IV) complex [Th(ImDippN){N(SiMe3)2}3] (1) was applied as a precatalyst for the addition of E-H (E=N, P, S) bonds to the Y≡C≡X core (Y=R2N; X=NR2, O, S) of carbodiimides, isocyanates, and isothiocyanates. The respective insertion products were obtained in high yields under mild reaction conditions, with complex 1 displaying high tolerance toward functional groups and heteroatoms. New reactivity: The mono(imidazolin-2-iminato) thorium complex [Th(ImDippN){N(SiMe3)2}3] was successfully applied as an active catalyst for the addition of E-H (E=N, P, S) bonds across the central Y≡N≡C≡X linkage of carbodiimides, isocyanates and isothiocyanates, yielding the respective insertion products in high yields and under mild reaction conditions.
AB - Unprecedented catalytic reactivity of actinide coordination complexes toward heterocumulenes, such as carbodiimides, isocyanates, and isothiocyanates is reported. The mono(imidazolin-2-iminato) thorium(IV) complex [Th(ImDippN){N(SiMe3)2}3] (1) was applied as a precatalyst for the addition of E-H (E=N, P, S) bonds to the Y≡C≡X core (Y=R2N; X=NR2, O, S) of carbodiimides, isocyanates, and isothiocyanates. The respective insertion products were obtained in high yields under mild reaction conditions, with complex 1 displaying high tolerance toward functional groups and heteroatoms. New reactivity: The mono(imidazolin-2-iminato) thorium complex [Th(ImDippN){N(SiMe3)2}3] was successfully applied as an active catalyst for the addition of E-H (E=N, P, S) bonds across the central Y≡N≡C≡X linkage of carbodiimides, isocyanates and isothiocyanates, yielding the respective insertion products in high yields and under mild reaction conditions.
KW - actinide catalysis
KW - carbodiimides
KW - isocyanates
KW - nucleophilic insertion
KW - thioisocyanates
UR - http://www.scopus.com/inward/record.url?scp=84943199835&partnerID=8YFLogxK
U2 - 10.1002/anie.201502041
DO - 10.1002/anie.201502041
M3 - 文章
AN - SCOPUS:84943199835
SN - 1433-7851
VL - 54
SP - 12422
EP - 12425
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 42
ER -