Reactivity of Dianionic β-Diketiminato Samarium Amide LSmN(SiMe3)2(THF) (L = {(2,6-iPr2C6H3)NC(CH2)CHC(CH3)N(2,6-iPr2C6H3)}2–) toward ArC≡N (Ar = C6H5, p-MeOC6H4) and Ph2C═C═NtBu: A Facile Route for Modification of Dianionic β-Diketiminato Ligands
Peng Liu , Yong Zhang , and Qi Shen * （沈琪）
Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, People’s Republic of China
Organometallics 2013, 32, 1295–1299.
Dianionic β-diketiminato samarium amide LSmN(SiMe3)2(THF) (1) (L = {(2,6-iPr2C6H3)NC(CH2)CHC(CH3)N(2,6-iPr2C6H3)}2–) shows striking reactivity toward aromatic nitrile and ketenimine. Reaction of 1 with C6H5CN and p-MeOC6H4CN leads via nucleophilic addition followed by 1,5-H shift to entirely modified dianionic β-diketiminato samarium amides with two asymmetric alkylideneamido bridges, [L1SmN(SiMe3)2(C6H5CN)]2 (L1 = {μ-N═C(C6H5)CHC(CHC(CH3)NH(2,6-iPr2C6H3))N(2,6-iPr2C6H3)}2–) (2) and [L2SmN(SiMe3)2(p-MeOC6H4CN)]2 (L2 = {μ-N═C(p-CH3OC6H4)CHC(CHC(CH3)NH(2,6-iPr2C6H3))N(2,6-iPr2C6H3)}2–) (3), while conversion of Ph2C═C═NtBu affords the cycloadduct [L3SmN(SiMe3)2(THF)] (L3 = {(2,6-iPr2C6H3)NC(CHC(CH3)N(2,6-iPr2C6H3))CHC(CH(C6H5)2)N(C(CH3)3)}2–) (4) via nucleophilic addition and 1,3-H shift.
链接： //pubs.acs.org/doi/abs/10.1021/om301023u
