The scandium terminal imido complex supported by a monoanionic tetradentate NNNN ligand, [LSc=N(DIPP)](L = [MeC(N(DIPP))CHC(Me)(NCH2CH2N(Me)CH2CH2NMe2]-, DIPP = 2,6-(iPr)2C6H3)(1), undergoes a C–N bond cleavage at el...The scandium terminal imido complex supported by a monoanionic tetradentate NNNN ligand, [LSc=N(DIPP)](L = [MeC(N(DIPP))CHC(Me)(NCH2CH2N(Me)CH2CH2NMe2]-, DIPP = 2,6-(iPr)2C6H3)(1), undergoes a C–N bond cleavage at elevated temperature to give a mononuclear scandium anilido intermediate 2a, which subsequently aggregates into a binuclear scandium anilido complex 2. The mononuclear intermediate 2a reacts with alkyne or imine to provide two scandium anilido complexes 3 and 4, which contain a dianionic tetradentate NNNC ligand or a dianionic tetradentate NNNN ligand. DFT calculations on the reaction mechanism of C–N bond cleavage in 1 were also performed.展开更多
基金This work was supported by the National Natural Science Foundation of China(21325210,21132002,21121062)the State Key Basic Research&Development Program(2012CB821600)the CAS/SAFEA International Partnership Program for Creative Research Teams.
文摘The scandium terminal imido complex supported by a monoanionic tetradentate NNNN ligand, [LSc=N(DIPP)](L = [MeC(N(DIPP))CHC(Me)(NCH2CH2N(Me)CH2CH2NMe2]-, DIPP = 2,6-(iPr)2C6H3)(1), undergoes a C–N bond cleavage at elevated temperature to give a mononuclear scandium anilido intermediate 2a, which subsequently aggregates into a binuclear scandium anilido complex 2. The mononuclear intermediate 2a reacts with alkyne or imine to provide two scandium anilido complexes 3 and 4, which contain a dianionic tetradentate NNNC ligand or a dianionic tetradentate NNNN ligand. DFT calculations on the reaction mechanism of C–N bond cleavage in 1 were also performed.