601494-08-0Relevant academic research and scientific papers
Reduction of ketimines by samarium(II) complexes. Isolation and structural characterization of samarium(III) η1-amine/η 1-ketimido and η2-ketimine complexes
Hou, Zhaomin,Yoda, Chikako,Koizumi, Take-Aki,Nishiura, Masayoshi,Wakatsuki, Yasuo,Fukuzawa, Shin-Ichi,Takats, Josef
, p. 3586 - 3592 (2008/10/08)
The reaction of (C5Me5)2Sm(THF) 2 with 2 equiv of benzophenone imine (Ph2C=NH) in THF at room temperature gave the samarocene(III) amine/ketimido complex (C 5Me5)2Sm-(N=CPh2)(NH 2CHPh2) (1) in 58% isolated yield. The use of 1 equiv of Ph2C=NH also afforded 1 as the only isolable product, albeit in a lower yield (ca. 20%). Deuterium-labeling experiments suggest that 1 is formed via hydrogen abstraction by the in-situ-generated imine radical anion species, followed by acid-base reaction between the resulting amido species and another molecule of Ph2C=NH. The reactions of 2 equiv of Sm(OAr) 2(THF)3 (Ar = C6H2- tBu2-2,6-Me-4) with N-phenyl benzophenone imine (Ph 2C=NPh) and N-phenyl fluorenone imine (C12H 8C=NPh) yielded the Sm(III) η2-imine-diamon/aryloxide complexes Sm(η2-Ph2-CNPh)(OAr)(THF)3 (3, 65%) and Sm(η2-C12H8CNPh)(OAr)(THF) 3 (4, 77%), respectively, together with the byproduct Sm(OAr) 3. The reaction of 1 equiv of Sm(OAr)2(THF)3 with Ph2C=NPh also gave the imine-dianion complex 3, whereas an imine radical anion species was not observed. Similarly, the reactions of 2 equiv of Sm{N(SiMe3)2}2(THF)2 with Ph2-C=NPh and C12H8C==NPh yielded the η2-imine-dianion/silylamido complexes Sm(η 2-Ph2-CNPh){N(SiMe3)2}(THF) 3 (5, 87%) and Sm(η2-C12H 8CNPh){N(SiMe3)2}(THF)3 (6, 71%), respectively. Complexes 3-6 represent the first examples of structurally characterized trivalent lanthanide η2-imine complexes.
