Preparation and Reactivity of a Compartmental Schiff-Base Samarium Dinuclear Complex

SmI 2 (THF) 5 acted as a reducing agent in the reaction with phenylenebis(3,5-Bu t 4 salicylidene)iminatosodium, (3,5-Bu t 4 salophen)Na 2 (THF) 2, to yield a dimeric compound [Sm 2 (SB−SB)(THF) 3 ]·2toluene ( 2 ) [SB−SB = C−C bonded 3,5-Bu t 4 salophen dimer] arising from the reductive C−C coupling of two imine functional groups of two 3,5-Bu t 4 salophenSm units. Complex 2 reacts with MeLi, resulting in a novel oxo-bridged dimer, {[(Me 2 −SB)Sm(μ-CH 3 )Li(THF)][(Me 2 −SB)Sm(μ-CH 3 )Li(THF) 2 Li(THF) 2 ]}(μ-O)(μ-Li) 3 ( 3 ) [Me 2 SB = phenyl-enebis(3,5-Bu t 4 salycyl)dimethyldiamidato], featuring alkylation of both Sm atoms and arising from cleavage of the C−C bond connecting the two units, as well as complete reduction of the imine groups of the two salophen ligands and THF deoxygenation. Similar cleavage of the connecting C−C bond of complex 2 was also observed during the reaction with dry O 2 to form a distorted cuboid cluster in which four Sm atoms are bridged by four hydroxyl groups, [(3,5-Bu t 4 salophen)Sm(OH)] 4 ·4toluene ( 4 ). The structures of complexes 2, 3, and 4 were elucidated by X-ray crystallography.