Preparation and reactivity of a compartmental Schiff-base samarium dinuclear complex

SmI2(THF)(5) acted as a reducing agent in the reaction with phenylenebis(3,5 -Bu-4(t)-salicylidene)iminatosodium, (3,5-Bu(4)(t)salophen)Na-2(THF)(2), to yield a dimeric compound [Sm-2-(SB-SB)(THF)(3)]. 2toluene (2) [SB-SB = C-CI bonded 3,5-But4salophen dimer] arising from the reductive C - C coupling of two imine functional groups of two 3,5-Bu(4)(t)salophenSm units. Complex 2 reacts with MeLi, resulting in a novel ore-bridged dimer, {[(Mea-SB)Sm(mu-CH3)Li(THF)][(Me-2-SB)Sm(mu-CH3)Li(THF)(2)Li(THF)2]}(mu-O)(mu-Li)(3)(3)[Me2SB = phenylenebis(3,5- Bu(4)(t)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(4)(t)salophen)Sm(OH)](4). 4toluene (4). The structures of complexes 2, 3, and 4 were elucidated by X-ray crystallography.