Triorganoantimony(V) complexes with internally functionallized oximes: synthetic, spectroscopic and structural aspects of [R3Sb(Br)L], [R3Sb(OH)L] and [R3SbL2], crystal and molecular structures of [Me3Sb{ONC(Me)C4H3O}2], [Me3Sb{ONC(Me)C4H3S}2], 2-OC4H3C

Triorganoantimony(V) complexes with internally functionallized oximes of the type [R3Sb{ONC(Me)Ar}2] (1) [R=Me, Pri; Ar=C5H4N, C4H3S, C4H3O] have been prepared by the reaction of R3SbBr2 with the corresponding oximes in 1:2 molar ratio in anhydrous benzene. Treatment of 1 with one equivalent of R3SbX2 afforded a redistribution product [R3Sb(X){ONC(Me)Ar}] (2) [X=(a):Br, (b):OH]. The species, R3Sb(OH)L, may also be obtained by the controlled hydrolysis of 1 (R=Pri; Ar=C5H4N). All of these complexes have been characterized by elemental analyses, and IR and NMR (1H and 13C) spectroscopic studies. Crystal structures of [Me3Sb{ONC(Me)C4H3O-2}2] (3), [Me3Sb{ONC(Me)C4H3S-2}2] (4) 2-OC4H3C(Me)NOH (5) and 2-SC4H3C(Me)NOH (6) are reported. The geometry around the antimony atom in 3 and 4 is distorted trigonal bipyramidal with the carbon atoms of the SbMe3 unit in equatorial positions and the two oxygen atoms of the oxime group occupying axial positions (O(1)SbO(2) 171.67(12) in 3 and 169.14(13) in 4). The free oxime is clearly hydrogen bonded (HN 2.08 Å in 6) to essentially form a dimer.