First complexes of scandium and yttrium with NNO and NNS heteroscorpionate ligands.

The reaction of ScCl(3)(THF)(3) or YCl(3) in a 1:1 molar ratio under reflux for 8 h with [{Li(bdmpza)(H(2)O)}(4)] [bdmpza = bis(3,5-dimethylpyrazol-1-yl)acetate], [{Li(bdmpzdta)(H(2)O)}(4)] [bdmpzdta = bis(3,5-dimethylpyrazol-1-yl)dithioacetate], and (Hbdmpze) [bdmpze = 2,2-bis(3,5-dimethylpyrazol-1-yl)ethoxide] affords the corresponding complexes [MCl(2)(kappa(3)-bdmpzx)(THF)] (x = a, M = Sc (1), Y (2); x = dta, M = Sc (3), Y (4); x = e, M = Sc (5), Y (6)). However, when the reaction was carried out for 1 h under reflux between ScCl(3)(THF)(3) and [{Li(bdmpzdta)(H(2)O)}(4)], a new anionic complex [Li(THF)(4)][ScCl(3)(kappa(3)-bdmpzdta)] (7) was obtained. Reaction of [{Li(bdmpza)(H(2)O)}(4)] with YCl(3) in a 2:1 molar ratio under reflux for 8 h gave the complex [YCl(kappa(3)-bdmpza)(2)] (8). The same reaction, but with the lithium compound [{Li(bdmpzdta)(H(2)O)}(4)], led to the formation of an anionic complex [Li(THF)(4)][YCl(3)(kappa(3)-bdmpzdta)] (9). The X-ray crystal structures of 7 and 9 were established. Finally, the addition of 1 equiv of [{Li(bdmpza)(H(2)O)}(4)] or [{Li(bdmpzdta)(H(2)O)}(4)] to a solution of YCl(3) in THF under reflux, followed by the addition of 1 equiv of 1,10-phenanthroline, resulted in the formation of the corresponding complexes [YCl(2)(kappa(3)-bdmpzx)(phen)] (x = a (10), x = dta (11)). These complexes are the first examples of group 3 metals stabilized by heteroscorpionate ligands. In addition, we have explored the reactivity of some of these complexes with alcohols and amides. For example, the direct reaction of [YCl(2)(kappa(3)-bdmpza)(THF)] (2) with several alcohols gave the alkoxide complexes [YCl(kappa(3)-bdmpza)(OR)] (R = Et (12), iPr (13)). Finally, the reaction between [ScCl(2)(kappa(3)-bdmpzdta)(THF)] (3) or [Li(THF)(4)][ScCl(3)(kappa(3)-bdmpzdta)] (7) and LiN(SiMe(3))(2).Et(2)O in 1:1 and 1:2 molar ratios gave rise to the complexes [ScCl(kappa(3)-bdmpzdta){N(SiMe(3))(2)}] (14) and [Sc(kappa(3)-bdmpzdta){N(SiMe(3))(2)}(2)] (15), respectively.