Otero Antonio, Fernández-Baeza Juan, Antiñolo Antonio, Tejeda Juan, Lara-Sánchez Agustín, Sánchez-Barba Luis, Martínez-Caballero Emilia, Rodríguez Ana M, López-Solera Isabel
Departamento de Química Inorgánica, Orgánica y Bioquímica, Universidad de Castilla-La Mancha, 13071-Ciudad Real, Spain.
Inorg Chem. 2005 Jul 25;44(15):5336-44. doi: 10.1021/ic050525y.
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.
在回流条件下，将三氯化钪（四氢呋喃）₃（ScCl₃(THF)₃）或三氯化钇（YCl₃）与[Li(bdmpza)(H₂O)]₄ [bdmpza = 双（3,5 - 二甲基吡唑 - 1 - 基）乙酸酯]、[Li(bdmpzdta)(H₂O)]₄ [bdmpzdta = 双（3,5 - 二甲基吡唑 - 1 - 基）二硫代乙酸酯]以及（Hbdmpze）[bdmpze = 2,2 - 双（3,5 - 二甲基吡唑 - 1 - 基）乙醇盐]以1:1的摩尔比反应8小时，可得到相应的配合物[MCl₂(κ³ - bdmpzx)(THF)]（x = a，M = Sc（1），Y（2）；x = dta，M = Sc（3），Y（4）；x = e，M = Sc（5），Y（6））。然而，当在回流条件下将三氯化钪（四氢呋喃）₃（ScCl₃(THF)₃）与[Li(bdmpzdta)(H₂O)]₄反应1小时时，得到了一种新的阴离子配合物[Li(THF)₄][ScCl₃(κ³ - bdmpzdta)]（7）。在回流条件下，将[Li(bdmpza)(H₂O)]₄与三氯化钇（YCl₃）以2:1的摩尔比反应8小时，得到配合物[YCl(κ³ - bdmpza)₂]（8）。同样的反应，但使用锂化合物[Li(bdmpzdta)(H₂O)]₄，则生成阴离子配合物[Li(THF)₄][YCl₃(κ³ - bdmpzdta)]（9）。确定了7和9的X射线晶体结构。最后，在回流条件下，向三氯化钇（YCl₃）的四氢呋喃溶液中加入1当量的[Li(bdmpza)(H₂O)]₄或[Li(bdmpzdta)(H₂O)]₄，随后加入1当量的1,10 - 菲咯啉，生成相应的配合物[YCl₂(κ³ - bdmpzx)(phen)]（x = a（10），x = dta（11））。这些配合物是由杂蝎形配体稳定的第3族金属的首个实例。此外，我们还研究了其中一些配合物与醇和酰胺的反应活性。例如，[YCl₂(κ³ - bdmpza)(THF)]（2）与几种醇直接反应得到醇盐配合物[YCl(κ³ - bdmpza)(OR)]（R = Et（12），iPr（13））。最后，[ScCl₂(κ³ - bdmpzdta)(THF)]（3）或[Li(THF)₄][ScCl₃(κ³ - bdmpzdta)]（7）与二（三甲基硅基）胺锂（LiN(SiMe₃)₂）·Et₂O以1:1和1:2的摩尔比反应，分别生成配合物[ScCl(κ³ - bdmpzdta){N(SiMe₃)₂}]（14）和[Sc(κ³ - bdmpzdta){N(SiMe₃)₂}₂]（15）。
