Otero A, Fernández-Baeza J, Antiñolo A, Tejeda J, Lara-Sánchez A, Sánchez-Barba L, Fernández-López M, López-Solera I
Departamento de Química Inorgánica, Orgánica y Bioquímica, Universidad de Castilla--La Mancha, Campus Universitario, 13071-Ciudad Real, Spain.
Inorg Chem. 2004 Feb 23;43(4):1350-8. doi: 10.1021/ic035067c.
A series of zirconium and hafnium heteroscorpionate complexes have been prepared by the reaction of MCl4 (M = Zr, Hf) with the compounds [Li(bdmpza)(H2O)] [bdmpza = bis(3,5-dimethylpyrazol-1-yl)acetate], [Li(bdmpzdta)(H2O)] [bdmpzdta = bis(3,5-dimethylpyrazol-1-yl)dithioacetate], and (Hbdmpze) [bdmpze = 2,2-bis(3,5-dimethylpyrazol-1-yl)ethoxide] (the latter with the prior addition of Bu(n)Li). Under the appropriate experimental conditions, mononuclear complexes, namely, [MCl3(kappa3-bdmpzx)] [x = a, M = Zr (1), Hf (2); x = dta, M = Zr (3), Hf (4); x = e, M = Zr (5), Hf (6)], and dinuclear complexes, namely, [[MCl2(mu-OH)(kappa3-bdmpzx)]2] [x = a, M = Zr (7), Hf (8); x = dta, M = Zr (9); x = e, M = Zr (10)], were isolated. A family of alkoxide-containing complexes of the general formula [ZrCl2(kappa3-bdmpzx)(OR)] [x = a, R = Me (11), Et (12), iPr (13), tBu (14); x = dta, R = Me (15), Et (16), iPr (17), tBu (18); x = e, R = Me (19), Et (20), (i)Pr (21), (t)Bu (22)] was also prepared. Complexes 11-14 underwent an interesting hydrolysis process to give the cluster complex [Zr6(mu3-OH)8(OH)8(kappa2-bdmpza)8] (23). The structures of these complexes have been determined by spectroscopic methods, and the X-ray crystal structures of 7, 8, and 23 were also established.
通过MCl₄（M = Zr，Hf）与化合物[[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]（后者预先加入正丁基锂）反应，制备了一系列锆和铪的异蝎形配合物。在合适的实验条件下，分离得到了单核配合物，即[MCl₃(κ³ - bdmpzx)] [x = a，M = Zr (1)，Hf (2)；x = dta，M = Zr (3)，Hf (4)；x = e，M = Zr (5)，Hf (6)]，以及双核配合物，即[[MCl₂(μ - OH)(κ³ - bdmpzx)]₂] [x = a，M = Zr (7)，Hf (8)；x = dta，M = Zr (9)；x = e，M = Zr (10)]。还制备了通式为[ZrCl₂(κ³ - bdmpzx)(OR)] [x = a，R = Me (11)，Et (12)，iPr (13)，tBu (14)；x = dta，R = Me (15)，Et (16)，iPr (17)，tBu (18)；x = e，R = Me (19)，Et (20)，(i)Pr (21)，(t)Bu (22)]的含醇盐配合物家族。配合物11 - 14经历了一个有趣的水解过程，生成簇状配合物[Zr₆(μ₃ - OH)₈(OH)₈(κ² - bdmpza)₈] (23)。这些配合物的结构已通过光谱方法确定，并且还确定了7、8和23的X射线晶体结构。
