Otero A, Fernández-Baeza J, Antiñolo A, Carrillo-Hermosilla F, Tejeda J, Lara-Sánchez A, Sánchez-Barba L, Fernández-López M, Rodríguez A M, López-Solera I
Departamento de Química Inorgánica, Orgánica y Bioquímica, Universidad de Castilla-La Mancha, Campus Universitario, 13071-Ciudad Real, Spain.
Inorg Chem. 2002 Oct 7;41(20):5193-202. doi: 10.1021/ic020319f.
The preparation of new "scorpionate" ligands in the form of the lithium derivatives [(Li(bdmpzdta)(H(2)O))(4)] (1) [bdmpzdta = bis(3,5-dimethylpyrazol-1-yl)dithioacetate], [Li(bdphpza)(H(2)O)(THF)] (2) [bdphpza = bis(3,5-diphenylpyrazol-1-yl)acetate], and [Li(bdphpzdta)(H(2)O)(THF)] (3) [bdphpzdta = bis(3,5-diphenylpyrazol-1-yl)dithioacetate] has been carried out. Furthermore, a series of titanium complexes has been prepared by reaction of TiCl(4)(THF)(2) with the lithium reagents [(Li(bdmpza)(H(2)O))(4)] (4) [bdmpza = bis(3,5-dimethylpyrazol-1-yl)acetate] and 1. Under the appropriate experimental conditions neutral complexes, namely [TiCl(3)(kappa(3)-bdmpza)] (5), [TiCl(3)(kappa(3)-bdmpzdta)] (6), and [TiCl(2)(kappa(2)-bdmpzdta)(2)] (7), and cationic complexes, namely [TiCl(2)(THF)(kappa(3)-bdmpza)]Cl (8) and [TiCl(2)(THF)(kappa(3)-bdmpzdta)]Cl (9), were isolated. Complexes 8 and 9 undergo an interesting nucleophilic THF ring-opening reaction to give the corresponding alkoxide-containing species [TiCl(2)(kappa(3)-bdmpza)(O(CH(2))(4)Cl)] (10) and [TiCl(2)(kappa(3)-bdmpzdta)(O(CH(2))(4)Cl)] (11). A family of alkoxide-containing complexes of general formulas [TiCl(2)(kappa(3)-bdmpza)(OR)] [R = Me (12); R = Et (14); R = (i)Pr (16); R = (t)Bu (18)] and [TiCl(2)(kappa(3)-bdmpzdta)(OR)] [R = Me (13); R = Et (15); R = (i)Pr (17)] was also prepared. The structures of these complexes have been determined by spectroscopic methods, and in addition, the X-ray crystal structures of 3, 7, 10, and 11 were also established.
已制备出锂衍生物形式的新型“蝎形”配体，即[(Li(bdmpzdta)(H₂O))₄] (1) [bdmpzdta = 双(3,5 - 二甲基吡唑 - 1 - 基)二硫代乙酸酯]、[Li(bdphpza)(H₂O)(THF)] (2) [bdphpza = 双(3,5 - 二苯基吡唑 - 1 - 基)乙酸酯]和[Li(bdphpzdta)(H₂O)(THF)] (3) [bdphpzdta = 双(3,5 - 二苯基吡唑 - 1 - 基)二硫代乙酸酯]。此外，通过TiCl₄(THF)₂与锂试剂[(Li(bdmpza)(H₂O))₄] (4) [bdmpza = 双(3,5 - 二甲基吡唑 - 1 - 基)乙酸酯]和1反应制备了一系列钛配合物。在适当的实验条件下，分离出了中性配合物，即[TiCl₃(κ³ - bdmpza)] (5)、[TiCl₃(κ³ - bdmpzdta)] (6)和[TiCl₂(κ² - bdmpzdta)₂] (7)，以及阳离子配合物，即[TiCl₂(THF)(κ³ - bdmpza)]Cl (8)和[TiCl₂(THF)(κ³ - bdmpzdta)]Cl (9)。配合物8和9发生了有趣的亲核四氢呋喃开环反应，生成了相应的含醇盐物种[TiCl₂(κ³ - bdmpza)(O(CH₂)₄Cl)] (10)和[TiCl₂(κ³ - bdmpzdta)(O(CH₂)₄Cl)] (11)。还制备了通式为[TiCl₂(κ³ - bdmpza)(OR)] [R = Me (12); R = Et (14); R = (i)Pr (16); R = (t)Bu (18)]和[TiCl₂(κ³ - bdmpzdta)(OR)] [R = Me (13); R = Et (15); R = (i)Pr (17)]的含醇盐配合物家族。这些配合物的结构已通过光谱方法确定，此外，还确定了3、7、10和11的X射线晶体结构。
