Monegan Jessie D, Bunge Scott D
Department of Chemistry, Kent State University, Kent, Ohio 44242-0001, USA.
Inorg Chem. 2009 Apr 6;48(7):3248-56. doi: 10.1021/ic8022776.
The synthesis and structural characterization of several 1,1,3,3-tetramethylguanidine (H-TMG) solvated magnesium aryloxide complexes are reported. Bu(2)Mg was successfully reacted with H-TMG, HOC(6)H(3)(CMe(3))(2)-2,6 (H-DBP), and either ethanol, a carboxylic acid, or diphenyl phosphate in a 1:1 ratio to yield the corresponding Mg(mu-L)(DBP)(H-TMG) where L = OCH(2)CH(3) (OEt, 1), O(2)CC(CH(3))(3) (OBc, 2), O(2)C(C(6)H(2)-2,4,6-(CH(3))(3)) (TMBA, 3), or O(2)P(OC(6)H(5))(2) (DPP, 4). Bu(2)Mg was also reacted with two equivalents of H-TMG and HOC(6)H(3)(CMe(3))-2-(CH(3))-6 (BMP) or HO-2,6-Ph(2)C(6)H(3) to yield [Mg(BMP)(2)(H-TMG)(2)] (5) and [Mg(O-2,6-Ph(2)C(6)H(3))(2)(H-TMG)(2)] (6). Compounds 1-6 were characterized by single-crystal X-ray diffraction. Polymerization of l- and rac-lactide with 1 was found to generate polylactide (PLA). A discussion concerning the relevance of compounds 2 - 4 to the structure of Mg-activated phosphatase enzymes is also provided. The bulk powders for all complexes were found to be in agreement with the crystal structures based on elemental analyses, FT-IR spectroscopy, and (1)H, (13)C and (31)P NMR studies.
报道了几种1,1,3,3-四甲基胍（H-TMG）溶剂化芳氧基镁配合物的合成及结构表征。二丁基镁（Bu₂Mg）成功地与H-TMG、2,6-二叔丁基苯酚（H-DBP）以及乙醇、羧酸或磷酸二苯酯按1:1的比例反应，生成相应的[Mg(μ-L)(DBP)(H-TMG)]₂，其中L = OCH₂CH₃（OEt，1）、O₂CC(CH₃)₃（OBc，2）、O₂C(C₆H₂-2,4,6-(CH₃)₃)（TMBA，3）或O₂P(OC₆H₅)₂（DPP，4）。二丁基镁还与两当量的H-TMG和2-甲基-6-叔丁基苯酚（BMP）或2,6-二苯基苯酚反应，生成[Mg(BMP)₂(H-TMG)₂]（5）和[Mg(O-2,6-Ph₂C₆H₃)₂(H-TMG)₂]（6）。化合物1 - 6通过单晶X射线衍射进行了表征。发现用1引发左旋丙交酯和外消旋丙交酯的聚合可生成聚丙交酯（PLA）。还提供了关于化合物2 - 4与镁激活的磷酸酶结构相关性的讨论。基于元素分析、傅里叶变换红外光谱以及¹H、¹³C和³¹P核磁共振研究，发现所有配合物的块状粉末与晶体结构一致。
