Coordination Diversity of Aluminum Centers Molded by Triazole Based Chalcogen Ligands

Equimolar and excess ratio reactions of AlMe3 and AliBu3 with the ligands 4,5-(P(E)Ph2)2tzH (tz = 1,2,3-triazole; E = O (1), S (2), Se(3)) were performed, showing a vast variety of coordination modes. The products obtained, [AlR2{κ2-O,O′-[4,5-(P(O)Ph2)2tz]}] (R = Me (4), iBu (5)), [AlR2{κ3-N,N′,S-[4,5-(P(S)Ph2)2tz]}(μ-tz)]2 (R = Me (6), R = iBu (7)), [AlMe2{κ2-N,Se-[4,5-(P(Se)Ph2)2tz]}] (8), [Al{κ2-N,Se-[4,5-(P(Se)Ph2)2tz]}3] (9), [AlR2{κ2-O,O′-[4,5-(P(O)Ph2)2tz]}-(N′-AlR3)] (R = Me (10), iBu (11)), and [AlR2{κ2-N,S-[4,5-(P(S)Ph2)2tz]}-(N′-AlR3)] (R = Me (12), R = iBu (13)), were characterized by spectroscopic methods, and the structures of 1, 4, 6, 7, 9, 10, and 12 were obtained through X-ray diffraction studies. Theoretical calculations were performed on the deprotonated ligands and on selected compounds to obtain information regarding the coordination variety observed for these compounds.

以等摩尔及过量摩尔比，将三甲基铝（AlMe3）与三异丁基铝（AliBu3）分别与配体4,5-二(二苯基膦基取代)-1,2,3-三氮唑（4,5-(P(E)Ph2)2tzH，其中tz代表1,2,3-三氮唑，E分别为氧(O,1)、硫(S,2)、硒(Se,3)）进行反应，结果表明该体系存在极为丰富的配位模式。所合成的产物包括：[AlR2{κ2-O,O′-[4,5-(P(O)Ph2)2tz]}]（R=Me(4)、iBu(5)）、二聚体[AlR2{κ3-N,N′,S-[4,5-(P(S)Ph2)2tz]}(μ-tz)]2（R=Me(6)、iBu(7)）、[AlMe2{κ2-N,Se-[4,5-(P(Se)Ph2)2tz]}] (8)、[Al{κ2-N,Se-[4,5-(P(Se)Ph2)2tz]}3] (9)、[AlR2{κ2-O,O′-[4,5-(P(O)Ph2)2tz]}-(N′-AlR3)]（R=Me(10)、iBu(11)）以及[AlR2{κ2-N,S-[4,5-(P(S)Ph2)2tz]}-(N′-AlR3)]（R=Me(12)、iBu(13)）。上述产物均通过光谱学方法完成表征，其中化合物1、4、6、7、9、10及12的晶体结构经X射线衍射（X-ray diffraction）分析得以确定。本研究对去质子化配体及部分目标化合物开展了理论计算，以获取该类化合物配位多样性的相关信息。