Wang Y, Parkin S, Atwood D
Department of Chemistry, University of Kentucky, Lexington, KY 40506-0055, USA.
Inorg Chem. 2002 Feb 11;41(3):558-65. doi: 10.1021/ic0110326.
When the reagents LAlMe (L = N,N'-(alkylene or arylene)bis(3,5-di-tert-butyl)salicylideneimine (alkylene = ethylene (Salen(tBu))(1), propylene (Salpen(tBu))(2), and butylene (Salben(tBu)) (3); arylene = phenylene (Salophen(tBu) (4), 3,4-dimethylphenylene (Salomphen(tBu) (5)) are combined with Ph(H)P(O)OH in tetrahydrofuran (thf) the unique aluminophosphinate compounds, L(tBu)Al[O(2)P(H)Ph] with L, n = Salen,(infinity)(6), Salpen, 2 (7), Salben, 2 (8), Salophen, (infinity)(9) and Salomphen, (infinity)(10) are produced. The yields for the latter two reactions are low, and it was subsequently found that the unique thf-coupled compounds appear in the thf filtrates of the original reaction mixture. These compounds are, L-thf(tBu)Al[O(2)P(H)Ph], L = Salophen (13) and Salomphen (14). The thf connects through an alpha-carbon to only one of the two possible imine carbons of the ligand. While trying to determine how this coupling proceeds, the six-coordinate, solution-state species LAlMe(thf) (L = Salophen (11) and Salomphen (12) were discovered and implicated as intermediates. All of the compounds are characterized by melting point, NMR, IR, and X-ray analyses for 5-8, 13, and 14. A possible mechanism for the thf coupling event is presented.
当试剂LAlMe（L = N，N'-（亚烷基或亚芳基）双（3,5-二叔丁基）水杨基亚胺（亚烷基 = 亚乙基（Salen（tBu））（1）、亚丙基（Salpen（tBu））（2）和亚丁基（Salben（tBu））（3）；亚芳基 = 亚苯基（Salophen（tBu））（4）、3,4-二甲基亚苯基（Salomphen（tBu））（5））与Ph（H）P（O）OH在四氢呋喃（thf）中混合时，会生成独特的铝膦酸盐化合物[L（tBu）Al[O₂P（H）Ph]]ₙ，其中L、n分别为Salen，∞（6）、Salpen，2（7）、Salben，2（8）、Salophen，∞（9）和Salomphen，∞（10）。后两个反应的产率较低，随后发现独特的thf偶联化合物出现在原始反应混合物的thf滤液中。这些化合物是[L-thf（tBu）Al[O₂P（H）Ph]]₂，L = Salophen（13）和Salomphen（14）。thf通过一个α-碳仅连接到配体两个可能的亚胺碳中的一个。在试图确定这种偶联如何进行时，发现了六配位的溶液态物种LAlMe（thf）（L = Salophen（11）和Salomphen（12））并认为它们是中间体。所有化合物均通过熔点、核磁共振、红外光谱和X射线分析对5 - 8、13和14进行了表征。提出了thf偶联事件的一种可能机制。
