A Ligand Protonation Series in Aluminum(III) Complexes of Tridentate Bis(enol)amine Ligand
A Ligand Protonation Series in Aluminum(III) Complexes of Tridentate Bis(enol)amine Ligand
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DOI：
10.1021/acs.organomet.8b00628
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发表时间：
2018-10
期刊：
影响因子：
2.8
通讯作者：
Nathan A. Phan;J. Fettinger;Louise A. Berben
中科院分区：
文献类型：
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作者：
Nathan A. Phan;J. Fettinger;Louise A. Berben
合成了一系列三齿双烯醇胺配体（ONO，1，1 ′-氮烷二基双（3，3-二甲基-2-丁酮））负载的两种质子化状态的铝（III）配合物，并对其结构进行了表征. AlCl_3与单去质子化的H_2ONO-反应得到假八面体[（H_2ONO-）_2Al][AlCl_4]（1）。AlCl_3还与双去质子HONO_2-反应，得到五配位的假三角双锥配合物（HONO_2-）AlCl（THF）（2）。配合物2与HCl的反应产生配合物1，这表明配体骨架的可逆质子化。使用各种刘易斯碱不能合成ONO 3-的Al（III）络合物。尝试用tBuOK去质子化配合物2得到[（HONO 2-）Al]（μ-tBuO）（3），配体质子化状态没有变化。
A series of aluminum(III) complexes supported by the tridentate bis(enol)amine ligand (ONO, 1,1′-azanediylbis(3,3-dimethylbutan-2-one)) in two protonation states have been synthesized and characterized structurally. Reaction of AlCl3 with singly deprotonated H2ONO– afforded pseudo-octahedral [(H2ONO–)2Al][AlCl4] (1). AlCl3 was also reacted with doubly deprotonated HONO2– to afford the five-coordinate, pseudotrigonal bipyramidal complex (HONO2–)AlCl(THF) (2). The reaction of complex 2 with HCl yielded complex 1, which demonstrates reversible protonation of the ligand backbone. Synthesis of an Al(III) complex of ONO3– was not achieved using a variety of Lewis bases. An attempt to deprotonate complex 2 with tBuOK yielded [(HONO2–)Al](μ-tBuO) (3), with no change to the ligand protonation state.