Optically active bis(aminophenols) and their metal complexes
Optically active bis(aminophenols) and their metal complexes
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光学活性双(氨基酚)及其金属配合物
DOI：
10.1039/d3dt02436a
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发表时间：
2023
影响因子：
4
通讯作者：
Brown, Seth N.
中科院分区：
文献类型：
--
作者：
Carbonel, Halen;Mikulski, Timothy D.;Nugraha, Kahargyan;Johnston, James;Wang, Yichun;Brown, Seth N.
以(R)-2，2‘-二氨基二苯基(BiniqH4)和(R，R)-2，3-丁二基二苯甲酸酯(BdanH4)为原料，与3，5-二叔丁基邻苯二酚缩合，合成了具有光学活性的C2-对称双(氨基苯酚)化合物。通过氧化金属化合成了第10族双(亚氨基半喹酮)配合物(R)-(Biniq)M(M=Pd，Pt)和(C，R，R)-(Bdan)Pd。在(R)-(Biniq)M中，C2轴穿过双(亚氨基二喹酮)金属核的近似正方形平面，而在(C，R，R)-(Bdan)Pd中，C2轴垂直于该平面。在后一种化合物中，(R，R)-丁二基环选择性地结合在金属络合物的一个对映体表面上，形成甲基相互反对的构象。通过OSO(OCH2CH2O)2与(R，R)-BdanH4的金属化反应，得到了具有固有手性的Oso(氨基苯氧化物)2发色团的Os氧配合物。可观察到(A，R，R)和(C，R，R)非对映异构体，甲苯回流金属化选择性地生成(C，R，R)非对映异构体。结合光学光谱和TDDFT计算，用圆二色谱说明了配合物的电子结构。
Optically active C2-symmetric bis(aminophenols) based on (R)-2,2′-diaminobinaphthyl (BiniqH4) and (R,R)-2,3-butanediyldianthranilate (BdanH4) have been prepared by condensation of the diamines with 3,5-di-tert-butylcatechol. Group 10 bis(iminosemiquinone) complexes (R)-(Biniq)M (M = Pd, Pt) and (C,R,R)-(Bdan)Pd have been prepared by oxidatively metalating the corresponding ligands. In (R)-(Biniq)M, the C2 axis passes through the approximate square plane of the bis(iminosemiquinone)metal core, while in (C,R,R)-(Bdan)Pd the C2 axis is perpendicular to this plane. In the latter compound, the (R,R)-butanediyl strap binds selectively over one enantioface of the metal complex in a conformation where the methyl groups are anti to one another. Osmium oxo complexes with the intrinsically chiral OsO(amidophenoxide)2 chromophore are obtained by metalation of OsO(OCH2CH2O)2 with (R,R)-BdanH4. Both the (A,R,R) and (C,R,R) diastereomers can be observed, with metalation in refluxing toluene selectively giving the latter isomer. The electronic structures of the complexes are illuminated by the circular dichroism spectra, in conjuction with the optical spectra and TDDFT calculations.