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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Hydrogen-bond-supported dimeric boron complexes of potentially tetradentate β-diketiminate ligands
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Hydrogen-bond-supported dimeric boron complexes of potentially tetradentate β-diketiminate ligands

机译：氢键支撑的潜在四齿β-二酮配体的二聚硼配合物

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摘要

Two dimeric boron complexes of potentially tetradentate and trianionic β-diketiminate ligands bearing phenol substituents were prepared and characterized. The synthetic routes employed were designed to circumvent the undesirable formation of β-ketimines and 2-methylbenzoxazoles observed when traditional synthetic routes toward the target β-diketiminate ligands were attempted. The title complexes were isolated via demethylation of β-diketimine ligands and boron difluoride complexes bearing 2-anisole N-aryl substituents using boron tribromide. The resulting complexes were found to contain a unique hydrogen-bond-supported boron-oxygen-boron bridge, as confirmed by X-ray crystallography. The stability of the resulting dimeric structures relative to the corresponding monomeric, tetradentate boron complexes was studied computationally, and theory confirmed that the dimeric structures were strongly favored. The absorption spectra of the dimers were red-shifted relative to the parent β-diketimine ligands. The complexes were irreversibly oxidized and reduced electrochemically and were weakly emissive at low concentrations (Stokes shifts between 23 and 31 nm), showing little solvent dependence.
机译：制备并表征了带有酚取代基的潜在四齿和三阴离子β-二酮基配体的二聚硼配合物。设计的合成路线旨在避免尝试向目标β-二酮化配体的传统合成路线时所观察到的β-酮亚胺和2-甲基苯并恶唑的不良形成。通过使用二溴化硼通过β-二酮亚胺配体和带有2-茴香醚N-芳基取代基的二氟化硼复合物的去甲基化分离标题复合物。如X射线晶体学所证实的，发现所得的络合物含有独特的氢键支撑的硼-氧-硼桥。通过计算研究了所得二聚体结构相对于相应的单体四齿硼配合物的稳定性，理论证实了二聚体结构受到强烈青睐。相对于母体β-二酮亚胺配体，二聚体的吸收光谱发生红移。络合物被不可逆地氧化和电化学还原，并且在低浓度（斯托克斯位移在23和31 nm之间）弱发射，几乎没有溶剂依赖性。

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