Wittwer Benjamin, Hett Florian, Seidl Michael, Hohloch Stephan
Faculty of Chemistry and Pharmacy, Institute of General, Inorganic and Theoretical Chemistry, Leopold-Franzens-University Innsbruck, Innrain 80-82, 6020 Innsbruck, Austria.
Inorg Chem. 2024 Oct 28;63(43):20448-20461. doi: 10.1021/acs.inorgchem.4c02897. Epub 2024 Oct 15.
We report a new synthetic entry to a series of -substituted anilidophosphine ligands (short HPN, R = pTol (), 3,5-dimethylphenyl (), 3,5-bis(trifluoromethyl)phenyl (), 2-methoxyphenyl (), diisopropylphenyl (), and adamantyl ()), allowing a detailed tuning of their steric (and electronic) properties. could be converted into their lithium salts , which are effective precursors for salt metathesis reactions. The new ligands are used for the synthesis of an array of lanthanide complexes using LaCl(THF) as a precursor. Depending on the steric bulk of the anilidophosphine ligand, either chloride-bridged dimers of the general formula [(PN)La(μ-Cl)La(PN)] (R = pTol (), 3,5-dimethylphenyl () and adamantyl ()) or mononuclear complexes of the general formula (PN)LaCl (R = diisopropylphenyl ()) are observed, if the complexation reaction is carried out in toluene. Contrary, if salt metathesis reactions are carried out in dimethoxyethane (DME) as a coordinating solvent, complexes of the general formula [(PN)La(μ-Cl)Li(DME)] (R = Adamantyl () and R = 2-methoxyphenyl ()) or [Li(DME)][(PN)LaCl] (R = 3,5-bis(trifluoromethyl)phenyl (), R = pTol () and R = 3,5-dimethylphenyl ()) are observed. All ligands and complexes have been thoroughly characterized by 1D and 2D NMR spectroscopy, IR, and X-ray crystallography. Finally, the steric demand of the new anilidophosphine ligands is evaluated using SambVca simulations.
我们报道了一种合成一系列β-取代苯胺基膦配体（简称为HPN，R = 对甲苯基（）、3,5-二甲基苯基（）、3,5-双（三氟甲基）苯基（）、2-甲氧基苯基（）、二异丙基苯基（）和金刚烷基（））的新方法，这使得能够对其空间（和电子）性质进行精细调节。 可以转化为它们的锂盐 ，锂盐是盐复分解反应的有效前体。使用LaCl(THF)作为前体，新配体用于合成一系列镧系配合物。根据苯胺基膦配体的空间体积大小，如果络合反应在甲苯中进行，则观察到通式为[(PN)La(μ-Cl)La(PN)]（R = 对甲苯基（）、3,5-二甲基苯基（）和金刚烷基（））的氯桥联二聚体或通式为(PN)LaCl（R = 二异丙基苯基（））的单核配合物。相反，如果盐复分解反应在作为配位溶剂的二甲氧基乙烷（DME）中进行，则观察到通式为[(PN)La(μ-Cl)Li(DME)]（R = 金刚烷基（）和R = 2-甲氧基苯基（））或[Li(DME)][(PN)LaCl]（R = 3,5-双（三氟甲基）苯基（）、R = 对甲苯基（）和R = 3,5-二甲基苯基（））的配合物。所有配体和配合物均已通过一维和二维核磁共振光谱、红外光谱和X射线晶体学进行了全面表征。最后，使用SambVca模拟评估了新苯胺基膦配体的空间需求。
