Clegg William, Davidson Matthew G, Graham David V, Griffen Gemma, Jones Matthew D, Kennedy Alan R, O'Hara Charles T, Russo Luca, Thomson Calum M
School of Natural Sciences (Chemistry), Newcastle University, Newcastle-upon-Tyne, UK.
Dalton Trans. 2008 Mar 14(10):1295-301. doi: 10.1039/b718186h. Epub 2008 Jan 22.
Two lithium and one sodium diamine bis(phenolate) complexes have been prepared and characterised by X-ray crystallography and NMR spectroscopy. Two parent diamine bis(phenol) ligands were utilised in the study (1-H2 and 2-H2). Dimeric (1-Li2)(2) was prepared by treating 1-H2 with two molar equivalents of n-butyllithium in hydrocarbon solvent. It adopts a ladder-like structure in the solid state, which appears to deaggregate in C6D6 solution. The monomeric (hence, dinuclear) TMEDA-solvated species [2-Li(2).(TMEDA)] has two chemically unique Li atoms in the solid state and is prepared by reacting 2-H2 with two molar equivalents of n-butyllithium in hydrocarbon solvent, in the presence of N,N,N',N'-tetramethylethylenediamine (TMEDA). Finally, the dimeric sodium-based 2-Na(2) x (OEt2 was prepared by reacting 1-H2 with two molar equivalents of freshly prepared n-butylsodium in a hydrocarbon-diethyl ether medium. The complex adopts a Na4O4) cuboidal structure in the solid state, which appears to remain intact in C6D6 solution.
已制备出两种锂和一种钠的二胺双(酚盐)配合物,并通过X射线晶体学和核磁共振光谱对其进行了表征。研究中使用了两种母体二胺双(酚)配体(1-H₂和2-H₂)。通过在烃类溶剂中用两摩尔当量的正丁基锂处理1-H₂制备了二聚体(1-Li₂)(2)。它在固态中呈梯状结构,在C₆D₆溶液中似乎会解聚。单体(因此是双核)的TMEDA溶剂化物种[2-Li₂·(TMEDA)]在固态中有两个化学性质不同的锂原子,它是通过在烃类溶剂中,在N,N,N',N'-四甲基乙二胺(TMEDA)存在下,使2-H₂与两摩尔当量的正丁基锂反应制备的。最后,通过在烃-二乙醚介质中使1-H₂与两摩尔当量新制备的正丁基钠反应制备了二聚体钠基配合物2-Na₂·(OEt₂)。该配合物在固态中呈Na₄O₄立方结构,在C₆D₆溶液中似乎保持完整。