新型二亞胺銅化合物的合成研究

近幾十年來二亞胺 (β-diketimine) 配位基的研究愈來愈熱門，主要是因為二亞胺配位基易形成較擁擠的配位環境，可用來穩定金屬中心稀有的氧化態和不飽合的配位環境。在二亞胺配位基的研究中，大部分著重在含氮芳香環取代基為主。相較於含氮芳香環取代基，含氮脂肪族取代基所形成的二亞胺配位基較不穩定，故較少為化學家所探討。在本論文中成功利用具有不對稱三芽基的二亞胺配位基 (分別含有芳香環取代基及脂肪族取代基)，依據配位基手臂的不同可分為含吡啶 (PyMiPrDkH、PyEiPrDkH) 或三級胺 (NEiPrDkH、NPiPrDkH)，和丁基鋰反應分別合成出一系列的鋰化合物 (LiPyMiPrDk(2)、LiPyEiPrDk (3)、LiNEiPrDkH(4)、LiNPiPrDk(5))。並將鋰化合物和CuCl2•0.8THF反應可得到銅(II) 化合物(CuClNEiPrDkH(6)、CuClNPiPrDk (7))。銅(II) 化合物(CuClNEiPrDkH(6)亦可加入四氟硼銀和亞硝酸鈉得到銅(II) 化合物 (CuNO2NEiPrDkH(8))。若將二亞胺配位基和叔丁氧基銅反應，可得到銅(I) 化合物 (CuPyMiPrDk (9)、CuPyMiPrDk(10))，並探討二者不同的反應性比較。此外，所有化合物皆由光譜鑑定其結構。而配位基 PyMiPrDkH 以及化合物(2)、(3)、(4)、(6)、(7)、(8)、(9)和(10)皆成功得到其X-ray單晶繞射結構。

關鍵字

二亞胺；銅

並列摘要

The N,N`-substituted β-diketiminato ligands have been gaining increasing interest over the past several decades, mainly due to their suitability as sterically crowded spectator ligands to stabilize coordinatively unsaturated metal centers and unusual oxidation state. Most of N,N`-substituted β-diketiminato ligands are N-Ar-substituted due to the basicity of aryl amine. The alkyl amine give less stable imine compound. There are many study focus on the synthesis of new type N,N`-substituted β-diketiminato ligands to study their coordination chemistry in the biomimetic system as well as catalysts. Only few case report the synthesis of N-Alkyl-substituted β-diketiminate ligands. A new type asymmetry tridentate N, N`-substituted β-diketiminate ligand sets (one aryl and one alkyl substituted) with different kinds of arms, which contain pyridine (PyMiPrDkH, PyEiPrDkH) or tertiary amine (NEiPrDkH, NPiPrDkH), react with n-BuLi to give a series of lithium complexes (LiPyMiPrDk (2), LiPyEiPrDk (3), LiNEiPrDk (4), LiNPiPrDk (5)). Copper(II) complexes (CuClNEiPrDk (6), CuClNPiPrDk (7)) were obtained by reaction of the lithium complexes with CuCl2．0.8THF. Complexe (6) react with AgBF4 and NaNO2 to give Copper(II) complexe (CuNO2NEiPrDk (8)). Copper(I) complexes (CuPyMiPrDk (9), CuPyEiPrDk(10)) were obtained by reaction of β-diketiminate ligands (PyMiPrDkH, PyEiPrDkH) and CuOtBu, and we also discuss the reactivity of these two complexes. All of the complexes were characterized by spectroscopic, PyMiPrDkH ligand and complexes (2)、(3)、(4)、(6)、(7)、(8)、(9) and (10) were all characterized by X-ray crystallographic.

並列關鍵字

β-diketimine ； Copper

參考文獻

(1) (a) Mindiola, D. J.; Holland, P. L.; Warren, T. H. In Inorganic Synthesis; JOHN WILEY &SONS,INC., 2010; Vol. 35, p 1.(b) Bourget-Merle, L.; Lappert, M. F.; Severn, J. R. Chem. Rev. 2002, 102, 3031.