以聯萘酚衍生物作為配位基合成單核鎂金屬錯合物

Please use this identifier to cite or link to this item: http://ir.lib.ncu.edu.tw/handle/987654321/91821

Title:	以聯萘酚衍生物作為配位基合成單核鎂金屬錯合物
Authors:	李育蓁;Li, Yu-Chen
Contributors:	化學學系
Keywords:	聯萘酚衍生物;配位基;單核鎂金屬錯合物;開環聚合;BINOL derivative;ligand;monomeric magnesium metal complex;ring-opening polymerization
Date:	2023-08-15
Issue Date:	2023-10-04 14:43:21 (UTC+8)
Publisher:	國立中央大學
Abstract:	在以往的文獻發表中，以烷氧化物或酚鹽為配位基的鎂金屬錯合物，於開環聚合反應中展現高催化效率及良好分子量分布度。以2016年由I. E. Nifant’ev實驗室發表的文獻為例，將Butylated hydroxytoluene (BHT) 作為配位基，合成的單核鎂金屬錯合物，作為催化劑催化ε-己內酯聚合時表現出極高的催化效率 (1 min, conv. = 72%, Đ = 1.30)。　　到目前為止，以酚為配位基的單核鎂金屬錯合物，多於酚基鄰位設計龐大取代基，此高立體障礙可促使單核鎂金屬錯合物穩定化。反之，若無鄰位高立體障礙取代基，則鎂金屬錯合物傾向形成多核結構。綜上所述，我們將目光聚焦於1,1‘-Bi-2-naphthol (BINOL)，一種具有龐大剛性骨架的結構，希望可合成出弱化其一配位點的BINOL衍生配位基 (L-1-H) 作為鎂錯合物配位基。　　BINOL衍生物L-1-H可以三步反應合成製備，並與自製雙核鎂金屬錯合物[PhMg(O-tBu)(THF)]2反應，形成單核鎂金屬錯合物Mg(L-1)2(THF)3，並使用NMR及X-ray單晶繞射儀進行結構鑑定，經由晶體解析確認成功合成Mg(L-1)2(THF)3。 ;In previous literature publications, magnesium metal complexes with alkoxide or phenolate ligands have demonstrated high catalytic efficiency and good molecular weight distribution in ring-opening polymerization reactions. Taking a publication by I. E. Nifant′ev′s laboratory in 2016 as an example, a monomeric magnesium metal complex was synthesized using Butylated hydroxytoluene (BHT) as a coordinating ligand, and it exhibited extremely high catalytic efficiency (1 min, conv. = 72%, Đ = 1.30) in the polymerization of ε-caprolactone. 　　Until now, monomeric magnesium metal complexes with phenolate ligands have often been designed with bulky substituents in the ortho positions, which provide a high steric hindrance and stabilize the complexes. Conversely, in the absence of neighboring bulky substituents, magnesium metal complexes tend to form multinuclear structures. Based on the aforementioned observations, our focus is directed towards 1,1′-Bi-2-naphthol (BINOL), a compound with a large rigid framework, aiming to synthesize BINOL derivatives (L-1-H) as ligands for magnesium complexes. 　　The BINOL derivative L-1-H can be synthesized in three steps and reacted with a self-prepared dimeric magnesium metal complex [PhMg(O-tBu)(THF)]2 to form a monomeric magnesium metal complex Mg(L-1)2(THF)3. The structure of Mg(L-1)2(THF)3 was determined through NMR and X-ray single-crystal diffraction analysis, confirming the successful synthesis of Mg(L-1)2(THF)3.
Appears in Collections:	[Graduate Institute of Chemistry] Electronic Thesis & Dissertation

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