鎵、鋁、銅卡本錯合物的合成、探討及銅卡本錯合物應用於碳-氫烯丙基化反應
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2018
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Abstract
在有機金屬中,同碳雙碳烯 (carbodicarbene) 屬於較新穎的配位基 (ligand),結構、性質、應用上仍有許多探討及可發展的空間。本論文以片段組合方式,進行簡單的SN2反應合成出一系列不對稱的卡本 (carbones),再分別與氯化鎵進行反應,藉由所得出的晶體結構,氯化鎵角度總和的變化與已知的TEP數值比較,排序出不同卡本的σ電子給予能力,也成功利用卡本與氯化鋁反應得到相同的趨勢。同時,利用同碳膦烷碳烯 (carbophosphinocarbene, CPC) 作為路易士酸的偵測器,根據錯合物磷譜化學位移的改變,可以比較不同鋁試劑的路易士酸強度。
我們將卡本與氯化亞銅反應,合成卡本之銅錯合物並應用於碳-氫烯丙基化反應 (C-H allylation),利用烯丙基鹵化物與氟苯進行反應,可得到預期之偶合產物。我們成功得到催化劑與叔丁醇鈉配位基置換 [(CDC)CuOtBu] 2e及反應中間體 [(CDC)CuC6F5] 2f之晶體結構,藉此推導合理反應機制。
Carbodicarbenes is a novel ligand with a strong σ donor, and there are many studies related to its structures, properties and applications in the field of organometallic chemistry. In this work of thesis, a series of asymmetric carbones were synthesized by simple SN2 reaction in a modular design, which is subsequently reacted with gallium and aluminum complexes to obtain the crystal structures.. The sigma donation ability of different gallium and aluminum carbone complexes were also correlated with the parameter of the molecular structures and other spectroscopy data. In second part of thesis, copper(I) complexes were synthesized by using carbones and copper (I) chloride, and were applied to C-H allylation. Reaction of the allylic halides with fluorobenzenes gave the desired coupling products. We succeeded in obtaining the crystal structure of the catalyst and sodium tert-butoxide ligand exchange [(CDC)CuOtBu] 2e and the reaction intermediate [(CDC)CuC6F5] 2f, thereby deriving a reasonable reaction mechanism.
Carbodicarbenes is a novel ligand with a strong σ donor, and there are many studies related to its structures, properties and applications in the field of organometallic chemistry. In this work of thesis, a series of asymmetric carbones were synthesized by simple SN2 reaction in a modular design, which is subsequently reacted with gallium and aluminum complexes to obtain the crystal structures.. The sigma donation ability of different gallium and aluminum carbone complexes were also correlated with the parameter of the molecular structures and other spectroscopy data. In second part of thesis, copper(I) complexes were synthesized by using carbones and copper (I) chloride, and were applied to C-H allylation. Reaction of the allylic halides with fluorobenzenes gave the desired coupling products. We succeeded in obtaining the crystal structure of the catalyst and sodium tert-butoxide ligand exchange [(CDC)CuOtBu] 2e and the reaction intermediate [(CDC)CuC6F5] 2f, thereby deriving a reasonable reaction mechanism.
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同碳雙碳烯, carbodicarbene