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  • 學位論文

含二胺基吡啶及2-胺基-6-膦基吡啶的金屬錯合物合成

Synthesis of Metal Complexes Containing Diamidopyridyl and 2-amido-6-phosphinopyridyl Ligands

指導教授 : 蔡易州
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摘要


中文摘要 本實驗室過去嘗詴以雙氮基脒為配基合成雙鎢金屬多重鍵的錯 合物,但是在還原的過程中皆會發生分子內碳氫鍵的活化,造成無法 得到雙鎢五重鍵之錯合物。因而本篇論文第一部分嘗詴以二胺基吡啶 配基H2N2NR = [2,6-bis(R2phenylamido)-4-methylpyridine] (R = Dipp or Dep) ( Dipp = diisopropyl or Dep = diethyl) 與 WCl4(DME) (DME = dimethoxyethane)反應,期望得到具有雙鎢五重鍵的產物。其合成步 驟的部分與過去常見的方式不同,是以未去質子化的配位基與 WCl4(DME) 反應後再加入鹼進行去質子化,兩種形式的二胺基吡啶 配基分別可得到錯合物 W2Cl4[μ-κ2-4-Me-2-(HN-2,6-iPr2C6H3)-6-(N-2,6-iPr2C6H3)C5H2N]2 (1)與 錯合物 W2Cl4[μ-κ2-4-Me-2-(HN-2,6-Et2C6H3)-6-(N-2,6-Et2C6H3)C5H2N]2 (2),兩 者皆為雙鎢三重鍵的產物且配基上皆有一邊的胺基沒有進行去質子 化,隨後將兩錯合物進行還原,錯合物1 還原之產物並不穩定會隨時 間不斷的分解,而錯合物2 之產物無法與自由配基分離,因此皆尚未 得到X-ray 單晶繞射的結果。 第二部分嘗詴將二胺基吡啶修飾為2-胺基-6-膦基吡啶,藉由此 不對稱之配基期望合成具有異核金屬鍵的錯合物。此配位基與二氯化 II 鈷 和二氯化錳皆得到四方錐的結構, 分別為錯合物 (Et2O)Co[κ2-2-(N-2,6-iPr2C6H3)-6-P(C6H5)2C5H3N]2 (5) 與錯合物 (THF)Mn[κ2-2-(N-2,6-iPr2C6H3)-6-P(C6H5)2C5H3N]2 (6),此二結構中膦 基皆未與金屬配位。而與碘化亞銅反應的情況則有所不同,得到錯合 物(CuI)Cu2[μ3-κ1:κ2-2-(N-2,6-iPr2C6H3)-6-P(C6H5)2C5H3N]2 (7),類似過 去本實驗室以二胺基吡啶為配基的三銅錯合物,惟三個銅原子並不在 同一直線上,其還原反應中並沒有得到還原產物,產物為合成錯合物 7 時之中間產物, 為錯合物 Cu2[μ-κ2-2-(N-2,6-iPr2C6H3)-6-P(C6H5)2C5H3N]2 (8),以錯合物7 與 Pd(PEt3)3、Ni(PEt3)4、Fe2(CO)9 三個含有零價金屬的詴劑進行反應, 可得到錯合物 (PEt3)PdCu2[μ3-κ1:κ2-2-(N-2,6-iPr2C6H3)-6-P(C6H5)2C5H3N]2 (9) 錯合物 (PEt3)NiCu2[μ3-κ1:κ2-2-(N-2,6-iPr2C6H3)-6-P(C6H5)2C5H3N]2 (10) 錯合 物(CO)3FeCu2[μ3-κ1:κ2-2-(N-2,6-iPr2C6H3)-6-P(C6H5)2C5H3N]2 (13)三個 晚期異核金屬的錯合物,僅有錯合物13 的三個金屬在同一直線,而 鐵原子上的三個羰基夾角並不相等,以最靠近銅的夾角明顯較大。嘗 詴以錯合物7 與二苯基胺反應形成錯合物 (CuNPh2)Cu2[μ3-κ1:κ2-2-(N-2,6-iPr2C6H3)-6-P(C6H5)2C5H3N]2 (14),再以 錯合物14 與溴化苯在紫外光的照射下進行碳氮耦合反應。

關鍵字

銅金屬錯合物

並列摘要


Abstract Treatment of the diamindopyridyl ligand, 4-Me-2,6-(HN-2,6-iPr2C6H3)2C5H3N, with WCl4(DME) (DME = dimethoxyethane) in the presence of 2 equiv of DBU (DBU=1,8-Diazabicyclo[5.4.0]undec-7-ene) gave the ditungsten complex, W2Cl4(μ-κ2-4-Me-2-(HN-2,6-iPr2C6H3)2-6-(N-2,6-iPr2C6H3)C5H2N)2 (1). NMR spectroscopy and X-ray studies showed that 1 have two amino arms and chloro groups point towards the protons of those two amino groups. We then reduced the bulk of the diamindopyridyl ligand by substituting Dep (2,6-Et2C6H3) for Dipp (2,6-iPr2C6H3), and the product W2Cl4(μ-κ2-4-Me-2-(HN-2,6-Et2C6H3)-6-(N-2,6-Et2C6H3)C5H2N)2 (2) structurally similar to 1 was isolated upon reacting with WCl4(DME). Subsequently, attempts to reduce 1 and 2 by KC8 were carried out. However, the reduced product of 1 decomposes rapidly in solutions, while the free ligand was the major product upon reduction of 2. In the second part of this thesis, we employed amidophosphinopyridiyl ligand 2-(HN-2,6-iPr2C6H3)-6-P(C6H5)2pyridine to stabilize metals. Treatment of CoCl2 or MnCl2 with (Et2O)Li[κ1-2-(N-2,6-iPr2C6H3)-6-P(C6H5)2C5H3N] yielded the mononuclear compounds (OEt2)Co[κ2-2-(N-2,6-iPr2C6H3)-6-P(C6H5)2C5H3N]2 (5) and (THF)Mn[κ2-2-(N-2,6-iPr2C6H3)-6-P(C6H5)2C5H3N]2 (6), respectively. Both metal centers adopt a square pyramidal configuration. The reaction between (Et2O)Li[κ1-2-(N-2,6-iPr2C6H3)-6-P(C6H5)2C5H3N] and CuI yielded the trinuclear complex IV (CuI)Cu2[μ3-κ1:κ2-2-(N-2,6-iPr2C6H3)-6-P(C6H5)2C5H3N]2 (7), where CuI is ligated by two phosphine groups. The structure of 7 is similar to the previously prepared tricopper complex Li{Cu3[μ-κ3-4-methyl-2,6-bis(N-2,6-iPr2C6H3)2pyridine]2}, in which three copper atoms are arranged in a linear conformation. Reduction of 7 gave the dicopper compound Cu2(μ-κ2-2-(N-2,6-iPr2C6H3)-6-P(C6H5)2C5H3N)2 (8) (vide infra), where each Cu is linear and ligated by two N atoms. Alternatively, compound 8 was isolated from the reaction of (Et2O)Li[κ1-2-(N-2,6-iPr2C6H3)-6-P(C6H5)2C5H3N] and CuI. Interestingly, treatment of 7 with Pd(PEt3)3, Ni(PEt3)4 and Fe2(CO)9 led to the formation of three heterotrinuclear complexes (PEt3)PdCu2[μ3-κ1:κ2-2-(N-2,6-iPr2C6H3)-6-P(C6H5)2C5H3N]2 (9), (PEt3)NiCu2[μ3-κ1:κ2-2-(N-2,6-iPr2C6H3)-6-P(C6H5)2C5H3N]2 (10) and (CO)3FeCu2[μ3-κ1:κ2-2-(N-2,6-iPr2C6H3)-6-P(C6H5)2C5H3N]2 (13), respectively. The conformation of these three heterotrinuclear complexes is roughly the same, in which Pd, Ni and Fe atoms replace the phosphine-bound CuI fragment. Notably, three metals in 13 are arranged in a linear mode. Although the iron center in 13 adopts a trigonal bipyrimidal conformation and three CO ligands are in equatorial positions, the angles between the three carbonyl groups are not equivalent; the angle close to the copper centers is larger than the other two. Reactions of 7 with 1 equivalent of LiNPh2 generateed the complex, (CuNPh2)Cu2[μ3-κ1:κ2-2-(N-2,6-iPr2C6H3)-6-P(C6H5)2C5H3N]2 (14), which reacted with bromobenzene via C-N coupling to give NPh3 upon ultraviolet radiation.

並列關鍵字

無資料

參考文獻


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