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

吳宏泰(Hung-Tai Wu)

指導教授 ： 蔡易州

國立清華大學/理學院/化學系/碩士(2014年)

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.

參考文獻

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