硒三鐵羰基化合物與無機及有機試劑的合成與其反應性探討

Abstract

1.Se─Fe─CuX系統 將[Et4N]2[SeFe3(CO)9]與CuX在不同條件比例下反應可成功合成出一系列新穎化合物 [Et4N]2[SeFe3(CO)9CuX] (X＝Cl [Et4N]2[1a]；Br [Et4N]2[1b] ；I [Et4N]2[1c])、[Et4N]2[SeFe3(CO)9Cu2X2] (X＝Cl [Et4N]2[2a]；Br[Et4N]2[2b])、[Et4N]2[{SeFe3(CO)9}2Cu4X2] (X＝Cl [Et4N]2[3a]；Br [Et4N]2[3b])和[Et4N]4[{SeFe3(CO)9Cu2Cl2}2] ([Et4N]4[4a])，並藉由DFT理論計算輔助，解釋IR吸收光譜、化合物相對穩定度與電化學上的氧化還原。

2.Se─Fe─Cu/dipyridine系統 將[Et4N]2[SeFe3(CO)9]加入[Cu(CH3CN)4][BF4]和不同dipyridine來源可成功自組裝得到一系列含羰基的新穎金屬團簇聚合物[SeFe3Cu2(tmdpy)2] (3)、[SeFe3(CO)9Cu2(dpy)3] (5)、[{(bpe)2(MeCN)2Cu}{SeFe3(CO)9Cu(bpe)}(MeCN)] (6)和[SeFe3Cu2(H2bpe)2.5] (7) (4,4′-trimethylene-dipyridine = tmdpy；4,4′-dipyridine = dpy；1,2-di(4–pyridine)ethylene = bpe；1,2-bis(4-pyridine)ethane = H2bpe)。

3.Se─Fe─CuOAc系統 將[Et4N]3[{SeFe3(CO)9Cu}2(─OAc)]與兩當量[Cu(CH3CN)4]BF4在冰浴反應5分鐘，可得到長鏈狀化合物[Et4N]3[{SeFe3(CO)9Cu2OAc}2(─OAc)] ([Et4N]3[2])，若[Et4N]3[{SeFe3(CO)9Cu}2(─OAc)]與[Cu(CH3CN)4]BF4和4,4´-dipyridine (dpy)同時反應則可得到4,4´-dipyridine取代掉OAc─ ligand當作橋接工具之化合物[Et4N]2[{SeFe3(CO)9Cu2OAc}2(─dpy)] ([Et4N]2[3])。

1.Se-Fe-CuX system When the selenium-capped triiron carbonyl cluster [Et4N]2[SeFe3(CO)9] was treated with 1~3 equiv of CuX, CuX-bridged SeFe3 complexes [Et4N]2[SeFe3(CO)9CuX] (X = Cl, [Et4N]2[1a]; Br, [Et4N]2[1b]; I, [Et4N]2[1c]), Cu2X2-bridged SeFe3 clusters [Et4N]2[SeFe3(CO)9Cu2X2] (X = Cl, [Et4N]2[2a]; Br, [Et4N]2[2b]), Cu4X2-bridged di-SeFe3 clusters [Et4N]2[{SeFe3(CO)9}2Cu4X2] (X = Cl, [Et4N]2[3a]; Br, [PPh4]2[3b]), and Cu4Cl4-bridged di-SeFe3 clusters [Et4N]4[{SeFe3(CO)9Cu2Cl2}2] ([Et4N]4[4a]) were obtained, respectively, in good yields. The nature, formation, stepwise cluster expansion, and electrochemical properties of these CuX-, Cu2X2-, Cu4X2-, and Cu4Cl4-bridged mono- or di-SeFe3-based clusters are elucidated in detail by molecular calculations at the B3LYP level of the density functional theory in terms of the effects of selenium, iron, copper halides, and the size of the metal skeleton.

2.Se-Fe-CuX/dipyridine When the selenium-capped triiron carbonyl cluster [Et4N]2[SeFe3(CO)9] was treated [Cu(CH3CN)4][BF4] and different dipyridine, self-assembly cluster polymers [SeFe3Cu2(tmdpy)2] (3), [SeFe3(CO)9Cu2(dpy)3] (5), [{(bpe)2(MeCN)2Cu}{SeFe3(CO)9Cu(bpe)}(MeCN)] (6), and [SeFe3Cu2(H2bpe)2.5] (7) (4,4′-trimethylene-dipyridine = tmdpy; 4,4′-dipyridine = dpy; 1,2-di(4–pyridine)ethylene = bpe; 1,2-bis(4-pyridine)ethane = H2bpe) were obtained, respectively.

3.Se-Fe-CuOAc system When [Et4N]3[{SeFe3(CO)9Cu}2(─OAc)] was treated with 2 equiv [Cu(CH3CN)4][BF4] in THF in an ice/water bath, the OAc-bridged di-SeFe3 Cu2OAc cluster [Et4N]3[{SeFe3(CO)9Cu2OAc}2(─OAc)] ([Et4N]3[2]) was obtained. If [Et4N]3[{SeFe3(CO)9Cu}2(─OAc)] was treated with [Cu(CH3CN)4][BF4] and 4,4´-dipyridine (dpy) in THF in an ice/water bath, [Et4N]3[{SeFe3(CO)9Cu2OAc}2(─OAc)] ([Et4N]3[2]) was found to undego ligand-exchange reaction to give the corresponding dpy-bridged di-SeFe3 Cu2OAc cluster [Et4N]2[{SeFe3(CO)9Cu2OAc}2(─dpy)] ([Et4N]2[3])