十六族 (硫、硒、碲) 鐵銅羰基與含磷、氮有機試劑及含氮異環碳烯 (NHC) 之團簇化合物的 合成、化性、物性與催化反應探討

Diphosphine-, Dipyridyl-, and N-Heterocyclic Carbene-Bridged EFe3Cu2 (E = S, Se, Te) Complexes: Synthesis, Reactivity, Optical properties, and Catalysis

王致欽(Wang Chih-Chin)

指導教授 ： 謝明惠

國立臺灣師範大學/理學院/化學系/碩士(2016年)

https://doi.org/10.6345/NTNU202204335

摘要

['E‒Fe3‒Cu2‒dppxn‒solvent (E = S, Se, Te; dppx = dppm, dppe; n = 1, 2; solvent = THF, acetone, MeCN) 系統之研究
利用溶劑輔助研磨之方法以 [EFe3(CO)9Cu2(MeCN)2] (E = S, Se, Te) 加入diphenylphosphino methane (dppm) 反應，得 [EFe3(CO)9Cu2(dppm)MeCN] (E = S, 1a-MeCN; Se, 1b-MeCN; Te, 1c-MeCN)，再由脫去 MeCN 配位得 [EFe3(CO)9Cu2(dppm)] (E = Se, 1b; Te, 1c)。進一步將 1a-MeCN‒1c-MeCN 進行溶劑配位轉換成 [EFe3(CO)9Cu2(dppm)THF] 或 [EFe3(CO)9Cu2(dppm)acetone] (E = S, 1a-THF, 1a-acetone; Se, 1b-THF, 1b-acetone)，可成功脫去 THF 得化合物 [SFe3(CO)9Cu2(dppm)] (1a)。再將 1a-MeCN、1b-MeCN、1a‒1c 外加 dppm、4,4’-bipyridine (dpy) 或 1,2-di(4-pyridyl)ethylene (dpee)，可得產物 [EFe3(CO)9Cu2(dppm)2MeCN] (E = S, 2a; Se, 2b)、[EFe3(CO)9Cu2(dppm)2] (E = S, 3a; Se, 3b; Te, 3c)、[{SeFe3(CO)9Cu2(dppm)}2(dpy)] (4) 及 [{SeFe3(CO)9Cu2(dppm)}2(dpee)] (5)，並釐清其間之轉換關係。
此外，利用溶劑輔助研磨之方式以 [EFe3(CO)9Cu2(MeCN)2] (E = S, Se, Te) 並加入 diphenylphosphino ethane (dppe)，可得 [EFe3(CO)9Cu2(dppe)] (E = Se, 6b; Te, 6c) 和 [{(uf06d4-S)Fe3(CO)9}Cu2(dppe)(MeCN)2]n (7)，並可將 7 轉換成 [SFe3(CO)9Cu2(dppe)] (6a)。再將 6a‒6c 與 [Et4N]2[EFe3(CO)9] (E = S, Se, Te) 反應，可得 dppe 橋接的化合物 [Et4N]2[{EFe3(CO)9Cu}2(dppe)] (E = S, 8a; Se, 8b; Te, 8c)；也可以 8b 及 8c 於外加 [Cu(MeCN)4][BF4] 和 dppe 下，進行逆反應得到化合物 6b 與 6c。藉由測量固態反射光譜 (Solid-UV) 探討 E‒Fe3‒Cu2‒dppxn‒solvent (E = S, Se, Te; dppx = dppm, dppe; n = 1, 2; solvent = THF, acetone, MeCN) 系列化合物之能隙大小並搭配固態堆疊進行分析，得知此系列化合物皆具半導體性質，其能隙範圍 (1.35 eV‒1.73 eV)，且固態堆疊之維度越高其能隙越低。

E‒Fe‒Cu‒NHC (E = Se, Te) 系統之研究
將起始物 [EFe3(CO)9Cu2(MeCN)2] (E = Se, 1a; Te, 1b) 與咪唑鹽類 (Imidazole salts) 1,3-dimethylimidazolium iodide (Me2Im•HI)、1,3-dimethyl- benzimidazolium iodide (Me2BenzIm•HI)、1,3-diisopropylbenzimidazolium iodide (iPr2BenzIm•HI) 和 4,5-dichloro-1,3-dimethylimdazolium iodide (4,5-Cl2Me2Im•HI) 和 tBuOK 於 THF 溶劑下反應，可得一系列主族鐵銅氮異環碳烯化合物 [EFe3(CO)9Cu2(Me2Im)2] (E = Se, 2a; Te, 2b), [EFe3(CO)9Cu2(Me2benzIm)2] (E = Se, 3a; Te, 3b), [EFe3(CO)9Cu2- (iPr2BenzIm)2] (E = Se, 4a; Te, 4b) 和 [EFe3(CO)9Cu2(4,5-dichloro-Me2Im)2] (E = Se, 5a; Te, 5b)。化合物 1a(b)‒5a(b) 皆以 EFe3(CO)9 為結構主體中心，而 Cu 以 Cu2L2 或 di-CuL 型式 (E = Se, Te; L = Me2Im, Me2BenzIm, iPr2BenzIm, 和 4,5-Cl2Me2Im) 對主體結構進行配位。
將含 Cu (I) 之化合物 1a(b)‒5a(b) 做為 4-bromophenylboronic acid 同偶合反應催化劑，可得E‒Fe‒Cu‒NHC (E = Se, Te) 系列催化劑的最佳催化條件，並根據產率 (Yield) 及催化效率 (Turnover frequency, TOF) 得知含 Te 系列之催化劑效能比 Se 系列為佳。
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關鍵字

溶劑輔助研磨 ； 團簇化合物 ； 含氮異環碳烯 ； 硫、硒、碲

並列摘要

['E‒Fe3‒Cu2‒dppxn‒solvent (E = S, Se, Te; dppx = dppm, dppe; n = 1, 2; solvent = THF, acetone, MeCN) System
When the [EFe3(CO)9Cu2(MeCN)2] (E = S, Se, Te) were ground with diphenylphosphino methane (dppm) under the liquid-assisted grinding (LAG) conditions, the adducts [EFe3(CO)9Cu2(dppm)MeCN] (E = S, 1a-MeCN; Se, 1b-MeCN; Te, 1c-MeCN) were obtained quantitatively. Further, the elimination of the MeCN ligand of 1b and 1c led to the formation of clusters [EFe3(CO)9Cu2(dppm)] (E = Se, 1b; Te, 1c). The solvent ligand substitution were found when the MeCN-coordinated 1a-MeCN‒1c-MeCN converted to the [EFe3(CO)9Cu2(dppm)THF] or [EFe3(CO)9Cu2(dppm)acetone] (E = S, 1a-THF, 1a-acetone; Se, 1b-THF, 1b-acetone) via LAG with corresponding solvents. The complex [SFe3(CO)9Cu2(dppm)] 1a was successfully obtained when the elimination of the labile THF ligand under appropriate condition. Furthermore, when 1a-MeCN‒1b-MeCN or 1a‒1c reacted with dppm, 4,4’-bipyridine (dpy), or 1,2-di(4-pyridyl)ethylene (dpee), a series of cluster-extended products [EFe3(CO)9Cu2(dppm)2MeCN] (E = S, 2a; Se, 2b), [EFe3(CO)9Cu2(dppm)2] (E = S, 3a; Se, 3b; Te, 3c), [{SeFe3(CO)9Cu2(dppm)}2(dpy)] (4), and [{SeFe3(CO)9Cu2(dppm)}2(dpee)] (5) were formed. The transformations and reversibilities of these compounds were studied.
In addition, the complexes [EFe3(CO)9Cu2(dppe)] (E = Se, 6b; Te, 6c) and [{(uf06d4-S)Fe3(CO)9}Cu2(dppe)(MeCN)2]n (7) were formed when the [EFe3(CO)9Cu2(MeCN)2] (E = S, Se, Te) were ground with diphenylphosphino ethane (dppe). The transformation of 7 to 6a was observed. The anionic cluster [{EFe3(CO)9Cu}2(dppe)]2‒ (E = S, 8a; Se, 8b; Te, 8c) were isolated when the reaction of 6a‒6c with [EFe3(CO)9]2‒ (E = S, Se, Te), respectively. The reversibility was also shown. Finally, the optical reflectance spectra of the series of E‒Fe3‒Cu2‒dppxn‒solvent (E = S, Se, Te; dppx = dppm, dppe; n = 1, 2; solvent = THF, acetone, MeCN) complexes were elucidated by the packing diagram in solid state.

E‒Fe‒Cu‒NHC (E = Se, Te) system
We reported one-pot syntheses of EFe3Cu2-based complexes (E = Se, Te) [EFe3(CO)9Cu2(Me2Im)2] (2a, 2b), [EFe3(CO)9Cu2(Me2BenzIm)2] (3a, 3b), [EFe3(CO)9Cu2(iPr2BenzIm)2] (4a, 4b), and [EFe3(CO)9Cu2- (4,5-dichloro-Me2Im)2] (5a, 5b), which were achieved from the reactions of [EFe3(CO)9Cu2(MeCN)2] (E = Se, 1a; Te, 1b) and N-heterocyclic carbenes salts (1,3-dimethylimidazolium iodide (Me2Im•HI), 1,3-dimethylbenzimidazolium iodode (Me2BenzIm•HI), 1,3-diisopropylbenzimidazolium iodide (iPr2BenzIm•HI), or 4,5-dichloro-1,3-dimethylimdazolium iodide (4,5-Cl2Me2Im•HI)) along with tBuOK in a 1: 2: 2 ratio in THF. These NHCs complexes were structurally characterized, in which 2a(b)‒5a(b) consisted of an EFe3(CO)9 core capped or bridged by the Cu2L2 or di-CuL fragments (E = Se, Te; L = Me2Im, Me2BenzIm, iPr2BenzIm, and 4,5-Cl2Me2Im). Moreover, we attempted to introduce the electron-donating and bulkly anionic clusters [EFe3(CO)9]2‒ (E = Se, Te) or/and NHCs as the ligands for the Cu(I) complexes used as catalysts in the homocoupling of arylboronic acids. Finally, the best catalytic efficiencies of a series of E‒Fe‒Cu‒NHC (E = Se, Te) could be obtained.
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並列關鍵字

liquid-assisted grinding ； carbonyl cluster ； NHC ； S、Se、Te

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