含十六族元素之異核金屬羰基團簇物:合成與電化學和電子吸收光譜以及理論計算探討 Bimetallic Carbonyl Chalcogenide Clusters: Synthesis, Electrochemistry, Optical Properties, and Computational Studies

Date
2011
Authors
繆佳曄
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Abstract
1. E/Mn/Cr/CO (E = S, Se) 系統之研究 當[PPN][E2Mn3(CO)9] (E = S, Se)、Cr(CO)6和PPNCl以莫耳比1:1:2或1:2:2於混合乙腈及甲醇之鹼性溶液(4M)中反應,可得到含hydride之混合錳鉻化合物[PPN]2[HE2Mn3Cr(CO)14] (E = S, [PPN]2[1a]; Se, [PPN]2[1b])。然而,起始物之陽離子來源為TMBA時,進而加入Cr(CO)6以莫耳比1:1於鹼性甲醇溶液(4M)中加熱迴流反應,可獲得八面體結構之混合錳鉻團簇物[TMBA]3[E2Mn3Cr(CO)12] (E = S, [TMBA]3[2a]; Se, [TMBA]3[2b])。化合物1a和1b亦可於鹼性甲醇溶液中加熱迴流並進行合環反應而轉變成化合物2a和2b。此外,若化合物1a和1b加入一或兩當量Cr(CO)6於二氯甲烷溶液中加熱迴流反應,則可進行擴核反應而得到含hydride之混合錳鉻化合物[HE2Mn3Cr2(CO)19]2─ (E = S, 3a; Se, 3b)。其化合物生成及相關性質、結構轉換以及電化學性質藉由理論計算進一步驗證。 2. E/Mn/Ru/CO (E = S, Se) 系統之研究 當[PPN][E2Mn3(CO)9] (E = S, Se)與Ru3(CO)12以莫耳比1:1於混合乙腈及甲醇溶液中加熱迴流反應,可得到八面體結構之同核含釕團簇物[HE2Ru4(CO)10]− (E = S, 3a; Se, 3b)和異核含混合錳釕團簇物[E2Mn2Ru2(CO)11]2− (E = S, 4a; Se, 4b)。此外,化合物4a和4b相較於等電子的八面體結構之同核含錳團簇物[E2Mn4(CO)12]2− (E = S, 1a; Se, 1b)和異核含混合錳鉻團簇物[E2Mn3Cr(CO)12]3− (E = S, 2a; Se, 2b)具有良好電子傳遞行為,其氧化位置發生在雙錳金屬羰基片段。紫外可見光吸收光譜顯示此系列同核及異核化合物之電子躍遷為MLCT (Mn→E or COs)或混合MLCT及MMCT (Mn→Cr or Ru)特性,並藉由反射光譜得知此系列化合物其能隙介於1.25至1.80 eV。其化合物生成及相關性質、電子吸收以及電化學性質藉由理論計算進一步驗證。 3. Te/Ru/Cu/CO 系統之研究 當[PPh4]2[TeRu5(CO)14]加入一當量[Cu(MeCN)4][BF4]於二氯甲烷溶液及低溫下反應,可得到三銅橋接之雙八面體結構的團簇物[PPh4]2[{TeRu5(CO)14}2Cu3Cl] ([PPh4]2[1])。若將上述反應之[Cu(MeCN)4][BF4]提高至兩當量,可獲得四銅橋接之雙八面體結構團簇物[PPh4]2[{TeRu5(CO)14}2Cu4Cl2]∙CH2Cl2 ([PPh4]2[2]∙CH2Cl2)和雙銅蓋接之八面體結構團簇物[TeRu5(-CO)2(CO)12Cu2(MeCN)2] (3a);然而,此反應若於室溫下進行,則可獲得化合物2以及化合物3a之結構異構物[TeRu5(-CO)3(CO)11Cu2(MeCN)2] (3b)。此外,化合物1和2的生成反應涉及二氯甲烷之碳氯鍵活化,而化合物3a和3b的生成是藉由反應溫度控制。化合物1─3的生成及相關性質、結構轉換、電子吸收以及電化學性質藉由理論計算進一步驗證。 4. Te/Fe/Cu/dipyridyl 系統之研究 當[TeFe3(CO)9{Cu(MeCN)}2]與不同有機含氮配子依劑量莫耳比於四氫呋喃溶液中反應,可獲得一維或二維含有機配子之混合鐵銅羰基的有機金屬-有機混合之配位聚合物1─4。此外,利用一鍋化方式將[TeFe3(CO)9]2─、[Cu(MeCN)4][BF4]與有機配子H2bpe or tmdpy於四氫呋喃溶液中反應,可得到聚合物3和4其結構中的陰離子之混合鐵銅團簇物[{TeFe3(CO)9Cu}2L]2─ (L = H2bpe, 5; tmdpy, 6)。化合物1─6之生成及相關性質、電子吸收以及導電性藉由理論計算進一步驗證。 關鍵字:第十六族元素、異核金屬、團簇物、電化學、電子吸收光譜、理論計算
1. E/Mn/Cr/CO (E = S, Se) System When trigonal-bipyramidal clusters, [PPN][E2Mn3(CO)9] (E = S, Se), were treated with Cr(CO)6 and PPNCl in a molar ratio of 1: 1: 2 or 1: 2: 2 in 4 M KOH/MeCN/MeOH solutions, mono-Cr(CO)5-incorporated HE2Mn3-complexes [PPN]2[HE2Mn3Cr(CO)14] (E = S, [PPN]2[1a]; Se, [PPN]2[1b]), respectively, were formed. However, when the TMBA+ salts for [E2Mn3(CO)9]─ were mixed with Cr(CO)6 in a molar ratio of 1: 1 in 4 M KOH/MeOH solutions and refluxed at 60 oC, mono-Cr(CO)3-incorporated E2Mn3Cr octahedral clusters [TMBA]3[E2Mn3Cr(CO)12] (E = S, [TMBA]3[2a]; Se, [TMBA]3[2b]), respectively, were obtained. Clusters 1a and 1b (with [TMBA] salts) underwent metal core closure to form octahedral clusters 2a and 2b upon treatment with KOH/MeOH at 60 oC. In addition, 1a and 1b were found to undergo cluster expansion to form di-Cr(CO)5-incorporated HE2Mn3-clusters [HE2Mn3Cr2(CO)19]2─ (E = S, 3a; Se, 3b), respectively, upon the addition of 1 or 2 equiv of Cr(CO)6 heated in refluxing CH2Cl2. The nature, cluster transformation, and electrochemical properties of the mixed manganese─chromium carbonyl sulfides and selenides were systematically discussed in terms of the chalcogen elements, the introduced chromium carbonyl group, and the metal skeleton, with the aid of molecular calculations at the BP86 level of the density functional theory. 2. E/Mn/Ru/CO (E = S, Se) System Heating trinuclear E2Mn3-trigonal-bipyramidal clusters, [E2Mn3(CO)9]− (E = S, Se) with Ru3(CO)12 in a molar ratio of 1: 1 in MeCN/MeOH solutions afforded two tetranuclear products, E2Ru4-octahedral clusters [HE2Ru4(CO)10]− (E = S, 3a; Se, 3b) and mixed-metal E2Mn2Ru2-octahedral clusters [E2Mn2Ru2(CO)11]2− (E = S, 4a; Se, 4b). In addition, 4a and 4b exhibited intense electronic communication through the M4 square during oxidation of Mn2(CO)6 fragment, which were compared to the analogous homonuclear group 7 clusters, [E2Mn4(CO)12]2− (E = S, 1a; Se, 1b) and the heteronuclear mixed-group 6/7 clusters, [E2Mn3Cr(CO)12]3− (E = S, 2a; Se, 2b). The electronic absorptions of [E2Mn3(CO)9]− and 1 were assigned as the MLCT (Mn→E or COs) transitions while those of 2 and 4 were attributed to the MLCT (Mn→E or COs) and MMCT (Mn→Cr or Ru) transitions. Moreover, these clusters also showed optical transitions with band gaps of 1.25 to 1.80 eV. Furthermore, the formation and electronic properties as well as electrochemical and optical properties of these E2M4-octahedral carbonyl sulfides and selenides were studied and elucidated with the aid of molecular calculations at the BP86 level of the density functional theory. 3. Te/Ru/Cu/CO System When [PPh4]2[TeRu5(CO)14] was treated with 1 equiv. of [Cu(MeCN)4][BF4] in dichloromethane (CH2Cl2) at low temperature, the Cu3Cl-incorporated di-TeRu5 carbonyl cluster [PPh4]2[{TeRu5(CO)14}2Cu3Cl] ([PPh4]2[1]) was formed. When [PPh4]2[TeRu5(CO)14] reacted with 2 equiv. of [Cu(MeCN)4][BF4] in CH2Cl2 at low temperature, both Cu4Cl2-incorporated di-TeRu5 carbonyl clusters [PPh4]2[{TeRu5(CO)14}2Cu4Cl2]∙CH2Cl2 ([PPh4]2[2]∙CH2Cl2) and [TeRu5(-CO)2(CO)12Cu2(MeCN)2] (3a) were obtained. However, similar reaction of [PPh4]2[TeRu5(CO)14] with 2 equiv. of [Cu(MeCN)4][BF4] in CH2Cl2 at room temperature produced complexes 2 and [TeRu5(-CO)3(CO)11Cu2(MeCN)2] (3b). The formation of 1 and 2 involved the abstraction of chloride from dichloromethane while the formation of isomers 3a and 3b was governed by the reaction temperature. The nature, transformation, electrochemical, and optical properties of these CuX (X = MeCN or Cl)-incorporated mono- or di-TeRu5-based clusters were discussed in terms of the effects of copper, tellurium, temperature, and the size of the metal skeleton, which was elucidated in detail by DFT calculations at the MPW1PW91 level of the density function theory. 4. Te/Fe/Cu/dipyridyl System Four new mixed-metal cluster-based 1D or 2D organometallic-organic hybrid polymers 1─4 were synthesized from the reactions of the neutral heterometallic cluster [TeFe3(CO)9{Cu(MeCN)}2] with various ditopic organic linkers such as 1,2-bis(4-pyridine)ethene (bpe), 1,2-bis(4-pyridine)ethane (H2bpe), and 4,4′-trimethylene-dipyridine (tmdpy) in the stoichiometric molar ratios in THF. Besides, the corresponding anionic clusters in 3 and 4, [{TeFe3(CO)9Cu}2L]2─ (L = H2bpe, 5; tmdpy, 6), could be isolated from a one-pot reaction of [TeFe3(CO)9]2─, [Cu(MeCN)4][BF4], and H2bpe or tmdpy. The ternary Te─Fe─Cu─dipyridyl complexes 1─6 were characterized spectroscopically and their nature, formation, and semiconducting properties were discussed systematically in terms of the nature of N-donor dipyridyl linkers, the dimensionalities, and the intermolecular hydrogen interactions with the aid of molecular calculations at the B3LYP level of the density functional theory. Keywords: group 16 elements, heteronuclear metals, clusters, electrochemistry, UV-vis spectra, computational studies.
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第十六族元素, 異核金屬, 團簇物, 電化學, 電子吸收光譜, 理論計算, group 16 elements, heteronuclear metals, clusters, electrochemistry, UV-vis spectra, computational studies
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