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研究生: 何莉芳
Li-Fang Ho
論文名稱: 含硒或碲之鉻金屬羰基化合物的系統研究
Synthesis and Characterization of Group 6 (M= Cr, Mo) Carbonyl Chalcogenides Complexes
指導教授: 謝明惠
Shieh, Ming-Huey
學位類別: 碩士
Master
系所名稱: 化學系
Department of Chemistry
論文出版年: 2000
畢業學年度: 88
語文別: 中文
論文頁數: 270
中文關鍵詞: 團簇化合物羰基
英文關鍵詞: cluster, carbonyl
論文種類: 學術論文
相關次數: 點閱:124下載:8
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  • [1] 硒(Se)-鉻(Cr)系統的研究
    使用Se金屬粉末或是其氧化物(Na2SeO3、SeO2),與Cr(CO)6、Et4NBr,以1:2的比例在鹼性甲醇溶液中,加熱反應可得雙三角錐結構的[Et4N]2[Se2Cr3(CO)10]。利用相同條件,[S2Cr3(CO)10]2-亦可成功地被合成出。
    將[Se2Cr3(CO)10]2-與MeOTf反應,可得單甲基及雙甲基化合物[MeSeCr3(CO)15]-、{MeSeCr(CO)4}2,並探討兩化合物之間的關係。然而,與其他有機試劑RX (R = C3H3, X = Cl, Br; R = CH3, X = I) 反應,則僅得穩定的單核產物[XCr(CO)5]-(X = Cl、Br、I)。
    此外,與第八族的異核金屬Fe(CO)5、Ru3(CO)12反應,分別得已知產物[SeFe3(CO)9]2-與具八面體結構的[HSe2Ru4(m-CO)2(CO)8]-、[Se2Ru4(m-CO)4(CO)8]2-。而將[Se2Cr3(CO)10]2-與1當量的Mo(CO)6在丙酮中反應,可得混合鉻鉬金屬的化合物 [Se2MoCr2(CO)10]2-;若以過量的Mo(CO)6反應,則得高產率完全取代的[Se2Mo3(CO)10]2- 。
    至於[Se2Cr3(CO)10]2-與 Mn(CO)5Br的反應在丙酮中反應,可得兩種不同形式且結構特殊的混合鉻-錳金屬化合物,分別是 [Me2CSe2Cr2Mn(CO)14]-與[ Se2Cr2Mn3(CO)20]-。
    [2] 碲(Te)-鉻(Cr)系統的研究
    將Te與Cr(CO)6、KOH以1:2的比例在甲醇溶液中反應,先形成[HTe{Cr(CO)5}2]-,但目前並無證據顯示其存在,再加入Et4NBr則可得綠色不安定化合物[Te{Cr(CO)5}2]2-。然而當我們改用鹼度較小的NaOH,依相同條件則得單甲基化合物[MeTe{Cr(CO)5}2]-,推測甲基是來自所使用的溶劑MeOH。若以[Te{Cr(CO)5}2]2-與MeOTf反應,僅生成雙甲基化合物Me2Te{Cr(CO)5}2。
    此外,[Te{Cr(CO)5}2]2-對O2、CH2Cl2極為敏感,會迅速反應生成雙聚合的[L{TeCr2(CO)10}2]2- (L = O, CH2)。 [Te{Cr(CO)5}2]2-再進一步與Cu(CH3CN)4BF4反應,可得已知平面型化合物[Te2Cr4(CO)20]2-。若改與NaOH/MeOH反應,則生成另一已知開放性結構的化合物[Te2Cr4(CO)18]2-。
    至於,提高Cr(CO)6的比例至1:3,所得產物亦很容易與CH2Cl2反應,而生成[CH2ClTe{Cr(CO)5}3]-。
    [3] 碲(Te)-鉬(Mo)系統的研究
    使用Te powder 與 Mo(CO)6 在鹼性甲醇溶液中反應,可得車輪狀化合物 [Te8Mo6(CO)18]2-,此化合物包含三個Te2Mo2平面並以Te22-相連結 ,故亦可由[Te2Mo4(CO)18]2-與Te/KOH反應而得 。若將[Te2Mo4(CO)18]2- 與溴丙烯 H2C=CHCH2Br反應,丙烯基取代起始物中的Mo(CO)5,而生成雙取代化合物[(C3H5)2Te2Mo2(CO)6] 。

    [1] Se-Cr system
    Reflux of Se powder or SeO2、SeO32- with Cr(CO)6、Et4NBr in KOH/MeOH solution yields the closo-cluster [Et4N]2[Se2Cr3(CO)10]. [S2Cr3(CO)10]2- also an be prepared in the similar conditions. Further methylation of [Se2Cr3(CO)10]2- with MeSO3CF3 produces the selenium-methylated complex [MeSe{Cr(CO)5}3]- and {MeSeCr(CO)4}2 . However, the reactions of [Se2Cr3(CO)10]2- with RX (R = C3H3, X = Cl, Br; R = CH3, X = I) form the known mononuclear compounds [XCr(CO)5]- (X = Cl, Br, I)
    Further, reaction of [Se2Cr3(CO)10]2- with Fe(CO)5/KOH gives [SeFe3(CO)9]2-, while treatment with Ru3(CO)12 produces the octahedral complexes [HSe2Ru4(m-CO)2(CO)8]- and [Se2Ru4(m-CO)4(CO)8]2-. Be- sides, [Se2Cr3(CO)10]2- can react with 1 equiv. of Mo(CO)6 in acetone to produce the mixed-metal Cr/Mo cluster [Se2MoCr2(CO)10]2-. On the other hand, reaction of [Se2Cr3(CO)10]2- with excess Mo(CO)6 leads to formation of [Se2Mo3(CO)10]2- in good yield. When [Se2Cr3(CO)10]2- was treated with Mn(CO)5Br in acetone at room temperature, two different types of the unusual mixed-metal clusters [Me2CSe2Cr2Mn(CO)14]- and [Se2Cr2Mn3- (CO)20]- were produced.
    [2] Te-Cr system
    The reaction of Te powder with Cr(CO)6/KOH in a molar ratio of 1:2 in methanol solution forms [HTe{Cr(CO)5}2]- , which can rapidly transform into a highly reactive species [Et4N]2[Te{Cr(CO)5}2] by the addition of Et4NBr . However, the mono-methylated complex [MeTe{Cr(CO)5}2]- can be obtained by using NaOH under the similar conditions, where the methyl group is likely to come from the methanol solvent.
    The reaction of [Te{Cr(CO)5}2]2- with MeSO3CF3 only affords the double-methylated complex Me2Te{Cr(CO)5}2 . [Te{Cr(CO)5}2]2- rapidly transforms to give [X{TeCr2(CO)10}2]2- (X = O, CH2) upon the attack of O2 and CH2Cl2. Besides, the reaction of [Te{Cr(CO)5}2]2- with Cu(CH3CN)4BF4 produces the known compound [Te2Cr4(CO)20]2- while treatment of [Te{Cr(CO)5}2]2- with NaOH/MeOH gives another known compound [Te2Cr4(CO)18]2-.
    When Te powder reacts with Cr(CO)6/KOH in a molar ratio of 1: 3 in methanol solution, the product is found to rapidly transform into a new complex [CH2ClTe{Cr(CO)5}3]- upon the addition of CH2Cl2.
    [3] Te-Mo system
    Reflux of Te powder and Mo(CO)6 in KOH/MeOH solution forms the tire-shaped cluster [Te8Mo6(CO)18]2-, which contains three Te2Mo2 planes linking by Te22- group. This product can be also obtained from the reaction of Te powder with [Te2Mo4(CO)18]2- in the basic alcoholic solution. When [Te2Mo4(CO)18]2- was treated with H2C=CHCH2Br, the double-substituted complex [(C3H5)2Te2Mo2(CO)6] was obtained where the Mo(CO)5 moiety of [Te2Mo4(CO)18]2- is replaced by the incoming C3H5 group.
    The study herein describes the similarities and differences among the reactions of group 6 (Cr, Mo) carbonyls with group 16 chalcogen atoms (S, Se, Te) and discusses as well the effect of basicity and metal size on cluster formation.

    中文摘要.................................... I 英文摘要……………… …………………………………….. III 1. 前言……………………………………………... 1 1.1. 背景………………..……………………………… 1 1.2 研究目標………………………………………... 11 2. 實驗………………………………………………... 12 2.1. 一般方法…………………………………………… 12 2.1-1. 實驗過程…………………………………………… 12 2.1-2. 使用的光譜儀器…………………………………… 12 2.1-3. 實驗溶劑…………………………………………… 13 2.1-4. 使用藥品……………………………………………… 14 2.1-5. 縮寫表………………………………………………… 14 2.2 合成[Et4N]2[Se2Cr3(CO)10]………………………. 16 2.3 [Et4N]2[Se2Cr3(CO)10]與有機試劑的反應….….. 17 2.3-1 [Et4N]2[Se2Cr3(CO)10]的甲基化反應……….… 17 2.3-2 [Et4N]2[Se2Cr3(CO)10]與C3H3X (X = Br, Cl) 的反應19 2.3-3 [Et4N]2[Se2Cr3(CO)10]的加壓反應………………. 20 2.4 [Et4N]2[Se2Cr3(CO)10]與異核金屬的反應………. 21 2.4-1 [Et4N]2[Se2Cr3(CO)10]與 Fe(CO)5 的反應….... 21 2.4-2 [Et4N]2[Se2Cr3(CO)10]與Ru3(CO)12的反應…... 22 2.4-3 [Et4N]2[Se2Cr3(CO)10]與Mo(CO)6的反應……. 22 2.4-4 [Et4N]2[Se2Cr3(CO)10]與Mn(CO)5Br的反應……. 24 2.5 [Et4N]2[S2Cr3(CO)10]的合成與相關反應………. 26 2.5-1 [Et4N]2[S2Cr3(CO)10]的合成…………………. 26 2.5-2 [Et4N]2[S2Cr3(CO)10] 與Mn(CO)5Br的反應……. 27 2.5-3 [Et4N]2[S2Cr3(CO)10] 與Mo(CO)6的反應……. 27 2.6 Te與不同比例Cr(CO)6反應………………..……. 28 2.7 [Et4N]2[Te{Cr(CO)5}2]的相關反應…..………. 31 2.7-1 [Et4N]2[Te{Cr(CO)5}2]與CH2Cl2的反應.………. 31 2.7-2 [Et4N]2[Te{Cr(CO)5}2]與O2的反應..……………. 32 2.7-3 [Et4N]2[Te{Cr(CO)5}2]與MeOH的反應..………. 32 2.7-4 [Et4N]2[Te{Cr(CO)5}2]與MeOTf的反應..………. 33 2.7-5 [K(18-Crown-6)]2[Te{Cr(CO)5}2]的合成.………. 34 2.7-6 [K(18-Crown-6)]2[Te{Cr(CO)5}2]與[Cu(CH3CN)4][BF4]的反應 34 2.8 [PPh4]2[Te2Mo4(CO)18]的相關反應….………. 35 2.8-1 [PPh4]2[Te2Mo4(CO)18]與H2C=CHCH2Br的反應.. 35 2.8-2 [PPh4]2[Te2Mo4(CO)18]與CBr4的反應…..………. 36 2.9 [PPh4]2[Te8Mo6(CO)18]的合成……..……..……. 36 2.10 {MeSeCr(CO)4}2的晶體結構解析…..…..……. 38 2.11 [Et4N][MeSeCr3(CO)15]的晶體結構解析…..……. 41 2.12 [Et4N][HSe2Ru4(m-CO)2(CO)8]的晶體結構解析…. 44 2.13 [Et4N]2[Se2Ru4(m-CO)4(CO)8]的晶體結構解析.. 47 2.14 [Et4N]2[Se2Cr2Mo(CO)10]的晶體結構解析……… 50 2.15 [Et4N]2[Se2Mo3(CO)10]的晶體結構解析……….. 53 2.16 [Et4N][Me2CSe2Cr2Mn(CO)14]的晶體結構解析…… 56 2.17 [Et4N][Se2Mn3Cr2(CO)20]的晶體結構解析…….. 59 2.18 [Et4N]2[S2Cr3(CO)10]的晶體結構解析……..…. 63 2.19 [Et4N]2[Te{Cr(CO)5}2]的晶體結構解析……….. 66 2.20 [PPN][CH2ClTe{Cr(CO)5}3]的晶體結構解析…… 69 2.21 [Et4N]2[O{TeCr2(CO)10}2]的晶體結構解析……. 72 2.22 [Et4N]2[CH2{TeCr2(CO)10}2]的晶體結構解析.…. 75 2.23 [Et4N]2[Te2Cr4(CO)18]的晶體結構解析…………. 78 2.24 [Et4N][MeTe{Cr(CO)5}2]的晶體結構解析……….. 81 2.25 Me2Te{Cr(CO)5}2的晶體結構解析…………….…… 84 2.26 {C3H5TeMo(CO)4}2的晶體結構解析………..……… 87 2.27 [PPh4]2[Te8Mo6(CO)18]的晶體結構解析….……… 90 2.28 [Et4N][Se2Mn3Cr2(CO)20]的磁性分析……..……. 94 3. 結果………………………………………………….. 95 3.1 Se-Cr-CO系統………………………………………… 95 3.1-1 [Et4N]2[Se2Cr3(CO)10]的合………………………. 95 3.1-2 [Et4N]2[Se2Cr3(CO)10]與有.………………... 96 3.1-3 [Et4N]2[Se2Cr3(CO)10]與第八族異核金屬羰基化合物的反應….. 99 3.1-4 [Et4N]2[Se2Cr3(CO)10]與第六族M(CO)6 (M = Mo, W)的反應... 101 3.1-5 [Et4N]2[Se2Cr3(CO)10]與Mn(CO)5Br的反應.…… 103 3.2 S-Cr-O 系統……………………………….…….... 104 3.3 Te-Cr-CO系統……………………………………… 106 3.3-1 Te與不同比例Cr(CO)6的反應………………..….. 106 3.3-2 [Et4N]2[Te{Cr(CO)5}2]的反應性………………. 108 3.3-3 不同鹼度對Te-Cr系統的影響……………………. 110 3.4 Te-Mo-CO系統…………………………………….. 113 3.4-1 Mo(CO)6與不同來源Te的反應…………………… 113 3.4-2 [PPh4]2[Te2Mo4(CO)18]與有機溴化物的反應……. 114 3.5 {MeSeCr(CO)4}2的晶體結構……………….……. 116 3.6 [Et4N][MeSeCr3(CO)15]的晶體結構……….……. 118 3.7 [Et4N][HSe2Ru4(m-CO)2(CO)8]的晶體結構..……. 120 3.8 [Et4N]2[Se2Ru4(m-CO)4(CO)8]的晶體結構.……. 122 3.9 [Et4N]2[Se2Cr2Mo(CO)10]的晶體結構.…..……. 124 3.10 [Et4N]2[Se2Mo3(CO)10]的晶體結構……….……. 126 3.11 [Et4N][Me2CSe2Cr2Mn(CO)14]的晶體結構…...…. 128 3.12 [Et4N][Se2Mn3Cr2(CO)20]的晶體結構….………. 130 3.13 [Et4N]2[S2Cr3(CO)10]的晶體結構………..……. 132 3.14 [Et4N]2[Te{Cr(CO)5}2]的晶體結構……….……. 134 3.15 [PPN][CH2ClTe{Cr(CO)5}3]的晶體結構….……. 136 3.16 [Et4N]2[O{TeCr2(CO)10}2]的晶體結構……….…. 138 3.17 [Et4N]2[CH2{TeCr2(CO)10}2]的晶體結構….……. 140 3.18 [Et4N]2[Te2Cr4(CO)18]的晶體結構……….……. 142 3.19 [Et4N][MeTe{Cr(CO)5}2]的晶體結構……….……. 144 3.20 Me2Te{Cr(CO)5}2的晶體結構….………….……. 146 3.21 {C3H5TeMo(CO)4}2的晶體結構……………….……. 148 3.22 [PPh4]2[Te8Mo6(CO)18]的晶體結構…….…….…. 150 3.23 電化學分析結果…………………………….……. 152 4. 討論………………………………………………… 153 4.1 Se-Cr-CO系統………………………………………… 153 4.1-1 [Et4N]2[E2Cr3(CO)10](E = S, Se)的合成探討…. 153 4.1-2 [Et4N]2[Se2Cr3(CO)10]與有機試劑的反應探討... 155 4.1-3 [Et4N]2[Se2Cr3(CO)10]與Fe(CO)5、Ru3(CO)12的反應探討..…... 158 4.1-4 [Et4N]2[Se2Cr3(CO)10]與Mo(CO)6的反應探討.... 159 4.1-5 [Et4N]2[Se2Cr3(CO)10]與Mn(CO)5Br的反應探討. 162 4.2 Te-Cr-CO系統…………………………………… 165 4.2-1 Te與不同比例Cr(CO)6的反應探討…………..….. 165 4.2-2 [Et4N]2[Te{Cr(CO)5}2]的反應性探討…………. 168 4.2-3 不同鹼度對Te-Cr系統的影響….………………. 170 4.3 Te-Mo-CO系統…………………………………….. 174 4.4 晶體結構討論………………………………….…… 177 4.4-1 具雙三角錐E2M3形式的結構討論………….……. 177 4.4-2 [MeSeCr3(CO)15]-與{MeSeCr(CO)4}2的結構討論… 183 4.4-3 具八面體E2M4形式的結構討論………….………. 184 4.4-4 含Se-Cr-Mn的結構討論………………….………. 187 4.4-5 含Te{Cr(CO)5}2形式的結構討論…….….……. 190 4.4-6 含Te2Mo2形式的結構討論………………….………. 195 4.5 本研究綜合性討論………………………….………. 199 5. 結論……………………………………………... 204 6. 參考資料…………………………………………... 206 7. 附圖

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