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研究生: 洪登南
Horng, Den-Nan
論文名稱: 含磷多牙配子金屬羰基錯合物之合成及結構研究
Syntheses and Crystal Structures of Metal Carbonyl Complexes
指導教授: 翁春和
Ueng, Chuen-Her
學位類別: 博士
Doctor
系所名稱: 化學系
Department of Chemistry
畢業學年度: 83
語文別: 中文
論文頁數: 345
中文關鍵詞: 合成;晶體結構;含磷錯合物
英文關鍵詞: synthesis; crystal structure; phosphine
論文種類: 學術論文
相關次數: 點閱:279下載:3
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  • 本文使用六羰金屬[M(CO)6](M=Cr,Mo,W)及含雙鐵錯合物[C5H5Fe
    (CO)2]2 分別與含磷三牙配子Pf-Pf-Pf(Pf-Pf-Pf=PhP(CH2CH2PPh2)2),
    C-Pf3(C-Pf3=MeC(CH2PPh2)3)及含磷四牙配子P-Pf3(P-Pf3=P(CH2CH2PPh2
    )3)進行反應,共得到三十一個錯合物,可分為六種類型:
    (a)多核單取代錯合物六個:[Cr3(CO)15(Pf-Pf-Pf)](Ⅰa1),[Mo3
    (CO)15(Pf-Pf-Pf)](Ⅰa2),[Cr3(CO)15(C-Pf3)](Ⅱa1),[Mo3(CO)15
    (C-Pf3)](Ⅱa2),[Cr4(CO)20(P-Pf3)](Ⅲa1),[Mo4(CO)20(P-Pf3)](Ⅲa2)
    (b)異金屬雙核錯合物八個:[Cr(CO)4(Pf-Pf-Pf)Mo(CO)5](Ⅰb1),
    [Cr(CO)4(Pf-Pf-Pf)W(CO)5](Ⅰb2),[Mo(CO)4(Pf-Pf-Pf)Cr(CO)5](Ⅰb3)
    [Mo(CO)4(Pf-Pf-Pf)W(CO)5](Ⅰb4),[Cr(CO)4(C-Pf3)Mo(CO)5](Ⅱb1),
    [Mo(CO)4(C-Pf3)Cr(CO)5](Ⅱb2),[Mo(CO)3(P-Pf3)W(CO)5](Ⅲb1),
    [W(CO)3(P-Pf3)Mo(CO)5](Ⅲb2).
    (c)同金屬雙核錯合物九個:[Cr(CO)4(Pf-Pf-Pf)Cr(CO)5](五員環)
    (Ⅰc1),[Cr(CO)4(Pf-Pf-Pf)Cr(CO)5](八員環)(Ⅰc2),[Mo(CO)4)Pf-Pf-
    Pf)Mo(CO)5](Ⅰc3),[W(CO)4(Pf-Pf-Pf)Mo(CO)5](Ⅰc4),[Cr(CO)4(C-Pf3
    )Cr(CO)5](Ⅱc1),[Mo(CO)4(C-Pf3)Mo(CO)5](Ⅱc2),[Cr2(CO)8(P-Pf3)]
    (Ⅲc1),[Mo2(CO)8(P-Pf3)(Ⅲc2),[W2(CO)8(P-Pf3)](Ⅲc3).
    (d)單核二取代錯合物二個:[Cr(CO)4(C-Pf3)](Ⅱd1),[Mo(CO)4(C-Pf3
    )](Ⅱd2).
    (e)單核三取代錯合物二個:[Cr(CO)3(C-Pf3)](Ⅱe1),[Mo(CO)3(C-Pf3
    )](Ⅱe2).
    (f)含雙鐵之VIB金屬羰基錯合物四個:[(C5H5)2(CO)2Fe2(Pf-Pf-Pf)
    (Ⅳ),[C5H5)2(CO)2Fe2(Pf-Pf-Pf)Cr(CO)5](Ⅳ1),[C5H5)2(CO)2Fe2
    (Pf-Pf-Pf)Mo(CO)5](Ⅳ2),[(C5H5)2(CO)2Fe2(Pf-Pf-Pf)W(CO)5](Ⅳ3).
    其中(a)類錯合物是以TMNO為起始劑在0℃下以化學氧化法製得;(b)類
    錯合物是以中間物[M(CO)4(NBD)](M=Cr,Mo)或[M(CO)3(PMTA)](M=Mo,W)取
    代法配合化學氧化法製得;(c)類錯合物製備方法與(a)類相同,但反應須在
    室溫下進行,其中Ⅰc1,Ⅰc3,Ⅲc1及Ⅲc2亦可使用中間物取代法製得;(d)
    類錯合物是以中間物[M(CO)4(NBD)]取代法製得;(e)類化合物是以熱裂法
    製得;(f)類錯合物則由[C5H5Fe(CO)2]2與Pf-Pf-Pf反應而得到[(C5H5)2
    (CO)2Fe2(Pf-Pf-PF)],再與 [M(CO)5(MecN)](M=Cr,Mo,W)反應而得到
    [(C5H5)2(CO)2Fe2(Pf-Pf-Pf)M(CO)5].

    The reactions of [M(CO)6](M=Cr,Mo,W)or[C5H5Fe(CO)2]2 with
    tridentate phosphines, Pf-Pf-Pf(Pf-Pf-Pf=PhP(CH2CH2PPh2)2),
    C-Pf3(C-Pf3=MeC(CH2PPh2)3),or tetradentate phosphines, P-Pf3
    (P-Pf3=P(CH2CH2PPh2)3) yield 31 complexes,which were subdivided
    to the following 6 types:
    (a) Polynuclear monosubstituted complexes include 6 compounds
    :[Cr3(CO)15(Pf-Pf-Pf)](Ⅰa1),[Mo3(CO)15(Pf-Pf-Pf)(Ⅰa2),(Cr3
    (CO)15(C-Pf3)](Ⅱa1),[Mo3(CO)15(C-Pf3)](Ⅱa2),[Cr4(CO)20(P-Pf3)]
    (Ⅲa1),[Mo4(CO)20(P-Pf3)](Ⅲa2).
    (b) Hetero-bimetallic complexes include 8 compounds:[Cr(CO)4
    (Pf-Pf-Pf)Mo(CO)5](Ⅰb1),[Cr(CO)4W(CO)5](Ⅰb2),[Mo(CO)(Pf-Pf-Pf)
    Cr(CO)5](Ⅰb3),[Mo(CO)4(Pf-Pf-Pf)W(CO)5](Ⅰb4),[Cr(CO)4(C-Pf3)
    Mo(CO)5](Ⅱb1),[Mo(CO)4(C-Pf3)Cr(CO)5](Ⅱb2),[Mo(CO)3(P-Pf3)
    W(CO)5](Ⅲb1),[W(CO)3(P-Pf3)Mo(CO)5](Ⅲb2).
    (c)Homo-bimetallic complexes include 9 compounds:[Cr(CO)4
    (Pf-Pf-Pf)Cr(CO)5](5-member ring)(Ⅰc1),[Cr(CO)4(Pf-Pf-Pf)Cr
    (CO)5](8-member ring)(Ⅰc2),[Mo(CO)4(Pf-Pf-Pf)Mo(CO)5](Ⅰc3),
    [W(CO)4(Pf-Pf-Pf)W(CO)5](Ⅰc4),[Cr(CO)4(C-Pf3)Cr(CO)5](Ⅱc1),
    [Mo(CO)4(C-Pf3)Mo(CO)5](Ⅱc2),[Cr2(CO)8(P-Pf3)](Ⅲc1),[Mo2(CO)8
    (P-Pf3)](Ⅲc2),[W2(CO)8(P-Pf3)](Ⅲc3).
    (d)Mononuclear disubstituted complexes include 2 compounds:
    [Cr(CO)4(C-Pf3)](Ⅱd1),[Mo(CO)4(C-Pf3)](Ⅱd2).
    (e)Mononuclear trisubstituted complexes include 2 compounds:
    [Cr(CO)3(C-Pf3)](Ⅱe1),[Mo(CO)3(C-Pf3)](Ⅱe2).
    (f)Mixed metal complexes containing iron and VIB metal
    include 4 compounds:[(C5H5)2(CO)2Fe2(Pf-Pf-Pf)](Ⅳ),[(C5H5)2
    (CO)2Fe2(Pf-Pf-Pf)Cr(CO)5](Ⅳ1),[(C5H5)2Fe2(Pf-Pf-Pf)Mo(CO)5]
    (Ⅳ2),[(C5H5)2(CO)2Fe2(Pf-Pf-Pf)W(CO)5](Ⅳ3).
    The reactions of [M(CO)6](M=Cr,Mo,W)or[C5H5Fe(CO)2]2 with

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