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:280 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