含硒、碲之過渡金屬(錳、鐵、釕)團簇化合物之合成及其物性、化性研究

楊惠雅(Huey-Yea Yang)

指導教授 ： 謝明惠

國立臺灣師範大學/理學院/化學系/碩士(1999年)

摘要

[1]含鐵(Fe)系統研究─
以[SeFe3(CO)9(COC3H3)]–為起始物與Ru3(CO)12依莫耳數1：1的比例，於丙酮中加熱反應可得SeRu4(CO)11(C3H3)及[Fe3(CO)9(C3H3)]–。當提高比例至1：1.67時，於甲醇、氰化烷及丙酮混合溶液中加熱，可得[HSeRu3(CO)9]–及[Ru6(CO)16C]2–。
運用理論計算來比較已知化合物(m3-E)Fe3(CO)9(m3-η2:η1:η3-
C(COCH3)(H)CCH2) (E = Se或Te)、Te2Fe2(CO)6(CHCCH2)2及Te2Fe2(CO)6(CHCCH2)(CH2C≡CH)，其不同構形在能量上的差異。
[2]含釕(Ru)系統研究─
以Na2SeO3與Ru3(CO)12為起始物，依原子數比1：2.5於甲醇溶液中加熱，會產生一有趣結構的錯合物[Se4Ru10(CO)24(O2CCH3)]3–，因而激發其相關的高壓反應催化研究。再將此起始物於PPh3及CO的存在下加熱，則產生Ru3(CO)9(PPh3)3．THF；若只是在CO存在下加熱，則會得到[HSeRu3(CO)9]–。
[3]含錳(Mn)系統研究─
[Te2Mn4(CO)12]2–與Hg(OAc)2或者[Te2Mn3(CO)9]2–與Cu+ 進行反應，均可氧化得到一個三角雙錐結構的[Te2Mn3(CO)9]–。若[Te2Mn4-
(CO)12]2- 與過量Hg(OAc)2反應則會進一步產生雙錳化合物[Mn2(CO)6(m-OCOCH3)3]–。另一雙錳化合物[Mn2(CO)6(m-OCH3)3]–，則是利用[Te2Mn3(CO)9]–與4 M KOH於CH2Cl2/MeOH中反應生成。又[Te2Mn3(CO)9]2–/–、[Te2Mn4(CO)12]2–與Ru3(CO)12在不同條件下均會生成[HTeRu3(CO)9]–。另外由K2TeO3．H2O與Mn2(CO)10的反應系統中，得一結構特殊的化合物[Te4Mn6(CO)20] 2–．CH2Cl2。
利用電化學分析研究[E2Mn3(CO)9]–、[E2Mn3(CO)9]2–、[E2Mn4-
(CO)12]2-及[EFe3(CO)9]2–(E = S、Se或Te)的氧化還原性質。

關鍵字

過渡金屬(錳、鐵、釕)團簇化合物

並列摘要

[1]in Fe-system
The reaction of [SeFe3(CO)9(COC3H3)]– with Ru3(CO)12 in a molar ratio of 1:1 in acetone solution at 50℃ produces SeRu4(CO)11(C3H3) and [Fe3(CO)9(C3H3)]– . If the molar ratio of 1:1.67 is employed in refluxing MeOH/CH3CN/acetone mixed solutions, two different products, [HSeRu3(CO)9]– and [Ru6(CO)16C]2– , are obtained.
The minimal potential energies of the different conformations of the known compounds, (m3-E)Fe3(CO)9(m3-η2:η1:η3-C(COCH3)(H)CCH2) (E = Se or Te)、Te2Fe2(CO)6(CHCCH2)2 and Te2Fe2(CO)6(CHCCH2)(CH2C≡CH) are calculated and compared by Insight II program.
[2]in Ru-system
The treatment of Na2SeO3 and Ru3(CO)12 in an atom ratio of 1:2.5 in MeOH solution at 81℃ affords an interesting green cluster, [Se4Ru10-(CO)24(O2CCH3)]3- , which prompts us to explore the catalytic carbonylation of MeOH. If the reaction is pressurized with CO, [HSeRu3(CO)9]– is obtained. When the reaction is carried out in the presence of PPh3, Ru3(CO)9(PPh3)3．THF is yielded.
[3]in Mn-system
Trigonal bipyramidal cluster [Te2Mn3(CO)9]– can be prepared by oxidation of [Te2Mn4(CO)12]2– or [Te2Mn3(CO)9]2– . [Te2Mn3(CO)9]– can be further oxidized to form the dimanganese compound [Mn2(CO)6(m-OC(O)CH3)3]– or [Mn2(CO)6(m-OCH3)3]– under different conditions. On the other hand, the reaction of [Te2Mn3(CO)9]2–/– or [Te2Mn4(CO)12]2– with Ru3(CO)12 under different conditions leads to the formation of the triruthenium cluster [HTeRu3(CO)9]– . A novel new cluster, [Te4Mn6(CO)20] 2–．CH2Cl2, is synthesized from the reaction of K2TeO3．H2O and Mn2(CO)10.
Finally, the redox reactions of a series of clusters [E2Mn3(CO)9]–, [E2Mn3(CO)9]2– , [E2Mn4(CO)12]2- and [EFe3(CO)9]2– (E = S、Se or Te) are studied and compared by cyclic voltammetry
.

並列關鍵字

metal cluster

參考文獻

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