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

何莉芳(Li-Fang Ho)

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] 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] 。

關鍵字

團簇化合物 ； 羰基

並列摘要

[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.

並列關鍵字

cluster ； carbonyl

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