[Et4N]2[EFe3(CO)9] (E = S、Se、Te) 與 HC CCH2Br 反應可生成有趣的烯丙基醯基配位的產物: [Et4N][(m2-S)Fe3(CO)9(m2-h1:h3- C(O)C(H)CCH2) 以及 [Et4N][(m3-E)Fe3(CO)9(m3-h1:h1:h3- C(O)C(H)CCH2) (E = Se、Te ) ;若於反應最初通入 CO 氣體,均可使產物的產率明顯提高 ; 若將產物進一步與醯氯試劑 MeC(O)Cl 於低溫下 (-90 ~ -95℃) 反應,分別可以得到乙醯基成功配位的含酯基金屬碳烯化合物: (m2-S)Fe3(CO)9(m3-h2:h3:h1-C(OC(O)CH3)C(H) CCH2)以及(m2-Se)Fe2(CO)6(m2-h2:h1-C(OC(O)CH3)C(H)CCH2) ;若於合成的過程中通入 CO 氣體,也可使上述化合物的產率提高。此外,將對此一系列 CO 氣體扮演的角色,做反應機構上的推導及研究。 而 [Et4N]2[EFe3(CO)9] (E = S、Se、Te) 與雙鹵化合物 X(CH2)nX (Br(CH2)3Cl、I(CH2)4I、Br(CH2)5Br) 反應 ;在 S 的系統中,可得到一系列單取代產物 [Et4N][SFe3(CO)9(CH2)nX] (-(CH2)nX = -(CH2)3Cl、-(CH2)4I、-(CH2)5Br) ;而在 Se 及 Te 的系統中卻只能得到氧化性產物 [Et4N][HSeFe3(CO)9] 及 Fe2(CO)6(m-Te(CH2)3Te)。 若以 [Et4N]2[EFe3(CO)9] ( E = S、Se、Te ) 與 Hg(OAc)2 反應則可得到以Hg當作橋基的產物 [Et4N]2[{EFe3(CO)9}2Hg] (E = S、Se、Te) ,並發現此兩化合物在溶液中藉由加入有機試劑可互相轉變的情形。所有新的化合物均利用X-ray繞射解析、元素分析鑑定其結構,含有有機配位基的化合物則使用核磁共振光譜儀輔助鑑定其結構。
The reactions of [EFe3(CO)9]2- (E = S, Se, Te) with HC CCH2Br produce the novel clusters [(m2-S)Fe3(CO)9(m2-h1:h3-C(O)C(H)CCH2)]- and [(m3-E)Fe3(CO)9(m3-h1:h1:h3-C(O)C(H)CCH2)]- (E = Se, Te ), respectively, the yields of which are significantly increased upon the bubbling of CO. When [EFe3(CO)9(COC3H3)]- (E = S, Se) are treated with CH3C(O)Cl, two new novel acetate metal carbene compounds; (m2-S)Fe3(CO)9-(m3-h2:h3:h1-C(OC(O)CH3)C(H)CCH2) and (m2-Se) -Fe2(CO)6(m2-h2:h1-C(OC(O)CH3)C(H)CCH2) are obtained. Similarly, the yields of these two compounds are increased upon the bubbling of CO. The reaction of [SFe3(CO)9]2- with organic dihalides (X(CH2)nX = Br(CH2)3Cl, I(CH2)4I, Br(CH2)5Br) produces the mono-substituted complexes [SFe3(CO)9(CH2)nX]- (-(CH2)nX = -(CH2)3Cl, -(CH2)4I, -(CH2)5Br). However, in the case of Se, only the oxidized product [HSeFe3(CO)9]- is obtained. In the case of Te, the reaction with Br(CH2)3Cl produces the -(CH2)3- bridged product Fe2(CO)6(m-Te(CH2)3 Te). The reactions of [EFe3(CO)9]2- (E = S, Se, Te) with Hg(OAc)2, produce the Hg bridged compounds [{EFe3(CO)9}2Hg] (E= S, Se, Te). All the new compounds are fully characterized by IR , NMR , elemental analysis , or/ and X-ray diffraction methods.