含第十六族主族元素(S、Se、Te)三鐵錯合物與有機及無機試劑反應性之研究探討

• Main Author: 李長儒
• Other Authors: Shieh, Minghuey
• Format: Others
• Language: zh-TW
• Published: 2003
• Online Access: http://ndltd.ncl.edu.tw/handle/67953855946030199544

碩士 === 國立臺灣師範大學 === 化學研究所 === 91 === In the E-Fe-CO system, when [Et4N]2[EFe3(CO)9] (E = S (1), Se (2), Te (3)) react with C3H3Br, two different types of compounds formulated as [Et4N][(2-S)Fe3(CO)9(2-1:3-C(O)C(H)CCH2)] (4) and [Et4N][(2 -E)Fe3(CO)9(3-1:1:3-C(O)C(H)CCH2)] (E = Se (5), Te (6)) are obtained, respectively. The reactions of those compounds with HCl give a series of neutral compounds SFe3(CO)9(C3H4), SFe2(CO)6(C(O)C(CH3) -CH), SeFe3(CO)9(C3H4), SeFe2(CO)6(C(O)C(CH3)CH), and Te2Fe3(CO)9. The possible reaction pathway was attempted to be understood by the employment of DCl as the acid source. When compound 4 is treated with acid chlorides, a series of ester-containing neutral compounds SFe3(CO)9(C(OC(O)R)C3H3) (R = CH2Ph, (CH2)5CH3) are generated. In the E-Fe-Cu-CO system, a series of monocopper, dicopper, tetracopper-incorporated E-Fe clusters have been synthesized. When [Et4N]2[EFe3(CO)9] (E = S, Se, Te) react with CuX (X = Cl, Br, I) in different ratios, the monocopper-bridged complexes [Et4N]2[EFe3(CO)9 -(μ2-CuX)] (E = S, Se, Te; X = Cl, Br, I), the dicopper complexes [Et4N]2[(μ3-Se)Fe3(CO)9(μ3-CuX)2] (X = Cl, Br) and [Et4N]2[(μ4 -Te)Fe3(CO)9(μ2-CuX)2] (X = Cl, Br, I) and the tetracopper complexes [Et4N]2[{SeFe3(CO)9}2Cu4X2] (X = Cl, Br), and [Et4N]2[{SFe3(CO)9(μ2- CuCl)}2(CuX)2] (X = Cl, Br) are obtained. When [Et4N]2[TeFe3(CO)9] is treated with [Cu(CH3CN)4]+ and dppm, a novel complex (μ5-Te)Fe3(CO)9Cu2(μ-dppm)(CH3CN) is yielded with the novel μ5-Te bonding mode. In the S-Mn-Cr system, reaction of S powder and Mn2(CO)10 in KOH/MeOH solution produces a trigonal bypramidal complex [S2Mn3(CO)9]- which can incorporate with Cr(CO)6/KOH to give the scoop-like complex [HS2Mn3Cr(CO)14]2- that can proceed further to form the octahedral complex [S2Mn3Cr(CO)12]2-.