含硫三鐵錯合物 [SFe3(CO)9]2- 的化性研究與新系列 15 族-鉻錯合物的合成開發與相關反應探討

Abstract

[[abstract]]Abstract 1. S/Fe/CO System The reaction of Na2SO3 with Fe(CO)5/KOH in methanol forms the tetrahedral cluster [Et4N]2[SFe3(CO)9] (1) in good yield. Acidification of 1 with H+ forms the monohydrido cluster [Et4N][SFe3(m-H)(CO)9] and the dihydrido cluster SFe3(m-H)2(CO)9. Further methylation of 1 with CF3SO3CH3 produces the sulfur-methylated cluster [Et4N][MeSFe3(CO)9] (2). However, the reaction of 1 with BrCH2C(O)OCH3 forms [Et4N][SFe3(CO)8(m-CO)(CH2C(O)OCH3)] (3), in which the organic ligand CH2C(O)OCH3 bonds with Fe atom. When 1 is treated with Ru3(CO)12 in refluxing acetone, the octahedral cluster [Et4N]2[SFe2Ru3- (CO)14] (4) is obtained. Subsequent methylation of 4 with CF3SO3CH3 gives the octahedral cluster [Et4N][MeSFe2Ru3(CO)14] (5), in which the sulfur atom is pentacoordinated to one methyl group and two Ru and two Fe atoms. The reaction of 1 with propargyl bromide in CH3CN affords three novel products, (m3-S)Fe3(CO)9(m3-h1:h2:h1-C(H)=C(CH3)) (6), SFe2(CO)6(m2-h1:h2-CH=C(CH3)C(O)) (7) and the heterotetranuclear metal-(acylallenyl) complexes [Et4N][(m2-S)Fe3(CO)9(m2-h1:h3-C(O)- C(H)=C=CH2)] (8). When 8 is treated with [Cu(CH3CN)4][BF4], 6 and SFe2(CO)6(m2-h1:h2-C(O)CH=C(CH3)) (9) are obtained. Further reaction of 8 with CF3SO3CH3 yields the methylated cluster (m2-S)Fe3(CO)9(m3-h2:h2:h1-C(OCH3)C(H)=CCH2) (10). 2. Bi/Fe/CO System When [Et4N]2[Bi4Fe4(CO)13] is treated with Fe(CO)4(NCCH3), the expected product [Et4N]2[Bi4Fe5(CO)17] is obtained. Further treatment of [Et4N]2[Bi4Fe4(CO)13] with [Mn(CO)5(CH3CN)][PF6] forms the mixed-metal cluster [Et4N][Bi4Fe3Mn(CO)14] (11) instead of the expected complex [Et4N]2[Bi4Fe4Mn(CO)18]. 3. E/Cr/CO (E = As, Sb, Bi) System The new series of trigonal-pyramidal chromium complexes [Et4N]2[HE{Cr(CO)5}3] (E = As, 13a; Sb, 13b) are obtained from the reaction of E2O3 (E = As, Sb) with Cr(CO)6 in concentrated KOH methanolic solution. These are the first examples of group 6 complexes containing E-H fragment (E = As, Sb). In As case, we also obtain the dihydrido complex [Et4N][H2As{Cr(CO)5}2] (12). Subsequent reaction of 13a with RBr (R = PhCH2, HCoCCH2) forms the addition products [Et4N][(R)(Br)As{Cr(CO)5}2] (R = PhCH2, 14; CH3CoC, 15) and [BrCr(CO)5]-. However, 13b reacts with RX (R = PhCH2, X = Br; R = CH3(CH2)5C(O), X = Cl) respectively to produce the haloantimony complexes [XSb{Cr(CO)5}3]2- (X = Br, Cl). The mixed dihaloantimony complex [Bu4N][BrISb{Cr(CO)5}2] (17) can be produced from the bromoantimony complex [Bu4N]2[BrSb{Cr(CO)5}3] with CH2I2. However, if [Et4N]2[BrSb{Cr(CO)5}3] is treated with CH3C(O)Cl, a dicholoantimony complex [Et4N][Cl2Sb{Cr(CO)5}2] (16) is obtained instead of the expected mixed bromocholoantimony complex. The treatment of Na2BiO3 with Cr(CO)6 in concentrated KOH methanolic solution at low temperature (<20℃) gives the trianion complex [Et4N]3[Bi{Cr(CO)5}4] (18). If the reaction is at higher temperature (>30℃), the purple-red complex [Et4N]2[MeBi{Cr(CO)5}3] (19) is obtained, in which the methyl group is from methanol. When 18 is treated with RI (R = Me, Et), the bismuth-alkylated cluster [Et4N]2[RBi{Cr(CO)5}3] is obtained. Further reaction of 18 with CH2Cl2 produces the cholobismuth complex [Et4N]2[ClBi{Cr(CO)5}3] (20). Subsequent reaction of 19 with MeI yields [Et4N][Me2Bi{Cr(CO)5}2] (21).