[Fe2(μ-η1:η3-C(Me)=C(S)C=N(Me)(2,6-Me2C6H3))(μ-CO)(CO)(Cp)2] | 912568-30-0

• 英文名称: [Fe2(μ-η1:η3-C(Me)=C(S)C=N(Me)(2,6-Me2C6H3))(μ-CO)(CO)(Cp)2]
• CAS: 912568-30-0
• 化学式: C₂₅H₂₅Fe₂NO₂S
• 分子量: 515.239
• InChiKey: QONZZOHAVZWEFC-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  二氯甲烷 、 [Fe2(μ-η1:η3-C(Me)=C(S)C=N(Me)(2,6-Me2C6H3))(μ-CO)(CO)(Cp)2] 以 二氯甲烷 为溶剂， 以86%的产率得到[Fe2(μ-η1:η3-Cγ(Me)=Cβ(SCH2Cl)Cα=N(Me)(Xyl))(μ-CO)(CO)(Cp)2][Cl]
  参考文献：
  名称：

  Zwitterionic diiron vinyliminium complexes: Alkylation, metalation and oxidative coupling at the S and Se functionalities

  摘要：

  The zwitterionic vinyliminium complex [Fe(2){mu-eta(1):eta(3)-C(R')=C( S) C=N( Me)( Xyl)}(mu-CO)(CO)( Cp)(2)] ( 2a) ( R' = p-Me-C(6)H(4) ( Tol), Xyl = 2,6-Me(2)C(6)H(3)) undergoes electrophilic addition at the S atom by HSO(3)CF(3), MeSO(3)CF(3), SiMe(3)Cl, BrCH(2)Ph, ICH(2)CH=CH(2) affording the complexes [Fe(2){mu-eta(1):eta(3)-C( Tol)=C( SX)C=N (Me)(Xyl)}(mu-CO)( CO)(Cp)(2)][Y] ( X = H, Y = SO(3)CF(3), 4a; X = Me, Y = SO(3)CF(3), 4b; X = SiMe(3), Y = Cl, 4c; X = CH(2)Ph, Y = Br, 4d; X = CH(2)CH=CH(2), Y = I, 4e).Compound 2a and the corresponding vinyliminium complexes 2b and 2c ( R' = CH(2)OH, 2b; R' = Me, 2c) react also with etherated BF(3) leading to the formation of the corresponding S-adducts [ Fe(2){mu-eta(1):eta(3)-C( R')=C( SBF(3)) C=N( Me)( Xyl)}(mu-CO)(CO)(Cp)(2)] (R' = Tol, 5a; R' = CH(2)OH, 5b; R' = Me, 5c).In analogous reactions, the zwitterionic vinyliminium complexes undergo S-metalation upon treatment with in situ generated [Fp](+)[ SO(3)CF(3)] [Fp = Fe( CO)(2)(Cp)], leading to the formation of [ Fe(2){mu-eta(1):eta(3)-C( R')=C(S-Fp) C=N( Me)( Xyl)}(mu-CO)( CO)(Cp)(2)][ SO(3)CF(3)](R' = CH(2)OH, 6a; R' = Me, 6b; R' = Bu(n), 6c).Similarly, zwitterionic vinyliminium containing Se in the place of S also undergo Se-electrophilic addition. Thus, the complexes [ Fe(2){mu-eta(1):eta(3)-C( R')=C( SeX)C=N( Me)( R)}(mu-CO)( CO)( Cp)(2)][SO(3)CF(3)] (R = X = Me, R' = Tol, 7a; R = Xyl, R' = Me, X = Fp(+), 7b) are obtained upon treatment of the neutral zwitterionic precursors with MeSO(3)CF(3) and [ Fp][ SO(3)CF(3)], respectively.Alkylation at the S or Se atom of the bridging ligand is also accomplished by CH(2)Cl(2), used as solvent, although the reaction is slower compared to more efficient alkylating reagents. The complexes formed by this route are [ Fe(2){mu-eta(1):eta(3)-C(R')=C(E-CH(2)Cl) C=N( Me)(R)}(mu-CO)( CO)(Cp)(2)][ X] [ E = S, R = Xyl, R' = Tol, X = Cl, 8a; E = S, R = Xyl, R' = Me, X = Cl, 8b; E = Se, R = R' = Me, X = BPh(4), 8c].Finally, treatment of the zwitterionic vinyliminium complexes with I(2) results in the oxidative coupling with formation of S-S (disulfide) or Se-Se (diselenide) bond. The reactions, performed in the presence of NaBPh(4) afford the tetranuclear complexes [Fe(2){mu-eta(1):eta(3)-C(R')=C(E)C=N( Me)( R)}(mu-CO)(CO)(Cp)(2)](2)[BPh(4)](2) [R=Xyl, R' = CH(2)OH, E = S, 9a; R = Xyl, R' = Me, E = S, 9b; R = Xyl, R' = Bu(n), E = S, 9c; R = Xyl, R' = Me, E = Se, 9d; R = Me, R' = Bu(n), E = Se, 9e].The molecular structures of 4a, 8c and 9e have been determined by X-ray diffraction studies. (C) 2008 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2008.04.010
• 作为产物：
  描述：

  1,2,3,4,5,6,7,8-八硫杂环辛烷 、 [Fe2(μ-η1:η3-Cγ(Me)Cβ(H)CαN(Me)(C6H3-2,6-Me2))(μ-CO)(CO)(η5-cyclopentadienyl)2][SO3CF3] 在 NaH 作用下， 以 四氢呋喃 为溶剂， 以72%的产率得到[Fe2(μ-η1:η3-C(Me)=C(S)C=N(Me)(2,6-Me2C6H3))(μ-CO)(CO)(Cp)2]
  参考文献：
  名称：

  Diiron配合物中前所未有的两性离子亚胺基硫族化合物桥联配体

  摘要：

  该二铁vinyliminium络合物的[Fe 2 {μ-η 1：η 3 -C（R'）CHC N（Me）的（R）}（μ-CO）（CO）（CP）2 ] [SO 3 CF 3 ] [ R = Xyl，R'= Me，1a ; R = Xyl，R'= Tol，1b ; R = Xyl，R'= CO 2 Me，1c；R = Xyl，R'= CH 2 OH，1d；R = Xyl，R'= Bu n，1e ; R =我，R'=我，1f ; R = Me，R'= Tol，1g；R = Me，R'= CO 2 Me，1h；R =我，R'= Bu n，1i; R = Me，R'= CH 2 OH，1l；R = p -C 6 H 4 -CN，R'= Tol，1m ; R = p -C 6 H 4 -OMe，R'= Me，1n；Tol = 4-C 6 H 4 -Me; 的Xyl = 2,6-ME 2 ç 6 ħ 3

  DOI：

  10.1021/om060550r