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首页> 外文期刊>Zeitschrift fur Anorganische und Allgemeine Chemie >Synthesis and Charactertzation of Mononuclear and Dinuclear Manganese Bis-acetylide Complexes
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Synthesis and Charactertzation of Mononuclear and Dinuclear Manganese Bis-acetylide Complexes

机译:单核和双核锰双乙炔化物配合物的合成与表征

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The symmetric d(5) trans-bis-alkynyl complexes {Mn[(Me)(2)P(CH2)(n)P(Me)(2)](2)(C CC6H4R)(2)} (n = 2, R = -C CTIPS (2a); n = 3, R = -C CTIPS (2b); n = 2, R = F (4); n = 3; -C CTIPS) were prepared by the reaction of [Mn(dmPe)(2)Br-2] with two equivalents of the corresponding acetylide LiC CC6H4R (R = F, -C CTIPS). The reaction of compounds 2a, 2b and 4 with [Cp2Fe][PF6] yielded the corresponding d(4) complexes {Mn[(Me)(2)P(CH2)(n)P(Me)(2)](2)(C CC6H4R)(2)}[PF6] (n = 2, R =-C CTIPS, [2a](+); n = 3, R = -C CTIPS, [2b](+); n = 2, R = F, [4](+); n = 3; -C CTIPS). The unsymmetrically substituted trans-iodo-alkynyl complex [IMn(dmPe)(2)(C CC6H4-C CTIPS)] (5) was obtained by treating MeCpMn(dmpe)l with one equivalent of H-C CC6H4-C CTIPS in the presence of dmpe. Deprotection of the TIPS group with TBAF gave complex [IMn(dmPe)(2)(C CC6H4-C CTIPS)] (6) in 94 % yield. The neutral dinuclear complexes Mn-II/Mn-II compounds {[Mn((Me)(2)P(CH2CH2)P(Me)(2))(2)(C CC6H4R)](2)(mu-C-4)} (R = H, Me, n-pentyl, F) were prepared by the direct reaction of {Mn((Me)(2)P(CH2CH2)P(Me)(2)l](2)(mu-C-4)} with the corresponding LiC CC6H4R (R = H, n-pentyl, F). These Mn-II/Mn-II dinuclear compounds were further oxidized to the mixed-valent complexes and the dicationic complexes using [Cp2Fe][PF6]. All complexes have been characterized by NMR, IR, and Raman spectroscopy. X-ray diffraction studies were carried out on complexes 1c, 2a, 4, [4](+), and 6.
机译:对称的d(5)反式双炔基络合物{Mn [(Me)(2)P(CH2)(n)P(Me)(2)](2)(C CC6H4R)(2)}(n =式中,通过[1]的反应制备2,R = -C CTIPS(2a); n = 3,R = -C CTIPS(2b); n = 2,R = F(4); n = 3; -C CTIPS)。 Mn(dmPe)(2)Br-2]和两个等价的相应乙炔LiC CC6H4R(R = F,-C CTIPS)。化合物2a,2b和4与[Cp2Fe] [PF6]反应生成相应的d(4)配合物{Mn [(Me)(2)P(CH2)(n)P(Me)(2)](2 )(C CC6H4R)(2)} [PF6](n = 2,R = -C CTIPS,[2a](+); n = 3,R = -C CTIPS,[2b](+); n = 2 ,R = F,[4](+); n = 3; -C CTIPS)。不对称取代的反式-碘-炔基络合物[IMn(dmPe)(2)(C CC6H4-C CTIPS)](5)是通过在存在以下条件下用一当量的HC CC6H4-C CTIPS处理MeCpMn(dmpe)l来获得的dmpe。用TBAF对TIPS基团进行脱保护得到了复合物[IMn(dmPe)(2)(C CC6H4-C CTIPS)](6),产率为94%。中性双核配合物Mn-II / Mn-II化合物{[Mn((Me)(2)P(CH2CH2)P(Me)(2))(2)(C CC6H4R)](2)(mu-C- 4)}(R = H,Me,正戊基,F)是通过{Mn((Me)(2)P(CH2CH2)P(Me)(2)l](2)(mu -C-4)}和相应的LiC CC6H4R(R = H,正戊基,F)。这些[Mn-II / Mn-II]双核化合物进一步被[Cp2Fe]氧化成混合价配合物和双键配合物[PF6]。所有配合物均已通过NMR,IR和拉曼光谱表征,对配合物1c,2a,4,[4](+)和6进行了X射线衍射研究。

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