[(μ-acetato)bis(μ-acetohydroxamate)bis(N,N,N',N'-tetramethylethylenediamine)dicobalt(II)] trifluoromethanesulfonate | 380357-95-9

• 英文名称: [(μ-acetato)bis(μ-acetohydroxamate)bis(N,N,N',N'-tetramethylethylenediamine)dicobalt(II)] trifluoromethanesulfonate
• 英文别名: (Co2(μ-AA)2(μ-OAc)(tmen)2)(OTf)
• CAS: 380357-95-9；857680-40-1
• 化学式: CF₃O₃S*C₁₈H₄₃Co₂N₆O₆
• 分子量: 706.633
• InChiKey: DBRWNUOHUYZTKY-UHFFFAOYSA-L

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

• 作为产物：
  描述：

  [bis(μ-acetato)bis(μ-aqua)bis(N,N,N',N'-tetramethylethylenediamine)dicobalt(II)] trifluoromethanesulfonate 以 甲醇 为溶剂， 生成 [(μ-acetato)bis(μ-acetohydroxamate)bis(N,N,N',N'-tetramethylethylenediamine)dicobalt(II)] trifluoromethanesulfonate
  参考文献：
  名称：

  Mononuclear and dinuclear model hydrolases of nickel and cobalt

  摘要：

  Reaction between the dinuclear model hydrolases [M-2(mu-OAc)(2)(OAc)(2)(mu-H2O)(tmen)(2)]; M = Ni (1); M = Co (2) and trimethylsilyltrifluoromethanesulphonate (TMS-OTf) under identical reaction conditions gives the mononuclear complex [Ni(OAc) (H2O)(2)(tmen)][OTf]center dot H2O (3) in the case of nickel and the dinuclear complex [CO2(mu-OAC)(2)(mu-H2O)(2)(tmen)(2)][OTf](2) (4) in the case of cobalt.Reaction of (3) with urea gives the previously reported [Ni(OAc)(urea)(2)(tmen)][OTf] (5), whereas (4) gives [CO2(OAC)(3)(urea) (tmen)(2)][OTf] (6) previously obtained by direct reaction of (2) with urea. Both (3) and (4) react with monohydroxamic acids (RHA) to give the dihydroxamate bridged dinuclear complexes [M-2(mu-OAc)(mu-RA)(2)(tmen)(2)][OTf]; M = Ni (7); M = Co (8) previously obtained by the reaction of (1) and (2) with RHA, illustrating the greater ability of hydroxamic acids to stabilize dinuclear complexes over that of urea by means of their bridging mode, and offering a possible explanation for the inhibiting effect of hydroxamic acids by means of their displacing bridging urea in a possible intermediate invoked in the action of urease. (c) 2005 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2005.01.029

文献信息

• Magnetic, Spectroscopic, and Structural Studies of Dicobalt Hydroxamates and Model Hydrolases
  作者：David A. Brown、W. Errington、W. K. Glass、W. Haase、T. J. Kemp、H. Nimir、S. M. Ostrovsky、R. Werner

  DOI：10.1021/ic0103345

  日期：2001.11.1

  The cobalt(II) urease model complex [Co-2(mu -OAc)(3)(urea)(tmen)(2)][OTf] (2) prepared from the cobalt model hydrolase [Co-2(mu -H2O)(mu -OAc)(2)(OAc)(2)(tmen)(2)] (1) undergoes facile reaction with acetohydroxamic acid (ARA) to give the monobridged hydroxamate, complex [Co-2(mu -OAc)(2)(mu -AA)(urea)(tmen)(2)][OTf] (3) while 1 gives the dibridged hydroxamate complex [Co-2(mu -OAc)(mu -AA)(2)(tmen)(2)][OTf] (4). The structures and Co-Co distances of the hydroxamate derivatives of 1 and 2 are very close to those of their nickel analogues and suggest that hydroxamic acids can also inhibit cobalt-based hydrolases as well as inhibiting urease 1 also reacts, with glutarodihydroxamic acid (gluH(2)A(2)) to eliminate hydroxylamine with formation of [CO2(mu -OAC)(2)mu -O(N) (OC)2(CH2)(3)}(tmen)(2)][OTf] (5), the structure of which is very close to that of its, nickel analogue. Both 1 and 3 show weak antiferromagnetic coupling. Oxidation of 1 with H2O2 gives three dicobalt(M) hydroxy complexes (7-9), the first of which [Co-2(mu -OAc)(2)(OAc)(2) mu -OH)(tmen)(2)][OTf] (7) contains a bridging hydroxyl and the second [CO2(mu -OAc)(2)(OAc)(mu -OH)(OH)(tmen)(2)][OTf] (8) containing both a bridging and terminal hydroxyl, while the third [Co-2(mu -OAc): (OAC)(2)(mu -OM)(2)(tmen)(2)][OTf] (9) contains, two bridging OH groups with mixed-valence Co(II)/(Co(III) intermediates.