bis-(kemp's triacid imide)

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: bis-(kemp's triacid imide)
• 英文别名: 3-[5-(7-Carboxy-1,5,7-trimethyl-2,4-dioxo-3-azabicyclo[3.3.1]nonan-3-yl)-2,4-dimethylphenyl]-1,5,7-trimethyl-2,4-dioxo-3-azabicyclo[3.3.1]nonane-7-carboxylic acid
• 化学式: C₃₂H₄₀N₂O₈
• 分子量: 580.678
• InChiKey: CJHROTDIOMOYLJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  42
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  149
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  bis-(kemp's triacid imide) 在 NaOH 作用下， 以 甲醇 为溶剂， 生成
  参考文献：
  名称：

  Mono- and Dinuclear Zinc Complexes of XDK, H2XDK = m-Xylenediamine Bis(Kemp's triacid imide), and Their Reaction with Phosphate Esters

  摘要：

  The reaction of Zn(NO3)(2) . 6H(2)O with H(2)XDK and NaOH afforded the mononuclear zinc complex, [Zn(XDK)-(H2O] (1), in good yield. Treatment with pyridine converted complex 1 to [Zn(XDK)(py)(2)]. H2O (2 . H2O), which was characterized by X-ray crystallography (2 . CHCl3: monoclinic, P2(1)/c, a 12.324(4) Angstrom, b = 14.902(3) Angstrom c = 24.674(5) Angstrom, beta = 102.86(3)degrees, V = 4418(2) Angstrom(3), Z = 4, and R = 0.088 and R(w) = 0.089 for 3833 independent reflections having I > 3 sigma(I)). Complex 2 has two Zn-O and two Zn-N bonds at average distances of 2.04 and 2.07 Angstrom, respectively, contributed by a distorted XDK and two pyridine ligands. There is also a longer interaction to a third oxygen atom of the XDK ligand, Zn-O = 2.39 Angstrom. Recrystallization of 2 . H2O from a methanol/pyridine mixed solvent gave {Zn(eta(1)-carboxylato)(2)(py)(2)} (2'), which was isolated and structurally characterized (2'. CH3OH: monoclinic, P2(1)/n, a 12.257(2) Angstrom, b = 16.448(2) Angstrom, c = 20.432(3) Angstrom, beta = 103.46(1)degrees, V = 4006.0(9) Angstrom(3), Z = 4, and R = 0.048 and R(w) = 0.054 for 4140 independent reflections with I > 3 sigma(I)). Complex 1 readily reacted with Zn(NO3)(2) . 6H(2)O to give the dizinc complex, [Zn-2(XDK)(NO3)(2)(CH3OH)(H2O)(2)] (3), and a similar reaction in the presence of pyridine gave [Zn-2(XDK)(py)(2)(NO3)(2)]. 2H(2)O (4 . 2H(2)O). Complex 4 was characterized by X-ray crystallography (4 . CH(2)Cl(2)Et(2)O: monoclinic, P2(1)/n, a = 17.938(3) (A)ngstrom, b = 21.232(4) Angstrom, c = 15.436(3) Angstrom, beta = 112.48(1)degrees, V = 5432(2) Angstrom(3), Z = 4, and R = 0.072 and R(w) = 0.082 for 3590 independent reflections with I > 3 sigma(I)). The Zn ... Zn separation is 3.739(2) Angstrom, and both zinc atoms adopt a tetrahedral geometry. When complex 1 was treated with Zn(acac)(2) .2H2O, the asymmetrical dinuclear zinc complex, [Zn-2(XDK)(acac)(2)(CH3-OH)(2)]. H2O (5 . H2O), was obtained in good yield. An X-ray crystallographic analysis revealed a dizinc structure bridged by XDK and acac ligands; one zinc atom has trigonal bipyramidal geometry, and the other, octahedral geometry. The Zn ... Zn interatomic distance is 3.463(1) Angstrom (5: monoclinic, P2(1)/c, a = 17.629(3) Angstrom, b = 12.373(1) Angstrom, c 21.731(4) Angstrom, beta = 90.11(2)degrees, V = 4740(1) Angstrom(3), Z = 4, and R = 0.049 and R(w) = 0.054 for 5137 independent reflections with I > 3 sigma(I)). Reaction of complex 3 with phosphate ester salts NaC{RO)(2)PO2}, R = Ph or p-NO2-Ph, yielded the phosphate-bridged dinuclear zinc complexes, [Zn-2(XDK){mu-(RO)(2)PO2}(CH3OH)(2)](NO3) (6a, R = Ph; 6b, R = p-NO(2)Ph), which were further transformed into [Zn-2(XDK)mu-{RO)(2)PO2}(py)(2)(NO3) (7a, R = Ph; 7b, R = p-NO(2)Ph) by treatment with pyridine.These phosphate ester-bridged dizinc compounds are structural models for postulated intermediates in the mechanism proposed for phosphate ester hydrolysis by Escherichia coli alkaline phosphatase and DNA polymerase I, both of which contain a pair of zinc atoms in their active sites.

  DOI：

  10.1021/ic00120a030

文献信息

• Carboxylate-Bridged Diiron(II) Complexes:  Synthesis, Characterization, and O₂-Reactivity of Models for the Reduced Diiron Centers in Methane Monooxygenase and Ribonucleotide Reductase
  作者：Susanna Herold、Stephen J. Lippard

  DOI：10.1021/ja9628563

  日期：1997.1.1

  Diiron(II) complexes with an oxygen-rich coordination environment were assembled with the dinucleating dicarboxylate ligands m-xylylenediamine bis(Kemp's triacid)imide (H2XDK) and the more soluble analogue m-xylylenediamine bis(propyl Kemp's triacid)imide (H2PXDK). X-ray crystallographic analysis revealed that, in most of the complexes, only one monodentate N-donor ligand is bound to each iron(II)

  具有富氧配位环境的二铁 (II) 配合物与双核二羧酸配体间苯二甲胺双（坎普三酸）亚胺（H2XDK）和更易溶解的类似物间苯二甲胺双（丙基坎普三酸）亚胺（H2PXDK）组装在一起。X 射线晶体学分析表明，在大多数配合物中，只有一个单齿 N 供体配体与每个铁 (II) 离子结合。除了 XDK 和 PXDK 之外，还有多种其他配体桥接双金属核，包括氯化物、氟化物、三氟甲磺酸盐或羧酸盐。三（羧酸盐桥接）配合物 [Fe2(μ-XDK)(μ-O2CPh)(ImH)2(O2CPh)(MeOH)] (3) 和 [Fe2(μ-O2CC(CH3)3)(μ-PXDK )(N-MeIm)2(O2CC(CH3)3)] (4) 与甲烷单加氧酶 (MMO) 的羟化酶成分和核糖核苷酸还原酶 (RNR) 的 R2 蛋白中的二铁 (II) 核心具有相同的配体组成）。3和4中两个铁中心的配位环境是不等价的，一个铁是6配位的，另一个是4配位的。桥
• Carboxylate-Bridged Diiron(II) Complexes, Including a New Model for Reduced Methane Monooxygenase Hydroxylase and the R2 Protein of Ribonucleotide Reductase
  作者：Susanna Herold、Laura E. Pence、Stephen J. Lippard

  DOI：10.1021/ja00127a032

  日期：1995.6
• Dinuclear Manganese(II) Complexes with the {Mn2(.mu.-carboxylato)2}2+ Core and Their Transformation to (.mu.-Oxo)bis(.mu.-carboxylato)dimanganese(III) Complexes
  作者：Tomoaki Tanase、Stephen J. Lippard

  DOI：10.1021/ic00122a027

  日期：1995.8

  Dinuclear Mn(II) complexes having a substitutionally labile Mn-2(mu-carboxylato)(2)}(2+) core were readily synthesized by using the dinucleating ligand XDK, where H(2)XDK = m-xylenediamine bis(Kemp's triacid imide). Reaction of Mn(NO3)(2) . 6H(2)O With Na(2)XDK .4H2O resulted in quantitative formation of [Mn-2(XDK)(NO3)(CH3OH)(4)(H2O)(2)]-(NO3) (1), which was characterized by X-ray crystallography (monoclinic, P2(1)/c, a = 11.226(1) Angstrom, b = 13.120-(1) Angstrom, c = 30.467(3) Angstrom, beta = 98.739(8)degrees, V = 4435.2(7) Angstrom(3), Z = 4, and R = 0.034 and R(w) = 0.045 for 4957 independent reflections with I > 3 sigma(I)). The cation in 1 contains two octahedral Mn(II) ions bridged by the two carboxylate groups of XDK (Mn...Mn = 4.8497(7) Angstrom), the terminal positions being occupied by labile solvent molecules and a nitrate anion. Compound 1 proved to be a good precursor for preparing a series of bis(mu-carboxylato)dimanganese(II) complexes with N-donor bidentate terminal ligands. Reaction of 1 with 2,2'-dipyridyl (bpy), 4,4'-dimethyl-2,2'-dipyridyl (4,4'-Me(2)bpy), or 1,10-phenanthroline (phen) afforded [Mn-2(XDK)-L(2)(NO3)(2)(H2O)] (L = bpy (2), 4,4'-Me(2)bpy (3), or phen (4)) in high yields. The structure of 2 . CH2Cl2 was shown by X-ray crystallography to have an asymmetric dinuclear Mn(II) core bridged by XDK with a Mn...Mn distance of 4.557(2) Angstrom. One Mn(II) atom adopts an octahedral geometry while the other has a distorted trigonal bipyramidal environment (monoclinic, P2(1)/c, a = 14.491(2)Angstrom b = 17.954(2) Angstrom c = 22.492(3) Angstrom, beta = 108.787-(9)degrees, V = 5537(1) Angstrom(3), Z = 4, and R = 0.055 and R(w) = 0.058 for 4438 independent reflections with I > 3 sigma(I)). Compounds 2 and 3 are readily oxidized by excess tert-butyl hydroperoxide in methanol to afford (mu-oxo)bis(mu-carboxylato)dimanganese(III) complexes, [Mn-2(mu-O)(XDK)L(2)(NO3)(2)] (L = bpy (5) and 4,4'-Me(2)bpy (6)). The crystal structure of 6 . 2.5CH(3)OH revealed two octahedral Mn(III) ions symmetrically bridged by two carboxylate groups of XDK and an oxo ligand. The metal-metal separation is 3.170(2) Angstrom, and the two 4,4'-Me(2)bpy ligands lie in anti arrangement with respect to the Mn-O-Mn plane (orthorhombic, Pbcn, a = 41.636(9) Angstrom, b = 13.108-(1) Angstrom, c = 22.422(9) Angstrom, V = 12237(2) Angstrom(3), Z = 8, and R = 0.073 and R(w), = 0.085 for 3731 independent reflections with I > 3 sigma(I)). Complexes 5 and 6 could be prepared in low yields by air oxidation of 2 and 3, respectively, a reaction that was readily reversed by treatment with hydrogen peroxide. Reaction of 2-4 with an excess amount of hydrogen peroxide quite slowly evolved dioxygen, whereas the solvento dimanganese(II) compound 1 efficiently disproportionated hydrogen peroxide by first converting to a heterogeneous catalyst. A mononuclear complex, [Mn(HXDK)(2)(H2O)(2)] (7), prepared independently, and MnO2 were isolated from the heterogeneous mixture, and the latter was shown to be the active species for disproportionating hydrogen peroxide.
• Steinhuebel, Dietrich P.; Fuhrmann, Peter; Lippard, Stephen J., Inorganica Chimica Acta, 1998, vol. 270, # 1-2, p. 527 - 536
  作者：Steinhuebel, Dietrich P.、Fuhrmann, Peter、Lippard, Stephen J.

  DOI：——

  日期：——
• Alkali metal-responsive geometric and spectral changes in a cobalt(II) complex of a constrained dicarboxylate: a carboxylate shift-mediated metallochromoionophore
  作者：Stephen P. Watton、Mindy I. Davis、Laura E. Pence、Julius Rebek、Stephen J. Lippard

  DOI：10.1016/0020-1693(95)90061-a

  日期：1995.7

  A mononuclear Co(II) complex of the convergent dicarboxylate ligand xylenediamine bis-(Kemp's triacid imide) (XDK) and neocuproine (neo, 2,9-dimethyl-1,10-phenanthroline) has be en prepared both by demetallation of a dinuclear precursor with neocuproine and by direct synthesis. The X-ray structure of this complex, [Co(XDK)(neo)]. 3CH(3)OH (1 . 3CH(3)OH) (monoclinic P2(1)/c, a = 13.352(2), b = 16.026(3), c = 23.145(7) Angstrom, beta = 96.64(2)degrees, V = 4919(2) Angstrom(3), Z = 4, T = 173 K) shows the cobalt ion to be in a highly distorted trigonal bipyramidal environment, with asymmetrical binding by the carboxylates of XDK. Complex 1 reacts readily with alkali metal salts to afford heterodimetallic complexes, such as [KCo(XDK)(neo)(PF6)] (2) and [Rb2Co2(XDK)(2)-(neo)(2)(H2O)(BPh(4))(2)] (3). The X-ray structures of 2 . 2CH(3)CN: and 3 . 2CHCl(3) reveal that XDK undergoes a carboxylate shift upon formation of the alkali metal adducts, resulting in a highly unusual distorted trigonal pyramidal geometry at the cobalt ion (2 . 2CH(3)CN: monoclinic P2(1)/c, a = 14.261(2), b = 14.275(2), c = 26.113(4) Angstrom, beta = 100.95(1)degrees, V = 5219(1) Angstrom(3), Z = 4, T = 188 K. 3 . 2CHCl(3): triclinic, P ($) over bar 1, a = 12.130(2), b = 16.409(3), c = 17.315(3) Angstrom, alpha = 100.09(2), beta = 103.83(1), gamma = 96.35(2)degrees, V = 3252(1) Angstrom(3), Z = 1, T = 213 K). The alkali metal ions bind to the carboxylate and amide carbonyl oxygen atoms as well as to the PF6- or BPh(4)(-) anion. The alteration in Co(II) geometry upon binding of the alkali metal ions to 1 is reflected by significant changes in its visible spectrum. These changes permit the reactions to be monitored spectroscopically, from which their 1:1 stoichiometries were clearly evident.