Ni2(μ-H2O)(μ-OOC-tert-Bu)2(OOC-tert-Bu)2(tert-BuCOOH)4 | 515845-82-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: Ni2(μ-H2O)(μ-OOC-tert-Bu)2(OOC-tert-Bu)2(tert-BuCOOH)4
• 英文别名: Ni2(μ-water)(μ-pivaloate)2(pivaloate)2(pivalic acid)4；Ni2(μ-H2O)(OOCCMe3)4(HOOCCMe3)4；Ni2(μ-H2O)(μ-Piv)2(Piv)2(HPiv)4；Ni2(water)(pivalate)4(pivalic acid)4；(Ni2(m-H2O)(O2CCMe3)4(HO2CCMe3)4；2,2-dimethylpropanoate;2,2-dimethylpropanoic acid;nickel(2+);hydrate
• CAS: 515845-82-6
• 化学式: C₄₀H₇₈Ni₂O₁₇
• 分子量: 948.429
• InChiKey: LVEMQMKSCYDMBT-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  2.77
• 重原子数：
  59
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  311
• 氢给体数：
  5
• 氢受体数：
  17

反应信息

• 作为反应物：
  描述：

  Ni2(μ-H2O)(μ-OOC-tert-Bu)2(OOC-tert-Bu)2(tert-BuCOOH)4 以 癸烷 为溶剂， 以98%的产率得到nickel(II) pivalate
  参考文献：
  名称：

  VIII族3d金属的高自旋羧酸盐聚合物[M(OOCCMe3)2]n

  摘要：

  通式 [Co(OOCCMe3)2]n (2) 的配位聚合物是通过对不同组成 [(HOOCCMe3)xCo(OH)n(OOCCMe3)2−n]m 的配位聚合物温和热解制备的，双核钴络合物 Co2(μ-H2O)(OOCCMe3)4(HOOCCMe3)4、四核钴簇 Co4(μ3-OH)2(OOCCMe3)6(HOEt)6 和六核簇 [Co6(μ4-O)2( μn-OOCCMe3)10(C4H8O)3(H2O)]·1.5(C4H8O) (7) 在有机溶剂中。在晶体中，聚合物具有链状结构。与新戊酸钴的热解不同，双核配合物 Ni2(μ-H2O)(OOCCMe3)4(HOOCCMe3)4 的热解产生六核配合物 Ni6(μ2-OOCCMe3)6(μ3-OOCCMe3)6 (3)。化合物 2 的磁性能与 3 有很大不同。 化合物 2 在 Tc = 3.4 K (H = 1 Oe) 时经历磁相变到有序状态，而化合物

  DOI：

  10.1007/s11172-006-0532-4
• 作为产物：
  描述：

  三甲基乙酸 、 basic nickel carbonate 以 neat (no solvent) 为溶剂， 以86.7%的产率得到Ni2(μ-H2O)(μ-OOC-tert-Bu)2(OOC-tert-Bu)2(tert-BuCOOH)4
  参考文献：
  名称：

  新戊酸镍配合物：结构变化和磁化率以及非弹性中子散射研究。

  摘要：

  据报道三个小镍（II）笼的合成和结构表征，均由新戊酸酯配体稳定。通过结合磁化率测量和非弹性中子散射来研究笼子的磁性。对于双核笼，[Ni2（mu-OH2）（O2CCMe3）4（HO2CCMe3）4] 1，基态为S = 2，在J = 0.32 meV的Ni（II）中心与D（在基态下S = 2）=-0.09 meV。对于四核杂化笼，[Ni4（mu（3）-OMe）4（O2CCMe3）4（MeOH）4] 2，发现两个铁磁交换相互作用，并观察到S = 4基态。尽管不能明确确定该状态的零场分裂，但最可能的值为DS = 4 = -0.035 meV。对于四核镍蝴蝶，[Ni4（mu3-OH）2（O2CCMe3）6（EtOH）6] 3，需要三种交换相互作用，两种是反铁磁性的，一种是弱铁磁性的。结果基态为S = 0。数据使我们能够将笼中涉及的单个Ni（II）离子的零场分裂估计为Di = + 1.0 meV。因此，两者都有望成为新的单分子磁体。

  DOI：

  10.1039/b406112h

文献信息

• Solid-phase thermal decomposition of polynuclear nickel(II) and cobalt(II) complexes
  作者：Zh. V. Dobrokhotova、I. G. Fomina、M. A. Kiskin、A. A. Sidorov、V. M. Novotortsev、I. L. Eremenko

  DOI：10.1007/s11172-006-0246-7

  日期：2006.2

  Solid-phase thermal decomposition of polynuclear NiII and CoII pivalate complexes was studied by differential scanning calorimetry and thermogravimetry. The decomposition of the polynuclear (from bi-to hexanuclear) CoII carboxylate complexes is accompanied by aggregation to form a volatile octanuclear complex. Thermolysis of the polynuclear NiII carboxylates results in their destructure, and the phase

  通过差示扫描量热法和热重法研究了多核 NiII 和 CoII 新戊酸酯配合物的固相热分解。多核（从双核到六核）CoII 羧酸盐配合物的分解伴随着聚集形成挥发性八核配合物。多核 NiIII 羧酸盐的热解导致它们的解构，分解产物的相组成由配位配体的性质决定。
• Carboxylate clusters with the M4O4 cubane-like core: pivalate cocrystal containing CoII and NiII
  作者：I. G. Fomina、Zh. V. Dobrokhotova、G. G. Aleksandrov、M. L. Kovba、V. I. Zhilov、A. S. Bogomyakov、V. M. Novotortsev、I. L. Eremenko

  DOI：10.1007/s11172-010-0149-5

  日期：2010.4

  Joint thermolysis of the dinuclear pivalate complexes M2(μ-H2O)(μ-Piv)2(Piv)2(HPiv)4 (M = Co (1) and Ni (2), Piv- is the pivalate anion), in decane at 174 °C at the reactant ratio 1: 1 followed by treatment of the dry thermolysis product with methanol afforded crystals of a new cocrystallization product of the molecules containing the heterometallic cubane-like core M4(Co,Ni)O4. According to the X-ray diffraction data and the results of magnetic measurements, inductively coupled plasma atomic emission spectrometry (ICP-AES), and investigations of the solid-state thermal decomposition products, the isolated cocrystallization product has the general formula [Co1.6Ni2.4(μ3-OMe)4(μ2-Piv)2(pg2 -Piv)2(MeOH)4] ·4MeOH (3·4MeOH). Thermolysis of the crystals of the solvate 3·4MeOH is a destructive process accompanied by the intramolecular redox reaction. A mixture of metallic Ni and cobalt oxide (CoO) are the final solid decomposition products of 3 · 4MeOH in an argon atmosphere, whereas a mixture of the phases NiO, Co3O4, and NiCo2O4 is formed in air.

  M2(μ-H2O)(μ-Piv)2(Piv)2(HPiv)4 (M = Co (1)和 Ni (2)，Piv- 为新戊酸阴离子)的双核新戊酸配合物在癸烷中于 174 °C、反应物比为 1：然后用甲醇处理干燥的热解产物，得到了含有异金属立方体状核 M4(Co,Ni)O4的分子的新共结晶产物晶体。根据 X 射线衍射数据和磁性测量、电感耦合等离子体原子发射光谱（ICP-AES）以及固态热分解产物的研究结果，分离出的共晶体产物的通式为[Co1.6Ni2.4(μ3-OMe)4(μ2-Piv)2(pg2 -Piv)2(MeOH)4] -4MeOH（3-4MeOH）。溶解物 3-4MeOH 晶体的热分解是一个伴随着分子内氧化还原反应的破坏过程。在氩气环境中，3-4MeOH 的最终固体分解产物是金属镍和氧化钴（CoO）的混合物，而在空气中则会形成 NiO、Co3O4 和 NiCo2O4 三相的混合物。
• On the Possibility of Magneto-Structural Correlations: Detailed Studies of Dinickel Carboxylate Complexes
  作者：James P. S. Walsh、Stephen Sproules、Nicholas F. Chilton、Anne-Laure Barra、Grigore A. Timco、David Collison、Eric J. L. McInnes、Richard E. P. Winpenny

  DOI：10.1021/ic501036h

  日期：2014.8.18

  A series of water-bridged dinickel complexes of the general formula [Ni-2(mu(2)-OH2)(mu(2)-O2CtBu)(2)((O2CBu)-Bu-t)(2)(L)(L')] (L = (HO2CBu)-Bu-t, L' = (HO2CBu)-Bu-t (1), pyridine (2), 3-methylpyridine (4); L = L' = pyridine (3), 3-methylpyridine (5)) has been synthesized and structurally characterized by X-ray crystallography. The magnetic properties have been probed by magnetometry and EPR spectroscopy, and detailed measurements show that the axial zero-field splitting, D, of the nickel(II) ions is on the same order as the isotropic exchange interaction, J, between the nickel sites. The isotropic exchange interaction can be related to the angle between the nickel centers and the bridging water molecule, while the magnitude of D can be related to the coordination sphere at the nickel sites.
• Mikhailova; Fomina; Sidorov, Russian Journal of Inorganic Chemistry, 2003, vol. 48, # 10, p. 1505 - 1512
  作者：Mikhailova、Fomina、Sidorov、Golovaneva、Aleksandrov、Novotortsev、Ikorskii、Eremenko

  DOI：——

  日期：——
• Formation of amidine ligands in coordination spheres of Co^IIand Ni^IIatoms
  作者：T. B. Mikhailova、E. V. Pakhmutova、A. E. Malkov、I. F. Golovaneva、A. A. Sidorov、I. G. Fomina、G. G. Aleksandrov、V. N. Ikorskii、V. M. Novotortsev、I. L. Eremenko、I. I. Moiseev

  DOI：10.1023/b:rucb.0000011865.18994.5c

  日期：2003.10

  Reactions of polynuclear cobalt and nickel pivalates with amines in MeCN afforded compounds containing the amidine ligands (MeC(NHR)=NH). The reactions with 2,6-diaminopyridine yielded the Ni(Me3CCOO)(2)H2N(C5H3N)NHC(Me)=NH}, Co-2(Me3CCOO)(4)H2N(C5H3N)NHC(Me)=NH},Co(Me3CCOO)(2)H2N(C5H3N)NHC(Me)=NH} complexes and the solvate of the latter with Me3CCOH and C6H6. The reaction with S-(-)-alpha-methylbenzylamine gave rise to the ionic chiral compound with composition [PhCH(Me)NHC(Me)NH2](+)[Co-2(Me3CCOO)(5)](-) as a diastereomeric salt. According to the results of X-ray diffraction analysis, the asymmetric carbon atom in the cation and the asymmetric cobalt atom in the binuclear anion of this salt have the S absolute configuration.* The Compounds were characterized by elemental analysis data and the results of IR and electronic spectroscopy. Their structures were established by X-ray diffraction analysis. The chiroptical properties of the ionic compound in solution were studied by circular dichroism spectroscopy.