镍,[碳酸(2-)-κO]- | 719261-06-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机碳酸及其衍生物
• 中文名称: 镍,[碳酸(2-)-κO]-
• 英文名称: nickel(II) carbonate
• 英文别名: nickel carbonate；anhydrous nickel carbonate；Nickel, [carbonato(2-)-kappaO]-；nickel(2+);carbonate
• CAS: 719261-06-0
• 化学式: CO₃*Ni
• 分子量: 118.699
• InChiKey: ZULUUIKRFGGGTL-UHFFFAOYSA-L

物化性质

• 物理描述：
  DryPowder; Liquid; OtherSolid; WetSolid
• 颜色/状态：
  Green rhombohedral crystals
• 熔点：
  No melting point; decomposes on heating
• 溶解度：
  93 mg/l water @ 25 °C
• 密度：
  4.39 g/cu m
• 分解：
  Toxic gases and vapors (such as nickel carbonyl) may be released ... in the decomp of nickel cmpd. /Nickel & sol nickel cmpd/

计算性质

• 辛醇/水分配系数(LogP)：
  -2.45
• 重原子数：
  5
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  3

ADMET

代谢

镍主要通过肺和胃肠吸收。一旦进入体内，它会进入血液，在那里与白蛋白、L-组氨酸和_2-巨球蛋白结合。镍倾向于积累在肺、甲状腺、肾脏、心脏和肝脏中。吸收的镍通过尿液排出，而未被吸收的镍则通过粪便排出。(L41)

Nickel is absorbed mainly through the lungs and gastrointestinal tract. Once in the body it enters the bloodstream, where it binds to albumin, L-histidine, and _2-macroglobulin. Nickel tends to accumulate in the lungs, thyroid, kidney, heart, and liver. Absorbed nickel is excreted in the urine, wherease unabsorbed nickel is excreted in the faeces. (L41)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 毒性总结

碳酸镍不溶于水。在工作暴露期间，呼吸道吸收伴随后续的胃肠道吸收是不溶性镍化合物进入人体的主要途径。大量的吸入物质会在呼吸道粘液清除后随吞咽进入胃肠道。不良的个人卫生和工作习惯可能增加胃肠道暴露的风险。经皮吸收在数量上可以忽略不计，但在接触过敏性疾病的发病机制中很重要。吸收与化合物的溶解度有关，而碳酸镍被归类为不溶性盐。碳酸镍在多种实验动物中通过肌内、皮下、腹腔内、胸膜内、眼内、骨内、肾内、关节内、睾丸内或脂肪内给药后诱导了局部间充质肿瘤。

... Nickel carbonate is insoluble in water. ... Respiratory absorption with secondary gastrointestinal absorption of nickel (insoluble compounds) is the major route of entry during occupational exposure. A significant quantity of inhaled material is swallowed following mucocillary clearance from the respiratory tract. Poor personal hygiene & work practices can contribute to gastrointestinal exposure. Percutaneous absorption is negligible, quanitatively, but is important in the pathogenesis of contact hypersensitivity. Absorption is related to the solubility of the compound /& nickel carbonate is classified as an insoluble salt/. Nickel carbonate ... induced local mesenchymal tumors in a variety of experimental animals after im, sc, ip, intrapleural, intraocular, intraosseous, intrarenal, intra-articular, intratesticular or intra-adipose administration.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 毒性总结

镍已知可以在某些酶中替代其他必需元素，如钙调神经磷酸酶。它具有基因毒性，一些镍化合物已被证明可以促进细胞增殖。镍对染色质蛋白，特别是组蛋白和精蛋白具有高亲和力。镍离子与异染色质的结合会导致包括浓缩、DNA过度甲基化、基因沉默以及组蛋白乙酰化的抑制等一系列变化，这些变化已被证明会干扰基因表达。镍还被证明可以改变几个转录因子，包括低氧诱导转录因子、激活转录因子和NF-KB转录因子。还有证据表明，镍离子可以抑制DNA修复，要么直接抑制DNA修复酶，要么与锌离子竞争结合锌指DNA结合蛋白，导致DNA结构变化，阻止修复酶的结合。镍离子还可以与许多细胞配体结合，包括氨基酸、肽和蛋白质，从而导致氧自由基的产生，诱导碱基损伤、DNA链断裂和DNA蛋白质交联。（L41, A40）

Nickel is known to substitute for other essential elements in certain enzmes, such as calcineurin. It is genotoxic, and some nickel compounds have been shown to promote cell proliferation. Nickel has a high affinity for chromatin proteins, particularly histones and protamines. The complexing of nickel ions with heterochromatin results in a number of alterations including condensation, DNA hypermethylation, gene silencing, and inhibition of histone acetylation, which have been shown to disturb gene expression. Nickel has also been shown to alter several transcription factors, including hypoxia-inducible transcription factor, activating transcription factor, and NF-KB transcription factor. There is also evidence that nickel ions inhibit DNA repair, either by directly inhibiting DNA repair enzymes or competing with zinc ions for binding to zinc-finger DNA binding proteins, resulting in structural changes in DNA that prevent repair enzymes from binding. Nickel ions can also complex with a number of cellular ligands including amino acids, peptides, and proteins resulting in the generation of oxygen radicals, which induce base damage, DNA strand breaks, and DNA protein crosslinks. (L41, A40)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 致癌性证据

A1：已确认的人类致癌物。/镍，以Ni表示，不溶于无机化合物（NOS）/

A1: Confirmed human carcinogen. /Nickel, as Ni, Insoluble inorganic compounds (NOS)/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌性证据

评估：有足够的人类证据表明硫酸镍具有致癌性，以及镍精炼工业中遇到的镍硫化物和氧化物的组合也具有致癌性。关于金属镍和镍合金的人类致癌性证据不足。在实验动物中，有足够的证据表明金属镍、氧化镍、氢氧化镍和结晶镍硫化物具有致癌性。在实验动物中，对于镍合金、镍茂、镍羰基、镍盐、镍砷化物、镍锑化物、镍硒化物和镍碲化物具有有限的致癌性证据。在实验动物中，对于三氧化二镍、非晶镍硫化物和镍钛酸盐的致癌性证据不足。工作组根据流行病学研究、实验动物致癌性研究以及几种其他相关数据的结果，结合镍化合物在其靶细胞的关键位点可以生成镍离子的基本概念，对镍化合物这一组进行了整体评估。总体评估：镍化合物对人类具有致癌性（第1组）。金属镍可能对人类具有致癌性（第2B组）。/镍化合物/

Evaluation: There is sufficient evidence in humans for the carcinogenicity of nickel sulfate, and of the combinations of nickel sulfides and oxides encountered in the nickel refining industry. There is inadequate evidence in humans for the carcinogenicity of metallic nickel and nickel alloys. There is sufficient evidence in experimental animals for the carcinogenicity of metallic nickel, nickel monoxides, nickel hydroxides and crystalline nickel sulfides. There is limited evidence in experimental animals for the carcinogenicity of nickel alloys, nickelocene, nickel carbonyl, nickel salts, nickel arsenides, nickel antimonide, nickel selenides and nickel telluride. There is inadequate evidence in experimental animals for the carcinogenicity of nickel trioxide, amorphous nickel sulfide and nickel titanate. The Working Group made the overall evaluation on nickel compounds as a group on the basis of the combined results of epidemiological studies, carcinogenicity studies in experimental animals, and several types of other relevant data, supported by the underlying concept that nickel compounds can generate nickel ions at critical sites in their target cells. Overall evaluation: Nickel compounds are carcinogenic to humans (Group 1). Metallic nickel is possibly carcinogenic to humans (Group 2B). /Nickel compounds/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌物分类

1, 对人类致癌。

1, carcinogenic to humans. (L135)

来源:Toxin and Toxin Target Database (T3DB)

吸收、分配和排泄

碳酸镍以0.05毫克的剂量通过气管内给药给小鼠，并在给药后1-6天内测定镍的尿液排泄和肺清除情况。在第一天内排出的镍比一周的其余时间要多。碳酸镍从肺部的清除效果是适中的。

NICKEL CARBONATE WAS GIVEN INTRATRACHEALLY TO MICE (0.05 MG) & URINARY EXCRETION & LUNG CLEARANCE OF NICKEL DETERMINED 1-6 DAYS FOLLOWING ADMIN. MORE NICKEL EXCRETED IN URINE DURING 1ST DAY THAN REMAINDER OF WK. CLEARANCE OF NICKEL CARBONATE FROM LUNG WAS MODERATE.

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• 包装等级：
  III
• 危险类别：
  6.1
• 危险性防范说明：
  P501,P273,P272,P260,P270,P202,P201,P264,P280,P284,P302+P352,P391,P308+P313,P362+P364,P304+P340,P333+P313,P301+P310+P330,P405
• 危险品运输编号：
  3288
• 危险性描述：
  H301,H315,H360,H372,H317,H334,H341,H350,H410
• 储存条件：
  | 温度 | 环境 | | --- | --- | | 2-8°C | 惰性气体 |

反应信息

• 作为反应物：
  描述：

  镍,[碳酸(2-)-κO]- 以 neat (no solvent) 为溶剂， 生成 nickel(II) oxide
  参考文献：
  名称：

  一氧化碳加氢氧化镍结构转变的特殊性.I。催化剂活化初期

  摘要：

  利用原位X射线粉末衍射和透射电子显微镜研究了氧化镍形态对CO / H 2环境中活化过程中结构转变机理的影响。发现在初始反应阶段，氧化镍结构以两种方式转变：（i）通过形成Ni / NiO体系将NiO还原为Ni；（ii）随着Ni 3 C / NiO催化剂的发展而使NiO碳化。已经显示出特定的相变取决于母体氧化物的晶格与所得产物之间的结构相似性。所得数据表明NiO与CO / H 2的相互作用反应混合物是结构敏感的反应。还讨论了一氧化碳在两种拓扑化学过程中的作用。

  DOI：

  10.1006/jcat.1993.1313
• 作为产物：
  描述：

  在 air 作用下， 以 neat (no solvent) 为溶剂， 生成 镍,[碳酸(2-)-κO]-
  参考文献：
  名称：

  Zinkgraef, K.-F., Diss. Heidelberg 1968

  摘要：

  DOI：
• 作为试剂：
  描述：

  7-甲基辛醛 在 镍,[碳酸(2-)-κO]- 、 氢气 作用下， 130.0~140.0 ℃ 、5.0 MPa 条件下， 反应 1.0h， 生成 异壬醇
  参考文献：
  名称：

  一种含羰基化合物加氢制备醇类化合物的方法

  摘要：

  本发明提供了一种含羰基化合物加氢制备醇类化合物的方法，首先将含羰基化合物与镍催化剂前驱物接触，得到含镍溶液，然后将含镍溶液与氢气接触反应，其中所含的镍转化为镍催化剂并原位催化含羰基化合物的加氢反应，即制得醇类化合物。本发明提供的制备方法首次将镍催化剂的制备和含羰基化合物的加氢反应置于同一工艺过程之中，制备的镍催化剂催化活性好，使用寿命长，原位催化制得的醇类化合物产率高，选择性好，因此能够显著降低醇类化合物的生产成本，提高生产效率，特别适用于大规模的工业化生产。

  公开号：

  CN113087595B

文献信息

• Cation Distribution and Local Configuration of Fe2+ Ions in Structurally Nonequivalent Lattice Sites of Heterometallic Fe(II)/M(II) (M = Mn, Co, Ni, Cu, Zn) Diaquadiformato Complexes
  作者：M. Devillers、J. Ladrière

  DOI：10.1006/jssc.1993.1092

  日期：1993.3

  57Fe Mössbauer investigations are carried out on a wide series of heterometallic diaquadiformato Fe(II)/M(II) complexes with M = Mn, Co, Ni, Cu, and Zn to provide a local picture of the coordination environment of the 57Fe2+ ions as a function of (i) the nature of the host cation and (ii) the relative amounts of both metals in the matrix (between 50 and 0.25 at.% Fe). Information is obtained on the

  57次铁穆斯堡尔调查是对广泛系列异金属diaquadiformato的情况下进行的Fe（II）/中号（II）配合物中号=锰，钴，镍，铜，锌，以提供的配位环境的局部图像57的Fe 2+离子作为宿主阳离子和（ii）的相对量在基质两种金属的（50和0.25之间。％的Fe）的（i）的性质的函数。获得有关两种金属在两个结构上不等价的晶格位点之间的定量分布以及每个晶体位点中掺杂原子周围的局部几何结构的信息。在混合的Fe-Cu络合物中。的Fe 2+离子在tetrahydrated站点优先结合; 在铜富含Fe的XCu 1- x（HCO 2）2 ·2H 2 O，位于六甲酸酯配位位的57 Fe 2+离子被甲酸酯配体的轴向压缩八面体包围，这与在纯铁化合物和在其他混合系统中。根据四极分裂值的温度依赖性，提出了四方场分裂和金属-配体相互作用程度的半定量估计。
• Ordered Olivine‐Type Lithium–Cobalt and Lithium–Nickel Phosphates Prepared by a New Precursor Method
  作者：Violeta Koleva、Ekaterina Zhecheva、Radostina Stoyanova

  DOI：10.1002/ejic.201000400

  日期：2010.9

  deprotonated. For the Co precursor the formate and phosphates ions are randomly coordinated to both Co and Li cations, whereas for the Ni precursor there is a preferential coordination of the formate and phosphate ions around the Ni 2+ and Li + ion, respectively. Thermal treatment of the precursors yields single phases of olivine-type LiCoPO 4 at 450 °C and LiNiP0 4 at 700 °C. Structural analysis evidences

  橄榄石型LiCoPO 4 和LiNiPO 4 的单相是通过对均相锂金属磷酸盐甲酸盐前体进行热处理合成的，该前体是通过冷冻干燥相应金属甲酸盐和LiH 2 PO 4 的水溶液而获得的。通过红外光谱、DTA 和 SEM 研究了前驱体的结构、热行为和形貌。钴和镍磷酸甲酸前体的组成为 LiMH x (PO 4 )(HCOO) x ·yH 2 O，其中甲酸和磷酸基团主要去质子化。对于 Co 前驱体，甲酸根离子和磷酸根离子与 Co 和 Li 阳离子随机配位，而对于 Ni 前驱体，甲酸根和磷酸根离子分别优先配位在 Ni 2+ 和 Li + 离子周围。前体的热处理在 450°C 下产生橄榄石型 LiCoPO 4 和在 700°C 下的 LiNiPO 4 单相。结构分析表明，LiCoPO 4 和LiNiPO 4 都具有有序的橄榄石型结构，在金属位置和锂缺乏之间没有任何Li到M的紊乱。已经讨论了冻干溶液浓度和退火温度对LiCoPO
• Reactions of methyl fluorosulphate and triethyloxonium tetrafluoroborate with transition-metal complexes
  作者：Colin Eaborn、Nicholas Farrell、James L. Murphy、Alan Pidcock

  DOI：10.1039/dt9760000058

  日期：——

  Reactions of SFO2(OMe) and [Et3O][BF4] with a variety of transition-metal complexes have been examined and classified as ligand abstraction, oxidative additions, oxidation, ligand alkylation, or reactions in which an anion fragment is abstracted from a ligand. Factors influencing the mode of reaction and the mechanisms of some of the reactions are discussed.

  已经检查了SFO 2（OMe）和[Et 3 O] [BF 4 ]与多种过渡金属配合物的反应，并将其分类为配体抽象，氧化加成，氧化，配体烷基化或其中阴离子片段为从配体中提取。讨论了影响反应方式的因素和某些反应的机理。
• Synthesis and characterization of new metal(II) complexes with formates and some nitrogen donor ligands
  作者：D. Czakis-Sulikowska、A. Czylkowska、J. Radwańska-Doczekalska、R. Grodzki、E. Wojciechowska

  DOI：10.1007/s10973-006-7980-9

  日期：2007.11

  New mixed-ligands complexes with empirical formulae: M(2,4′-bpy)2L2·H2O (M(II)Zn, Cd), Zn(2-bpy)3L2·4H2O, Cd(2-bpy)2L2·3H2O, M(phen)L2·2H2O (where M(II)=Mn, Ni, Zn, Cd; 2,4′-bpy=2,4′-bipyridine, 2-bpy=2,2′-bipyridine, phen=1,10-phenanthroline, L=HCOO−) were prepared in pure solid state. They were characterized by chemical, thermal and X-ray powder diffraction analysis, IR spectroscopy, molar conductance in MeOH, DMF and DMSO. Examinations of OCO− absorption bands suggest versatile coordination behaviour of obtained complexes. The 2,4′-bpy acts as monodentate ligand; 2-bpy and phen as chelating ligands. Thermal studies were performed in static air atmosphere. When the temperature raised the dehydration processes started. The final decomposition products, namely MO (Ni, Zn, Cd) and Mn3O4, were identified by X-ray diffraction.

  新型的混合配体配合物，其经验公式为：M(2,4′-bpy)2L2·H2O (M(II)=Zn, Cd), Zn(2-bpy)3L2·4 , Cd(2-bpy)2L2·3 , M(phen)L2·2 (其中 M(II)=Mn, Ni, Zn, Cd; 2,4′-bpy=2,4′-联吡啶，2-bpy=2,2′-联吡啶，phen=1,10-菲啰啉，L=HCOO−) 在纯固态中制备。这些配合物通过化学、热分析和X射线粉末衍射分析、红外光谱、在MeOH、DMF和DMSO中的摩尔电导率进行了表征。OCO−吸收带的检测表明所得配合物具有多样的配位行为。2,4′-bpy作为单齿配体；2-bpy和phen作为螯合配体。热研究在静态空气氛围中进行。当温度升高时，脱水过程开始。最终分解产物，即MO (Ni, Zn, Cd) 和 Mn3O4，通过X射线衍射鉴定。
• Mechanosynthesis of multiferroic hybrid organic-inorganic [NH4][M(HCOO)3] M = Co2+,Mn2+,Zn2+,Ni2+, Cu2+ formate-based frameworks
  作者：Valentina Vit、Fabio Orlandi、Andrea Griesi、Danilo Bersani、Davide Calestani、Francesco Cugini、Massimo Solzi、Mauro Gemmi、Lara Righi

  DOI：10.1016/j.jallcom.2021.163288

  日期：2022.4

  divalent metal determines the occurrence of antiferromagnetic ordering below 30 K opening the avenue for a rational formulation of a new class of multiferroic materials. We demonstrate that this intriguing class of compounds can be synthetized with a mechanochemical approach. This novel route of synthesis was applied to the series [NH4][M(HCOO)3] with M= Cu2+, Co2+, Mn2+, Zn2+ and Ni2+ using as reactants ammonium

  具有式[NH 4 ][M(HCOO) 3 ]的化合物家族，其中M为二价d-金属，其特征在于承载NH 4 +阳离子的多孔骨架在低温下表现出自发的铁电极化。磁性活性二价金属的存在决定了低于 30 K 的反铁磁有序的发生，为合理配方的新型多铁性材料开辟了道路。我们证明了这一类有趣的化合物可以用机械化学方法合成。这种新的合成路线应用于 [NH 4 ][M(HCOO) 3 ] 系列，其中 M= Cu 2+ , Co 2+ , Mn2+、Zn 2+和Ni 2+使用甲酸铵和相应的二水合金属甲酸盐作为反应物。该过程的研磨持续时间与二水合金属甲酸盐的热稳定性相关，表明机械合成过程的第一步是去除水分子。最终产品的特征表明存在具有极好结晶度的单相[NH 4 ][M(HCOO) 3 ]化合物。