sodium nitrate | 7631-99-4

• 分子结构分类: 无机化合物 - 混合金属/非金属化合物 - 碱金属含氧阴离子化合物
• 英文名称: sodium nitrate
• 英文别名: NaNO₃；sodium nitrite；sodium;nitrate
• CAS: 7631-99-4
• 化学式: NNaO₃
• 分子量: 84.9947
• InChiKey: VWDWKYIASSYTQR-UHFFFAOYSA-N

物化性质

• 熔点：
  308 °C
• 密度：
  2.26 g/cm3
• 物理描述：
  Sodium nitrate appears as a white crystalline solid. Noncombustible but accelerates the burning of combustible materials. If large quantities are involved in fire or the combustible material is finely divided an explosion may result. May explode under prolonged exposure to heat or fire. Toxic oxides of nitrogen are produced in fires. Used in solid propellants, explosives, fertilizers, and for many other uses.
• 颜色/状态：
  Colorless, trigonal or rhombohedron crystals
• 气味：
  Odorless
• 味道：
  Saline, slightly bitter taste
• 沸点：
  Decomposes 716° F (USCG, 1999)
• 溶解度：
  ...is soluble in liquid ammonia and forms Na NO3.4NH3 below -42 °C. The solubility in anhydrous methanol is 2.8 wt% at 25 °C.
• 分解：
  380 °C
• 粘度：
  2.85 cP at 590 K; 1.53 cP at 730 K
• 折光率：
  Index of refraction = 1.587 (trigonal); 1.336 (rhombohedral)
• 稳定性/保质期：

  1. 当含有极少量氯化钠杂质时，其潮解性大为增加。在380 ℃时开始分解，在400～600 ℃时释放氮气和氧气；加热至700 ℃时产生一氧化氮；至775～865 ℃时生成少量二氧化氮和一氧化二氮。作为强氧化剂，它与有机物、硫磺等接触易引发燃烧或爆炸。

  2. 稳定性：稳定。

  3. 禁配物：强还原剂、活性金属粉末、强酸、易燃或可燃物质、铝。

  4. 应避免的条件：受热。

  5. 聚合危害：不聚合。

  6. 分解产物：氮氧化物。

计算性质

• 辛醇/水分配系数(LogP)：
  -3.24
• 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：
  62.9
• 氢给体数：
  0
• 氢受体数：
  3

ADMET

代谢

硝酸盐转化为亚硝酸盐通常发生在消化道内。亚硝酸盐是在羊和牛瘤胃中硝酸盐还原为氨的中间产物：看来在硝酸盐浓度超过一定水平时，亚硝酸盐还原为氨的速度成为限制因素，并且亚硝酸盐会积累。如果硝酸盐在瘤胃中被还原，或者如果迅速完全还原为氨，那么硝酸盐中毒的危险被认为是轻微的……/无机硝酸盐盐类/

Transformation of nitrate to nitrite usually occurs within alimentary tract. Nitrite is intermediary product in redn of nitrate to ammonia within rumen of sheep & cow: it appears that above certain concn of nitrate, rate of redn of nitrite to ammonia becomes limiting & ... nitrite accumulates. Danger of nitrate poisoning is considered slight if nitrate is reduced in rumen or if complete redn to ammonia occurs rapidly ... /Inorganic nitrate salts/

来源:Hazardous Substances Data Bank (HSDB)

代谢

细菌将硝酸盐还原为亚硝酸盐在人类胃中的情况已有报道，并且在31名接受了胃内灌注硝酸钠和二苯胺的人类受试者的胃内容物中发现了N-亚硝基二苯胺。

... Bacterial redn of nitrate to nitrite in human stomach was reported ... & n-nitrosodiphenylamine was identified in stomach contents of 31 human subjects who had received sodium nitrate & diphenylamine intragastrically.

来源:Hazardous Substances Data Bank (HSDB)

代谢

细菌存在并且环境可以是无氧的情况下，硝酸盐可以被还原成亚硝酸盐。这个反应的主要部位是口腔和胃，但在小肠和膀胱（尿路感染）中亚硝酸盐的形成也可能具有一些毒理学上的重要性。亚硝酸盐在某些条件下可以通过细菌进一步还原为氮气。在血液中，亚硝酸盐将血红蛋白转化为高铁血红蛋白，并同时被氧化为硝酸盐。正常情况下，高铁血红蛋白会通过酶促反应逐渐恢复为血红蛋白。亚硝酸盐具有血管舒张性质，可能是通过转化为一氧化氮（NO）或含有一氧化氮的分子作为平滑肌松弛的信号因子。在酸性环境中，亚硝酸盐容易转化为亚硝化剂，并且可以与多种化合物反应，例如抗坏血酸（维生素C）、胺、酰胺。亚硝化也可以通过细菌介导，例如在胃中。一些反应产物是致癌的（例如大多数亚硝胺和酰胺）。/硝酸盐和亚硝酸盐/

Where bacteria are present and the environment can be anaerobic, nitrate can be reduced to nitrite. The main site for this reaction is mouth and stomach, but nitrite formation in the lower intestine and in the bladder (urinary infection) may also be of some toxicological importance. Nitrite may be further reduced to nitrogen by bacteria under some conditions. In blood, nitrite transforms hemoglobin to methemoglobin and is simultaneously oxidized to nitrate. Normally methemoglobin gradually reverts to hemoglobin through enzymatic reactions. Nitrite has vasodilating properties, probably through transformation into nitric oxide (NO) or a NO-containing molecule acting as a signal factor for smooth muscle relaxation. Nitrite easily transforms into a nitrosating agent in an acidic environment and can react with a variety of compounds, eg ascorbic acid, amines, amides. Nitrosation can also be mediated by bacteria, eg in the stomach. Some reaction products are carcinogenic (eg most nitrosoamines and amides). /Nitrate and nitrite/

来源:Hazardous Substances Data Bank (HSDB)

代谢

硝酸盐本身并不比其他中性盐更有毒，但如果未被及时吸收，它们可能会在大肠中被细菌还原为亚硝酸盐... /硝酸盐/

Nitrate salts as such are no more toxic than other neutral salts, but if not promptly absorbed, they may be reduced to nitrites by bacteria in the bowel ... /Nitrate salts/

来源:Hazardous Substances Data Bank (HSDB)

代谢

摄入一定量的硝酸盐和亚硝酸盐是人类氮循环的正常部分。在适当的条件下，硝酸盐可以在胃肠系统中转化为亚硝酸盐，显著增加硝酸盐的毒性。硝酸盐的主要代谢途径是转化为亚硝酸盐，然后转化为氨。亚硝酸盐、硝酸盐及其代谢物通过尿液排出体外。

Intake of some amount of nitrates and nitrites is a normal part of the nitrogen cycle in humans. In vivo conversion of nitrates to nitrites can occur in the gastrointestional tract under the right conditions, significantly enhancing nitrates' toxic potency. The major metabolic pathway for nitrate is conversion to nitrite, and then to ammonia. Nitrites, nitrates, and their metabolites are excreted in the urine. (L1137)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 毒性总结

硝酸盐的毒性是由于它进入体内后转化为亚硝酸盐。亚硝酸盐导致氧合血红蛋白自催化氧化成过氧化氢和高铁血红蛋白。这种高铁血红蛋白水平的升高被称为高铁血红蛋白血症，其特点是组织缺氧，因为高铁血红蛋白不能结合氧气。

Nitrate's toxicity is a result of it's conversion to nitrite once in the body. Nitrite causes the autocatalytic oxidation of oxyhemoglobin to hydrogen peroxide and methemoglobin. This elevation of methemoglobin levels is a condition known as methemoglobinemia, and is characterized by tissue hypoxia, as methemoglobin cannot bind oxygen. (A2450, L1613)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 致癌性证据

食物中的硝酸盐对人类致癌性证据不足。饮用水中的硝酸盐对人类致癌性证据不足。实验动物中硝酸盐的致癌性证据不足。总体评估：在导致内源性亚硝化的条件下摄入硝酸盐或亚硝酸盐可能对人类致癌（2A组）。

There is inadequate evidence in humans for the carcinogenicity of nitrate in food. There is inadequate evidence in humans for the carcinogenicity of nitrate in drinking-water. There is inadequate evidence in experimental animals for the carcinogenicity of nitrate. Overall evaluation: Ingested nitrate or nitrite under conditions that result in endogenous nitrosation is probably carcinogenic to humans (Group 2A).

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌物分类

摄入硝酸盐或亚硝酸盐，在导致内源性亚硝化的条件下，可能对人类具有致癌性（2A组）。

Ingested nitrate or nitrite under conditions that result in endogenous nitrosation is probably carcinogenic to humans (Group 2A). (L135)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 健康影响

硝酸盐和亚硝酸盐中毒会导致高铁血红蛋白血症。亚硝酸盐可能会导致怀孕并发症和发育影响。它们也可能具有致癌性。

Nitrate and nitrite poisoning causes methemoglobinemia. Nitrites may cause pregnancy complications and developmental effects. They may also be carcinogenic. (L1137)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 暴露途径

该物质可以通过吸入其气溶胶和通过吞食被吸收进人体。

The substance can be absorbed into the body by inhalation of its aerosol and by ingestion.

来源:ILO-WHO International Chemical Safety Cards (ICSCs)

吸收、分配和排泄

人体摄入的硝酸盐从近端小肠迅速吸收并分布到全身。然后硝酸盐从血液进入大肠，在那里它被快速转化为高度活性的亚硝酸盐，部分由粪便微生物完成。形成的亚硝酸盐再次被吸收进入血液，它与脱氧血红蛋白中的二价铁（Fe2+）反应，形成高铁（Fe3+）价态的变性血红蛋白。高铁状态的铁无法运输氧气。硝酸盐在肝脏迅速转化为脱硝代谢物和无机亚硝酸盐，然后通过尿液排出。大约60%到70%的摄入硝酸盐剂量在24小时内通过尿液排出。大约25%通过活跃的血液硝酸盐运输系统通过唾液排出，并可能被重新吸收。母硝酸盐化合物的半衰期通常小于1小时；代谢物的半衰期从1小时到8小时不等。/硝酸盐/

In humans, ingested nitrate is rapidly absorbed from the proximal small bowel and distributed throughout the body. Nitrate then enters the large bowel from the blood, where it is rapidly converted to highly reactive nitrite, in part by fecal microorganisms. The formed nitrite is reabsorbed into the blood, where it reacts with the ferrous (Fe2+) iron of deoxyhemoglobin, forming methemoglobin with iron in the ferric (Fe3+) valence state. Ferric iron is unable to transport oxygen. Nitrates are rapidly converted in the liver to denitrated metabolites and inorganic nitrites, which are then excreted in urine. Approximately 60% to 70% of an ingested nitrate dose is excreted in urine within the first 24 hours. About 25% is excreted in saliva through an active blood nitrate transport system and potentially is reabsorbed. Half-lives of parent nitrate compounds are usually <1 hour; half-lives of metabolites range from 1 to 8 hours. /Nitrates/

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

硝酸盐在唾液中浓缩，其中一部分通过细菌硝酸盐还原酶被还原为亚硝酸盐。/作者/测试了摄入无机硝酸盐是否会影响唾液和系统中的亚硝酸盐和S-亚硝基硫醇的水平，这两个都被认为是NO的循环储存库。在摄入硝酸钠（10 mg/kg）之前和之后，测量了血浆、唾液和尿液中硝酸盐、亚硝酸盐和S-亚硝基硫醇的水平。摄入硝酸盐负荷后，唾液、血浆和尿液中的硝酸盐水平显著增加。唾液中的S-亚硝基硫醇也有所增加，但血浆水平保持不变。摄入硝酸盐后，观察到血浆中亚硝酸盐增加了4倍。然而，如果受试者在硝酸盐负荷后避免吞咽，就可以防止血浆中亚硝酸盐的增加，从而说明其唾液来源。我们证明硝酸盐是系统生成亚硝酸盐的底物。有几种途径可以将这种亚硝酸盐进一步还原为NO。这些结果挑战了硝酸盐在生物学上是不活跃的教条，并暗示存在一个完整的反向途径，用于从硝酸盐生成NO。

... Nitrate is concentrated in saliva, where a part of it is reduced to nitrite by bacterial nitrate reductases. /The authors/ tested if ingestion of inorganic nitrate would affect the salivary and systemic levels of nitrite and S-nitrosothiols, both considered to be circulating storage pools for NO. Levels of nitrate, nitrite, and S-nitrosothiols were measured in plasma, saliva, and urine before and after ingestion of sodium nitrate (10 mg/kg). Nitrate levels increased greatly in saliva, plasma, and urine after the nitrate load. Salivary S-nitrosothiols also increased, but plasma levels remained unchanged. A 4-fold increase in plasma nitrite was observed after nitrate ingestion. If, however, the test persons avoided swallowing after the nitrate load, the increase in plasma nitrite was prevented, thereby illustrating its salivary origin. We show that nitrate is a substrate for systemic generation of nitrite. There are several pathways to further reduce this nitrite to NO. These results challenge the dogma that nitrate is biologically inert and instead suggest that a complete reverse pathway for generation of NO from nitrate exists.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

亚硝酸盐迅速从绵羊的血浆中被消除（半衰期=0.49小时）。给药后三小时，亚硝酸根离子从血浆中消失。同时观察到硝酸盐的出现。在静脉注射硝酸钠或硝酸盐后，硝酸盐的动力学参数相似（消除常数分别为0.150/h和0.154/h）。亚硝酸盐通过尿液排出的量仅占给药剂量的0.29%±0.22。硝酸盐通过尿液排出的量占亚硝酸盐给药剂量的13.80%±5.78，略低于硝酸盐给药后的排出量（16.12%±6.95）。亚硝酸盐的快速消除似乎主要是由于它转化成硝酸盐，因为无论是给药亚硝酸盐还是硝酸盐，硝酸盐通过尿液排出以及其动力学参数的值都是相似的。从绵羊血浆中消除硝酸盐的80%与尿液中的未改变排出不同。

Nitrite was quickly eliminated from blood plasma of sheep (T1/2 = 0.49 hr). Three hours after its administration, nitrite ion disappeared from blood plasma. Simultaneously the appearance of nitrate was observed. After sodium nitrite or nitrate intravenous administration, the kinetic parameters for nitrate were similar (Kel = 0.150/ h and 0.154/ hr, respectively). Urine excretion of nitrite amounted to only 0.29%+/- 0.22 of the administered dose. Urine excretion of nitrate was 13.80%+/-5.78 of the administered dose of nitrite and was slightly lower than that observed after the administration of nitrate (16.12%+/- 6.95). The quick elimination of nitrite appears to be mainly from its conversion into nitrate, because the nitrate elimination in urine. as well as the values of its kinetic parameters, were similar after the administration of nitrite or nitrate. Elimination of nitrate from blood plasma of sheep over 80% was different than its excretion in urine in the unchanged.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

... 钠 ... 硝酸盐在口服摄入后大部分被迅速吸收并原样排出 ...

... Sodium ... nitrate /is/ for the most part rapidly absorbed & excreted unchanged ... /following oral ingestion/.

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• 安全说明：
  S17,S26,S27,S36,S36/37/39,S37/39,S45
• 危险品运输编号：
  UN 1498 5.1/PG 3
• WGK Germany：
  1
• 海关编码：
  3102500000
• 危险类别：
  5.1
• 危险品标志：
  O,Xn
• 危险类别码：
  R22,R8,R36/37/38
• RTECS号：
  WC5600000
• 包装等级：
  III
• 危险标志：
  GHS03,GHS07
• 危险性描述：
  H272,H319
• 危险性防范说明：
  P210,P220,P221,P305 + P351 + P338,P370 + P378

SDS

第一部分：化学品名称

制备方法与用途

制备方法

1. 吸收法
   用相对密度为1.24～1.30的纯碱溶液吸收硝酸盐或硝酸生产中排出的含有0.5%～1.5% NO和NO₂混合气的尾气，中和液中NaNO₃/NaNO₂的含量可通过控制尾气中的NO₂/NO比例来调节。在中和液中加入硝酸，将NaNO₂转化为NaNO₃。转化后的中和液用纯碱溶液中和至游离碱含量低于0.3g/L，在132℃时蒸发浓缩，冷却至75℃结晶后分离、干燥即得产品。

2. 复分解法
   在反应器中加入粉碎的工业硫酸钠、50%～52%的硝酸钙溶液和循环的硝酸钠溶液，在50～55℃下搅拌反应3～4小时；然后过滤，滤液经蒸发浓缩、冷却结晶、分离、干燥得产品。母液可以循环使用。

3. 直接提取法
   将钠硝石矿破碎至一定粒度，用淡水或卤水喷淋堆浸，得到一定浓度的硝酸钠卤水。经冷硝分离芒硝后，将卤水送入盐田中日晒蒸发，待有钠硝矾（NaNO₃·Na₂SO₄·H₂O）晶体出现时过滤，副产氯化钠后的卤水继续进行日晒蒸发，得到含有钠硝矾的半成品。然后将半成品用一定量的卤水或结晶母液加热溶解，过滤除去杂质，滤液冷却结晶、离心分离、干燥即得产品。母液返回用于加热溶解半成品。

4. 化学纯级制备
   将48kg纯水加到200kg工业品硝酸钠中，充分搅拌2～3小时后，离心甩干除去可溶性杂质，用蒸馏水细流冲洗2～3次再甩干。每100kg晶体约加入70kg热纯水使其全部溶解，趁热过滤得到澄清透明的滤液。将滤液直接加热浓缩至体积减少到原来的一半时，即有大量的结晶析出。此时需注意多加搅拌以免晶体粘附于容器底部受热过度而分解。取出晶体离心脱水后用蒸馏水细流冲洗2～3次再甩干即可得到化学纯级硝酸钠成品。

   脱水后的母液和洗液可循环处理，反复4～5次。若需进一步降低亚硝酸盐含量至不超过0.0005%，可以将成品硝酸溶解在热纯水中，并按计算量加入硝酸铵一起煮沸2小时以除去亚硝酸钠。

制备方法

1. 吸收法
   用相对密度为1.24～1.30的纯碱溶液吸收硝酸盐或硝酸生产中排出的含有0.5%～1.5% NO和NO₂混合气的尾气。中和液中NaNO₃/NaNO₂的比例可通过控制尾气中的NO₂/NO比例来调节。在中和液中加入硝酸，将NaNO₂转化为NaNO₃。转化后的中和液用纯碱溶液中和至游离碱含量低于0.3g/L，在132℃时蒸发浓缩，冷却至75℃结晶后分离、干燥即得产品。

2. 复分解法
   在反应器中加入粉碎的工业硫酸钠、50%～52%的硝酸钙溶液和循环的硝酸钠溶液，在50～55℃下搅拌反应3～4小时。然后过滤，滤液经蒸发浓缩、冷却结晶、分离、干燥得产品。母液可以循环使用。

3. 直接提取法
   将钠硝石矿破碎至一定粒度，用淡水或卤水喷淋堆浸，得到一定浓度的硝酸钠卤水。经冷硝分离芒硝后，将卤水送入盐田中日晒蒸发，待有钠硝矾（NaNO₃·Na₂SO₄·H₂O）晶体出现时过滤。副产氯化钠后的卤水继续进行日晒蒸发，得到含有钠硝矾的半成品。然后将半成品用一定量的卤水或结晶母液加热溶解，过滤除去杂质。滤液冷却结晶、离心分离、干燥即得产品。母液返回用于加热溶解半成品。

4. 化学纯级制备
   将48kg纯水加到200kg工业品硝酸钠中，充分搅拌2～3小时后，离心甩干除去可溶性杂质，用蒸馏水细流冲洗2～3次再甩干。每100kg晶体约加入70kg热纯水使其全部溶解，趁热过滤得到澄清透明的滤液。将滤液直接加热浓缩至体积减少到原来的一半时，即有大量的结晶析出（此时需注意多加搅拌以免晶体粘附于容器底部受热过度而分解）。取出晶体离心脱水后用蒸馏水细流冲洗2～3次再甩干即可得到化学纯级硝酸钠成品。

   脱水后的母液和洗液可循环处理，反复4～5次。若需进一步降低亚硝酸盐含量至不超过0.0005%，可以将成品硝酸溶解在热纯水中，并按计算量加入硝酸铵一起煮沸2小时以除去亚硝酸钠。

反应信息

• 作为反应物：
  描述：

  sodium nitrate 在 HCl 作用下， 以 neat (no solvent) 为溶剂， 以100%的产率得到sodium chloride
  参考文献：
  名称：

  Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Na: MVol., 72, page 280 - 282

  摘要：

  DOI：
• 作为产物：
  描述：

  sodium nitrite 在 水 作用下， 以 aq. phosphate buffer 为溶剂， 生成 sodium nitrate
  参考文献：
  名称：

  基于新型聚N-乙酰基-1-蛋氨酸（poly-NALM）薄膜的高选择性同时测定抗坏血酸，尿酸和亚硝酸盐†

  摘要：

  本文证明了N-乙酰基-L的简便制备-通过电聚合技术在玻璃碳电极（GCE）上生成蛋氨酸（NALM）聚合物薄膜。原子力显微镜（AFM），X射线光电子能谱（XPS），扫描电子显微镜（SEM）和电化学技术（例如循环伏安法（CV）和微分脉冲伏安法（DPV））用于表征修饰电极。这种多聚NALM / GCE不仅对抗坏血酸（AA），尿酸（UA）和亚硝酸盐的氧化表现出强大的电催化活性，而且氧化电位也向着较弱的一侧转移，而且还增强了在生理pH值下的峰值电流响应（7.2）条件。进一步，裸露的GC电极上三种分析物的重叠阳极伏安峰在聚NALM / GC修饰电极上被很好地解析为它们的独立氧化峰，AA–UA和UA–亚硝酸盐的峰间距分别为160和590 mV，分别。在最佳实验条件下，AA，UA和亚硝酸盐的阳极峰值电流在10–1000μM，1–600μM和1–500μM浓度范围内线性增加，相关系数分别为0.990、0.996和0

  DOI：

  10.1039/c6ra18440e
• 作为试剂：
  描述：

  carvedilol hydrochloride 在 sodium nitrate 作用下， 以 乙醇 、 水 为溶剂， 生成
  参考文献：
  名称：

  具有增加溶解度的卡维地洛药用盐作为增强药物作用的方法

  摘要：

  卡维地洛（CVD）是一种β受体阻滞剂抗高血压药物，常用于治疗心血管疾病。由于CVD口服生物利用度差的问题可以通过提高活性药物成分溶解度来直接改善，因此我们重点开发可溶性更高的多组分晶体（MCC），即通过使用CVD的无水盐和水合盐。采用溶剂蒸发和阴离子交换作为结晶方法，成功制备了八种含有 CVD 和成盐剂的 MCC，这些 MCC 被认为是安全的，并且经常用于制药常规。通过 X 射线衍射（单晶 X 射线衍射，PXRD）和热学（差示扫描量热法，热重分析）技术对这些 MCC 进行了深入的晶体学描述。在结构上，晶体结构中包含极性抗衡离子和水分子，产生离子 3D 排列，其中 CVD + /阴离子/ ( n ) H 2 O 或 CVD + /阴离子 H 键合在精心组装中彼此结合。通过在类似生理条件下的平衡溶解度研究，证实与纯 CVD 相比，所有 CVD 盐的 API 溶解度都有显着增强（高达 25 倍）。这些结果增强了本文合成的

  DOI：

  10.1021/acs.cgd.4c00547

文献信息

• Preparation, Characterization, and Some Properties of Novel Dinuclear Complexes with a Coordinated Bridging Disulfide Bond. Crystal Structures of<i>Δ</i>_R<i>Λ</i>_S-[M₂(2-aminoethanethiolato)₄(cystamine)]²⁺(M = Ir^III, Rh^III)
  作者：Yoshitaro Miyashita、Narumi Sakagami、Yasunori Yamada、Takumi Konno、Ken-ichi Okamoto

  DOI：10.1246/bcsj.71.2153

  日期：1998.9

  Novel dinuclear complexes, [M2(aet)4(cysta)]2+ (M = IrIII (1), RhIII (2); aet = NH2CH2CH2S−, cysta = NH2CH2CH2SSCH2CH2NH2), were prepared by the oxidation reactions of fac(S)-[M(aet)3]. The crystal structures of the complexes were determined by X-ray diffractions: 1Cl2·4H2O, monoclinic, P21/a, a = 12.427(2), b = 8.879(1), c = 13.387(1) A, β = 91.947(10)°, V = 1476.3(3) A3, Z = 2, and R = 0.031; 2Cl2·2H2O

  通过 fac(S) 的氧化反应制备了新型双核复合物 [M2(aet)4(cysta)]2+ (M = IrIII (1), RhIII (2); aet = NH2CH2CH2S−,cysta = NH2CH2CH2SSCH2CH2NH2) -[M(aet)3]。配合物的晶体结构由X射线衍射确定：1Cl2·4H2O，单斜晶系，P21/a，a = 12.427(2), b = 8.879(1), c = 13.387(1) A, β = 91.947( 10)°，V = 1476.3(3) A3，Z = 2，R = 0.031；2Cl2·2H2O, 单斜晶系, P21/c, a = 11.788(2), b = 8.485(1), c = 14.800(2) A, β = 112.980(9)°, V = 1362.9(3) A3, Z = 2，R = 0.023。在 1 和 2 的结构中，两个八面体
• Polyoxometalate catalyzed imine synthesis: Investigation of mechanistic pathways
  作者：Subhasis D. Adhikary、Debaprasad Mandal

  DOI：10.1016/j.tet.2020.131245

  日期：2020.6

  syntheses of imines by oxidative coupling of primary alcohols and amines were achieved by using 2 mol% polyoxometalate (POM) Na12[WZn3(H2O)2(ZnW9O34)2] (Zn–WZn3) catalyst in the presence of t-BuOK and di-oxygen with excellent conversion (up to 100%) and selectivity (up to 100%). Non-noble metal-based POM catalyst in the presence of base represents a new reaction protocol for the selective synthesis of imine

  伯醇和胺的氧化偶合合成亚胺是通过在甲醇中使用2 mol％的多金属氧酸盐（POM）Na 12 [WZn 3（H 2 O）2（ZnW 9 O 34）2 ]（Zn-WZn 3）催化剂来实现的。存在t -BuOK和双氧，具有出色的转化率（最高100％）和选择性（最高100％）。在碱存在下的基于非贵金属的POM催化剂代表了一种新的反应方案，用于从具有官能团耐受性的芳族和脂族伯胺选择性合成亚胺。对照实验表明形成双氧键的Zn–WZn 3活化物种。POM的电子密度主要位于W–O–W键的表面氧原子上，该键可以与醇性OH基团结合，并有助于亚胺合成的第二步中的亚胺选择性。
• Reactions involving transition metals. Part X. Reactions of the complexes α- and β-[L3RhHX2](L = tertiary phosphine or arsine, X = Cl or Br)
  作者：Christopher E. Betts、Robert N. Haszeldine、R. V. (Dick) Parish

  DOI：10.1039/dt9750002218

  日期：——

  The reactions of the complexes α- and β[LnRhHX2](n= 2 or 3; L = tertiary phosphine or arsine; X = Cl or Br) with acidic, basic, oxidising, and reducing reagents have been investigated. The α-isomers are inert to acids (except nitric acid) but are rapidly dehydrohalogenated by bases. With weak bases, equilibria are established, the positions of which show that stability to dehydrohalogenation increases

  研究了配合物α-和β[L n RhHX 2 ]（n = 2或3； L =叔膦或a； X = Cl或Br）与酸性，碱性，氧化和还原试剂的反应。α-异构体对酸（硝酸除外）呈惰性，但会被碱迅速脱卤化氢。在弱碱的情况下，建立了平衡，其位置表明，在系列L = Ph 2 RP
• Seven-coordinated molybdenum(II) complexes containing carbonyl, triphenylphosphine, and O-donor or S-donor anionic bidentate ligands
  作者：V. Riera、F.J. Arnaiz、G.G. Herbosa

  DOI：10.1016/0022-328x(86)80410-7

  日期：1986.11

  A series of seven-coordinate molybdenum(II) complexes containing carbonyl, triphenylphosphine, bromide and/or O-donor and S-donor anionic bidentate ligands have been prepared in high yield. The synthesis involves the reaction of the six-coordinate complex Mo(CO)2(PPh3)2Br2 with the sodium salt of the appropriate ligand, in dichloromethane/methanol solution. The new complexes Mo(CO)2(PPh3)2Br(XOCR)

  已经高产率地制备了一系列包含羰基，三苯基膦，溴化物和/或O-给体和S-给体阴离子二齿配体的七配位钼（II）配合物。合成涉及六配位络合物Mo（CO）2（PPh 3）2 Br 2与适当配体的钠盐在二氯甲烷/甲醇溶液中的反应。新的配合物Mo（CO）2（PPh 3）2 Br（XOCR）（X = O，R = H，Me，Et，Ph，Cl 3 C; X = S，R = Me，Ph）。Mo（CO）2（PPh 3（XOCR）2（X = O，R = H，Me，Et，Ph; X = S，R = Me，Ph），Mo（CO）（PPh 3）2（SOCR）2（R = Me，Ph）和Mo（CO）2（PPh 3）2 Br（NO 3）已通过元素分析，红外光谱和电导率测量进行了表征。描述了改进的Mo（CO）2（PPh 3）2（S 2 COCH 3）2的合成。
• Preparation and characterization of metastable trigonal layered MSb₂O₆ phases (M = Co, Ni, Cu, Zn, and Mg) and considerations on FeSb₂O₆
  作者：A. Yu. Nikulin、E. A. Zvereva、V. B. Nalbandyan、I. L. Shukaev、A. I. Kurbakov、M. D. Kuchugura、G. V. Raganyan、Yu. V. Popov、V. D. Ivanchenko、A. N. Vasiliev

  DOI：10.1039/c6dt04859e

  日期：——

  The formula volumes of the new phases show an excellent correlation with the ionic radii (except for M = Cu, for which a Jahn–Teller distortion is suspected) and are 2–3% larger than those for the known forms although all coordination numbers are the same. The crystal structure of CoSb2O6 was refined via the Rietveld method: P1m, a = 5.1318(3) Å, and c = 4.5520(3) Å. Compounds with M = Co and Ni antiferromagnetically

  MSb 2 O 6化合物（M = Mg，Co，Ni，Cu，Zn）以四方三方晶形式存在，由于Jahn–Teller效应，单临床略微扭曲，M = Cu。在这项研究中，利用钛铁矿型NaSbO 3和熔融的MSO 4 -KCl（或MgCl 2 -KCl）混合物之间的低温交换反应，首次将这五种组合物制备为三角层状硅藻土（PbSb 2 O 6）型阶段。与先前研究的同构MnSb 2 O 6相比，它们在加热后会通过非晶态中间体不可逆地转变为已知相。，其中稳定相在结构上与亚稳相有关。发现相同的方法可用于制备稳定的硅藻土型CdSb 2 O 6。新相的配方量显示出与离子半径的极佳相关性（M = Cu除外，怀疑是Jahn–Teller畸变，M = Cu除外），尽管所有配位数都为已知值，但比已知形式大2–3％相同。通过Rietveld方法精制CoSb 2 O 6的晶体结构：P 1 m，a = 5.1318（3）Å和c=