三氯化铬 | 10025-73-7

• 物质功能分类: 无机化工 - 无机盐 - 金属卤化物及卤酸盐
• 分子结构分类: 无机化合物 - 混合金属/非金属化合物 - 过渡金属盐
• 中文名称: 三氯化铬
• 中文别名: 氯化铬无水；无水三氯化铬；六水合氯化铬；无水三氯化铬(III)；氯化铬(III)
• 英文名称: chromium(III) chloride
• 英文别名: chromium chloride；chromium trichloride；chromic chloride；Chromtrichlorid；chromium(3+);trichloride
• CAS: 10025-73-7；39345-92-1
• 化学式: Cl₃Cr
• 分子量: 158.355
• InChiKey: QSWDMMVNRMROPK-UHFFFAOYSA-K

物化性质

• 熔点：
  1152 °C
• 沸点：
  1300°C
• 密度：
  2.87 g/mL at 25 °C(lit.)
• 溶解度：
  微溶于H2O
• 暴露限值：
  a/nm
• LogP：
  c/nm
• 物理描述：
  Liquid
• 分解：
  1300 °C
• 颜色/状态：
  Violet, lustrous, hexagonal, crystalline scales
• 稳定性/保质期：
  Stable under recommended storage conditions

计算性质

• 辛醇/水分配系数(LogP)：
  2.07
• 重原子数：
  4
• 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：
  0
• 氢给体数：
  0
• 氢受体数：
  0

ADMET

代谢

调查人员研究了豚鼠在通过气管内注射200微克铬后60天内对六水合铬(III)氯化物的代谢情况。注射后10分钟，剂量的69%仍留在肺部，仅有4%在血液中，以及在肝脏、肾脏和脾脏中发现了极少量的铬。到24小时时，仍有45%的铬留在肺部，6%通过尿液排出，其他组织中的铬含量非常小。脾脏是唯一显示出积累的组织，这种情况发生在前48小时内。到达血液中的铬在血浆中的量比在细胞中多。在30天结束时，仍有30%的Cr3+留在肺部；到60天时，这一比例为12%。六水合铬(III)氯化物。

/The investigators/ studied ... the metabolism of ... chromic chloride hexahydrate in guinea pigs for ... 60 days ... after intratracheal injection of 200 ug Cr. ... 10 min after injection, 69% of the dose remained in the lungs, & only 4% was found in the blood & ... /liver, kidneys, spleen/. By 24 hr, 45% was still in the lungs, 6% was excreted in the urine, & only a very small % was found in the other tissues. The spleen was the only tissue that showed accumulation & that occurred during the 1st 48 hr. The Cr that reached the blood was found in greater amt in the plasma than in the cells ... at the end of 30 days, 30% of Cr3+ was still in the lungs ... at 60 days ... 12% ... /Chromic chloride hexahydrate/

来源:Hazardous Substances Data Bank (HSDB)

代谢

铬通过口腔、吸入或皮肤接触被吸收，并分布到几乎所有组织中，肾脏和肝脏中浓度最高。骨骼也是一个主要的储存场所，并可能导致长期保留。六价铬与硫酸盐和铬酸盐的相似性使其能够通过硫酸盐运输机制进入细胞。在细胞内，六价铬首先被还原为五价铬，然后通过许多物质，包括抗坏血酸、谷胱甘肽和烟酰胺腺嘌呤二核苷酸还原为三价铬。铬几乎全部通过尿液排出。(A12, L16)

Chromium is absorbed from oral, inhalation, or dermal exposure and distributes to nearly all tissues, with the highest concentrations found in kidney and liver. Bone is also a major storage site and may contribute to long-term retention. Hexavalent chromium's similarity to sulfate and chromate allow it to be transported into cells via sulfate transport mechanisms. Inside the cell, hexavalent chromium is reduced first to pentavalent chromium, then to trivalent chromium by many substances including ascorbate, glutathione, and nicotinamide adenine dinucleotide. Chromium is almost entirely excreted with the urine. (A12, L16)

来源:Toxin and Toxin Target Database (T3DB)

代谢

铬酸铬六水合物在豚鼠体内的代谢：豚鼠在气管内注射200微克铬后60天，注射后10分钟，剂量的69%残留在肺部，仅有4%在血液、肝脏、肾脏和脾脏中发现。到了24小时，45%仍然在肺部，6%通过尿液排出，其他组织中的含量非常小。脾脏是唯一显示积累的组织，这种情况发生在前48小时内。

The metabolism of chromic chloride hexahydrate in guinea pigs for 60 days after intratracheal injection of 200 ug Cr 10 min after injection, 69% of the dose remained in the lungs, & only 4% was found in the blood & liver, kidneys, spleen. By 24 hr, 45% was still in the lungs, 6% was excreted in the urine, & only a very small % was found in the other tissues. The spleen was the only tissue that showed accumulation & that occurred during the 1st 48 hr.

来源:DrugBank

毒理性

• 毒性总结

识别和使用：氯化铬形成紫色六方板状。它用于铬化处理；制造Cr金属和化合物；作为烯烃聚合和其他有机反应的催化剂；作为纺织品媒染剂；在制革中；在腐蚀抑制剂中，以及作为防水剂。其溶液也用于全肠外营养。人类暴露和毒性：给全肠外营养患者静脉注射的氯化铬，在剂量水平高达250微克/天的情况下连续两周给药，已被证明是无毒的。有毒铬反应的症状包括恶心、呕吐、胃肠道的溃疡、肾和肝损伤，以及中枢神经系统的异常，最终导致抽搐和昏迷。对2211名疑似过敏性接触性皮炎的患者进行了0.5%重铬酸钾（Cr(VI)）和13%三氯化铬（Cr(III)）的贴片测试。共有71名（3.2%）患者对Cr(VI)呈阳性反应，其中31名也对Cr(III)呈阳性反应。没有Cr(VI)阴性的患者对Cr(III)呈阳性反应。与仅对Cr(VI)呈阳性反应的患者相比，对Cr(VI)呈阳性反应且对Cr(III)呈阳性或可疑反应的患者患足部皮炎的风险增加。氯化铬抑制了人皮肤成纤维细胞的纺锤体形成，但仅在测试的最高浓度下（100微摩尔），这比铬(IV)化合物（铬酸钠和铬酸钙）产生相同效果所需的浓度高出几个数量级。体外氯化铬暴露仅对人类细胞的端粒长度产生轻微影响。动物研究：将氯化铬晶体应用于兔子的完整角膜，导致永久性灰色血管化混浊。大鼠被喂食基础饮食，其中添加了0、5、25、50或100毫克/千克饮食的氯化铬，持续20周，未观察到任何毒性作用。怀孕小鼠在妊娠第8天接受单次腹腔注射(51)Cr氯化铬（19.5毫克/千克体重Cr），并在注射后4-192小时处死。与对照组相比，实验胚胎的神经板上观察到更多的固缩细胞，特别是在注射后8小时。在兔子的发育研究中，氯化铬诱导了矮小症、卷曲和短尾巴、肺发育不全、心脏肥大、胸腔内出血以及鼻腔和大脑侧脑室的扩张。体外氯化铬干扰了小鼠卵母细胞的减数成熟，降低了受精能力。在四个沙门氏菌菌株（TA1535、TA1537、TA98和TA100）的测试中，氯化铬没有显示出遗传毒性，无论是否经过代谢活化。生态毒性研究：在初步的急性水蚤测试中，氯化铬的24小时EC50为22毫克/升。21天的名义无观察效应浓度为0.70毫克/升，其中最敏感的参数是繁殖率。

IDENTIFICATION AND USE: Chromic chloride forms purple-hexagonal plates. It is used in chromizing; manufacture of Cr metal and compounds; as catalyst for polymerization of olefins and other organic reactions; as textile mordant; in tanning; in corrosion inhibitors, and as a waterproofing agent. It's solution is also used in total parenteral nutrition. HUMAN EXPOSURE AND TOXICITY: Chromic chloride administered intravenously to total parenteral nutrition patients has been shown to be nontoxic when given at dosage levels up to 250 ug/day for two consecutive weeks. Symptoms of toxic chromium reactions include nausea, vomiting, ulcers of the gastrointestinal tract, renal and hepatic damage, and abnormalities of the central nervous system culminating in convulsions and coma. 2211 consecutive patients with suspected allergic contact dermatitis were patch tested with 0.5% potassium dichromate (Cr(VI)) and 13% chromium trichloride (Cr(III)). A total of 71 (3.2%) patients had a positive reaction to Cr(VI), of which 31 also had a positive Cr(III) reaction. No Cr(VI) negative patients had a positive reaction to Cr(III). An increased risk of foot dermatitis was found in Cr(VI) positive patients with a concomitant positive or doubtful reaction to Cr(III) compared with Cr(VI) positive patients with no reactions to Cr(III). Chromic chloride inhibited spindle formation in human skin fibroblasts, but only at the highest concentration tested (100 uM), which was several orders of magnitude higher than the concentration required for chromium (IV) compounds (sodium chromate and calcium chromate) to produce the same effect. Chromic chloride exposure in vitro only had slight impact on the telomere length in human cells. ANIMAL STUDIES: Chromic chloride crystals applied to the intact cornea of rabbits resulted in permanent gray vascularized opacity. Rats were fed a stock diet to which was added 0, 5, 25, 50 or 100 mg of Cr per kg of diet as chloride for 20 weeks without any toxic effects. Pregnant mice were given a single intraperitoneal injection of (51)Cr chromic chloride (19.5 mg/kg body weight Cr) on day 8 of gestation and were sacrificed at intervals of 4-192 hr after injection. More pyknotic cells were observed in the neural plate of experimental embryos than controls, especially by 8 hours after injection. In developmental studies in rabbits chromic chloride induced dwarfism, kinky and short tails, lung hypoplasia, heart hypertrophy, intrathoracic hemorrhage and dilated nares and brain lateral ventricles. In vitro chromic chloride interfered with meiotic maturation of mouse oocyte resulting in reducing the ability of fertilization. Chromic chloride was not genotoxic in four Salmonella strains tested (TA1535, TA1537, TA98, and TA100) with or without metabolic activation. ECOTOXICITY STUDIES: In preliminary acute Daphnia tests, the 24 hr EC50 was 22 mg/L for chromic chloride. The nominal 21 day no observed effect concentration was 0.70 mg/L, with the most sensitive parameter being reproduction rate.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 毒性总结

三价铬还可能形成与肽、蛋白质和DNA的复合物，导致DNA-蛋白质交联、DNA链断裂、DNA-DNA链间交联、铬-DNA加合物、染色体重排和细胞信号通路改变。已经证明，它通过过度刺激细胞调控途径和通过激活某些丝裂原活化蛋白激酶增加过氧化氢水平来诱导癌变。它还可能通过将组蛋白去乙酰化酶1-DNA甲基转移酶1复合物与CYP1A1启动子染色质交联，从而抑制组蛋白修饰，导致转录抑制。铬可能通过修饰金属调控转录因子1，导致抑制锌诱导的金属硫蛋白转录，从而增加其自身的毒性。(A12, L16, A34, A35, A36)

Trivalent chromium may also form complexes with peptides, proteins, and DNA, resulting in DNA-protein crosslinks, DNA strand breaks, DNA-DNA interstrand crosslinks, chromium-DNA adducts, chromosomal aberrations and alterations in cellular signaling pathways. It has been shown to induce carcinogenesis by overstimulating cellular regulatory pathways and increasing peroxide levels by activating certain mitogen-activated protein kinases. It can also cause transcriptional repression by cross-linking histone deacetylase 1-DNA methyltransferase 1 complexes to CYP1A1 promoter chromatin, inhibiting histone modification. Chromium may increase its own toxicity by modifying metal regulatory transcription factor 1, causing the inhibition of zinc-induced metallothionein transcription. (A12, L16, A34, A35, A36)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 致癌性证据

证据权重特征：根据美国环保局（EPA）风险评估指南（1986年）中概述的评估人类致癌性的整体证据权重的标准，三价铬最合适地被指定为D组——关于其人类致癌性尚未分类。使用《致癌物风险评估指南（拟议）》（1996年），数据不足以确定三价铬的潜在致癌性……然而，六价铬作为已知人类致癌物的分类，引起了人们对三价铬致癌潜力的关注。人类致癌性数据：在铬酸盐制造和铁铬工业中，通过吸入三价铬和其他铬化合物进行职业暴露已经得到研究；然而，所有暴露都包括对Cr(III)和Cr(VI)的混合暴露。Cr(VI)物种可能是铬工作者超额癌症风险报告中的病因学因素。关于单独暴露于Cr(III)的数据不可用，数据不足以评估人类致癌潜力。……动物致癌性数据：动物口服和吸入三价铬的数据不支持三价铬致癌性的证明。国际癌症研究机构（IARC）认为动物数据不足以评估Cr(III)化合物的致癌性。此外，尽管有充分的证据表明与铬暴露相关的呼吸道致癌性，但无法阐明Cr(III)、Cr(VI)、金属铬或可溶性铬与不溶性铬对致癌性的相对贡献……/三价铬（III），不溶性盐类/

WEIGHT OF EVIDENCE CHARACTERIZATION: Applying the criteria for evaluating the overall weight of evidence for carcinogenicity to humans outlined in EPA's guidelines for risk assessment (1986), trivalent chromium is most appropriately designated a Group D -- Not classified as to its human carcinogenicity. Using the Proposed Guidelines for Carcinogen Risk Assessment (1996), there are inadequate data to determine the potential carcinogenicity of trivalent chromium ... However, the classification of hexavalent chromium as a known human carcinogen raises a concern for the carcinogenic potential of trivalent chromium. HUMAN CARCINOGENICITY DATA: Occupational exposure to trivalent chromium and other chromium compounds by inhalation has been studied in the chromate manufacturing and ferrochromium industries; however, exposures all include mixed exposures to both Cr(III) and Cr(VI). Cr(VI) species is the likely etiological agent in reports of excess cancer risk in chromium workers. Data addressing exposures to Cr(III) alone are not available and data are inadequate for an evaluation of human carcinogenic potential. ... ANIMAL CARCINOGENICITY DATA: The data from oral and inhalation exposures of animals to trivalent chromium do not support documentation of the carcinogenicity of trivalent chromium. IARC concluded that animal data are inadequate for the evaluation of the carcinogenicity of Cr(III) compounds. Furthermore, although there is sufficient evidence of respiratory carcinogenicity associated with exposure to chromium, the relative contribution of Cr(III), Cr(VI), metallic chromium, or soluble versus insoluble chromium to carcinogenicity cannot be elucidated... /Chromium (III), insoluble salts/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌性证据

A4；不可归类为人类致癌物。/铬和Cr(III)无机化合物/

A4; Not classifiable as a human carcinogen. /Chromium and Cr(III) inorganic compounds/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌性证据

评估：对于金属铬和铬(III)化合物的致癌性，在人类中的证据不足。在实验动物中，对于金属铬、铬酸钡和铬(III)化合物的致癌性证据也不足。总体评估：金属铬和铬(III)化合物在人类致癌性方面无法归类（第3组）。/金属铬和铬(III)化合物/

Evaluation: There is inadequate evidence in humans for the carcinogenicity of metallic chromium and of chromium(III) compounds. There is inadequate evidence in experimental animals for the carcinogenicity of metallic chromium, barium chromate and chromium(III) compounds. Overall evaluation: Metallic chromium and chromium(III) compounds are not classifiable as to their carcinogenicity to humans (Group 3). /Metallic chromium and chromium(III) compounds/

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

在大鼠中，大脑和肌肉对注射的铬(III)氯化物几乎没有亲和力，但肝脏、脾脏和骨髓对其有相当大的摄取。

In rats, brain and muscle appear to have little affinity for injected chromium (III) chloride, but there is a considerable uptake by liver, spleen and bone marrow.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

... 大鼠在通过胃管给药后5分钟内吸收了5%到10%的放射性三价铬（以氯化铬形式）。大鼠保留的铬从5分钟时的5%到10%下降到1小时内的不到1%。... 大部分快速吸收的铬通过胃肠道丢失。

... rats absorbed from 5% to 10% of radioactive trivalent chromium (as the chloride) within 5 min after it was admin by stomach intubation. The chromium retained by the rats decr from 5% to 10% at 5 min to less than 1% at 1 hr. ... most of the quickly absorbed chromium was lost via the gastrointestinal tract.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

各种(51)铬-铬化合物的排泄和全身保留在...小鼠中差异很大。在给小鼠静脉注射剂量后的7天内，保留的(51)铬是...CrCl3的40%。CrCl3在骨髓中有很高的摄取...

The excretion and whole-body retention of various (51)Cr-chromium cmpd differed greatly in ... mouse. ... 7 days after the iv dose to mice, retained (51)Cr was ... 40% of CrCl3 ... There was high uptake of ... CrCl3 in the bone marrow ...

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

瑞士雄性小鼠单次腹腔或皮下注射1 mmol CrCl3/kg体重后，跟踪了组织中的铬水平。两种治疗模式下的血液水平相似，半衰期为31-41小时。未经腹腔直接暴露的器官在两组中含量相似，顺序为肾脏 > 肺 > 心脏 > 大脑。然而，腹腔注射后，腹膜器官（肝脏、脾脏、胰腺和睾丸）的铬含量比皮下注射高出40至200倍。对腹膜下肝脏组织和通过阴囊切除的睾丸的检测表明，铬渗透到器官中，而不是表面的吸附。腹腔注射后的相对铬浓度顺序为肝脏 > 胰腺 = 脾脏 > 睾丸，而皮下注射后的顺序为肝脏 > 脾脏 > 睾丸 > 胰腺。因此，CrCl3的皮下治疗在吸收到血液中的效果与腹腔注射相当。腹腔注射导致直接吸收到腹膜器官中，是一种有效将这些器官暴露于高剂量铬的方法，但不模拟人类可能的暴露方式。

The tissue levels of chromium were followed after single intraperitoneal or subcutaneous injection of 1 mmol CrCl3/kg body wt. in Swiss male mice. Blood levels were similar after both treatment modes, with half-lives of 31-41 h. Organs not directly exposed by i.p. treatment contained similar amounts in the two groups, with kidneys > lungs > heart > brain. However, after i.p. treatment peritoneal organs (liver, spleen, pancreas and testis) had 40- to 200-fold more chromium compared with s.c. Assay of subsurface liver tissue and of testes removed via the scrotum indicated infiltration of the organs, rather than surface adsorption, of peritoneal chromium. Relative chromium concentrations after i.p. treatment were liver > pancreas = spleen > testis and after s.c. liver > spleen > testis > pancreas. Thus, s.c. treatment with CrCl3 is as effective as i.p. in terms of absorption into the blood. Treatment i.p., leading to direct uptake into peritoneal organs, is an effective way to deliver high chromium doses to these organs, but does not model likely human exposure.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

• 吸收

铬的吸收可以通过运动增加。

Chromium absorption can increase with exercise.

来源:DrugBank

安全信息

• TSCA：
  Yes
• 危险等级：
  8
• 危险品标志：
  Xn
• 安全说明：
  S24/25
• 危险类别码：
  R22,R36/37/38
• WGK Germany：
  1
• 海关编码：
  28273985
• 危险品运输编号：
  UN3260
• RTECS号：
  GB5425000
• 包装等级：
  III
• 危险类别：
  8
• 危险标志：
  GHS05,GHS07,GHS09
• 危险性描述：
  H302,H314,H411
• 危险性防范说明：
  P260,P280,P301 + P312 + P330,P303 + P361 + P353,P304 + P340 + P310,P305 + P351 + P338

制备方法与用途

化学性质
紫色单斜晶体，能溶于水和乙醇，微溶于丙酮，不溶于乙醚。

用途
三氯化铬（化学式：CrCl₃）常作为媒染剂和催化剂使用。该物质易潮解、升华，在高温下容易被氧气氧化。三氯化铬存在无水物和六水合物两种形式。

三氯化铬无水物是一种强烈发光的紫色结晶，几乎不溶于水；而其六水合物则形成一个配合物，具有三种不同的水合异构体：紫色、浅绿色和暗绿色固体。通常在市场上购买到的是暗绿色异构体。

三氯化铬晶体中含有连接成层的CrCl₆八面体单元，并存在螺旋状位错结构，不含金属-金属键。无水三氯化铬是有机金属化学中的重要原料，可用于制备多种有机铬化合物，例如结构上类似二茂铁的二苯铬。此外，它也是合成许多铬(III)配合物的基础原料。

反应信息

• 作为反应物：
  描述：

  三氯化铬 在 草酸 作用下， 以 not given 为溶剂， 生成 铬
  参考文献：
  名称：

  Chromium plating

  摘要：

  292,094号专利，由Potts, H. E.（Ternstedt Manufacturing Co.）于1928年5月11日提交。在1928年6月14日的法案第91节下，该专利规范已公开展示。铬沉积-该浴液包含铬酸盐和多种碱金属或碱土金属氯化物，浓度明显高于只用其中一种氯化物饱和的浓度。一个适当的浴液包含每升300克紫色改性的水合铬酸盐，250克氯化钾，150克氯化钠，150克氯化铵；这些量可以增加到（冷）饱和值。还可以添加每升3-5克氟化钠，每升75-100克草酸作为还原剂和1％的硝酸。也可以使用其他氟化物。阳极是铬或可溶性铬化合物，如铁铬。应用8-12伏特电压和每平方英尺阴极表面250-1000安培的电流密度。参考专利号19344/90和22855/91。

  公开号：

  US01838777A1
• 作为产物：
  描述：

  氯 在 ferrochromium 作用下， 以85.9%的产率得到三氯化铬
  参考文献：
  名称：

  Gmelin Handbuch der Anorganischen Chemie, Gmelin Handbook: Cr: MVol.A1, 6.1, page 234 - 236

  摘要：

  DOI：
• 作为试剂：
  描述：

  2-甲基二苯甲酮 在 三氯化铬 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以46%的产率得到1,2-二苯基-1,2-二(O-甲苯基)乙烷-1,2-二醇
  参考文献：
  名称：

  电有机反应。第25部分。铬（III）在改性松节油中的作用

  摘要：

  水合和无水氯化铬（III）的存在深刻改变了二苯甲酮，苯甲醛，β-紫罗兰酮，β-紫罗兰乙醛和视网膜的二甲基甲酰胺溶液中阴极还原的过程。戊四醇化作用以形成相应的醇为代价而得到增强。此外，相关的还原潜力也降低了。已使用伏安法和库仑法实验结合了在各种条件下对制备规模的还原反应的详细分析，研究了反应的机理。还考虑了反应的立体化学过程。总体而言，该结果提供了令人信服的证据，表明关键的可还原中间体为羰基化合物-Cr III配合物，该中间体形成通过相应的具有均匀内部球体的Cr II物种，再氧化起着至关重要的作用。这与先前提出的将电生成的Cr II作为还原剂参与的建议背道而驰。

  DOI：

  10.1039/p29840001361

文献信息

• Synthesis and structural characterization of L-histidinato-D-penicillaminatochromium(III) monohydrate
  作者：Patrice de Meester、Derek J. Hodgson

  DOI：10.1039/dt9770001604

  日期：——

  The novel chromium(III) amino-acid complex L-histidinato-D-penicillaminatochromium(III) monohydrate, [Cr(L-his)(D-pen)]·H2O (his = histidine, pen = penicillamine), has been prepared by the reaction of D-penicillamine with an aqueous solution containing chromium(III) chloride (or nitrate) and L-histidine. The crystal structure of the complex has been determined from three-dimensional X-ray counter data

  新颖的铬（III）氨基酸复合大号-histidinato- d -penicillaminatochromium（III）一水合物，[CR（大号-his）（d -pen）]·H 2 O（他=组氨酸，笔=青霉胺），具有通过使D-青霉胺与包含氯化铬（III）氯化物（或硝酸盐）和L-组氨酸的水溶液反应制备。配合物的晶体结构已经由三维X射线计数器数据确定。该复合物在单斜空间群P 2 1，Z中结晶= 2，在尺寸为a = 7.235（4），b = 12.150（8），c = 8.929（6）Å，β= 6.00（3）°的像元中。结构的全矩阵最小二乘优化。使用1 635强度，得出的最终R为0.035。该络合物是单体的，在铬处的八面体几何形状变形，导致顺式键角在79.8（2）–102.2（2）°范围内。三齿D-青霉胺部分作为二价阴离子，在S和O处被去质子化，Cr–S，Cr–N和Cr–O键长分别为2.332（2），2
• Organometallic Chemistry sans Organometallic Reagents: Modulated Electron‐Transfer Reactions of Subvalent Early Transition Metal Salts
  作者：John J. Eisch、Xian Shi、Joseph R. Alila、Sven Thiele

  DOI：10.1002/cber.19971300903

  日期：1997.9

  reductant, titanium dichloride, has been throughly examined, as well as the analogous ZrCl2 and HfCl2 reagents, all of which are readily obtainable by the alkylative reduction of the Group tetrachloride by butyllithium in THF. Noteworthy is that such interactions of MCl4 with butyllithium in hydrocarbon media lead, in contrast, to M(III) or M(IV) halide hydrides. Analogous alkylative reductions in THF

  低价，早期过渡金属试剂在有机化学中作为选择性还原剂的潜力已通过对McMurry反应及其众多变体中产生的不明确且不均一的亚价钛中间体的深入研究而得以预示。作为开发对有机底物具有调制和选择性活性的可溶，定义明确的过渡金属还原剂的长期研究工作的一部分，已彻底检查了可溶于THF的还原剂二氯化钛以及类似的ZrCl 2和HfCl 2试剂，通过在THF中用丁基锂对四氯化物进行烷基化还原，很容易获得所有这些试剂。值得注意的是，MCl 4的这种相互作用相反，在烃介质中用丁基锂制得的M（III）或M（IV）卤化物氢化物。应用于VCl 4，CrCl 3和MoCl 5的THF中类似的烷基化还原反应产生的还原剂与从Mcl 4获得的还原剂相似，但反应活性分级。已证明这种还原剂能够以与涉及两电子转移（TET）的氧化加成一致的方式偶联羰基衍生物，苄基卤化物，乙炔和某些烯烃。这种反应途径与观察到的由酮形成频哪醇的立体化学以及炔烃的还原性二聚化相一致。与CrCl
• Studies on the synthesis and electrochemistry of crown ether dithiocarbamates and the molecular dynamics of bis(aza-15-crown-5)thiuram disulphide. Crystal structure of cobalt tris[(aza-15-crown-5)dithiocarbamate]
  作者：Jaume Granell、Malcolm L. H. Green、Valerie J. Lowe、Seth R. Marder、Philip Mountford、Graham C. Saunders、Neil M. Walker

  DOI：10.1039/dt9900000605

  日期：——

  are present ΔG‡ falls to 54.5 ± 0.5 kJ mol–1. Complexes of the crown ether dithiocarbamates with Ni, Cu, Cr, Fe, Co, and Mo have been prepared and their electrochemistry investigated. Small shifts in the values of E½ were observed in the presence of alkali-metal cations. The molecular structure of cobalt tris[(aza-15-crown-5)dithiocarbamate] has been determined by X-ray crystallography.

  aza-15-crown-5（1,4,7,10-tetraoxa-13-azacyclopentadecane）与氢氧化钠和二硫化碳反应生成二硫代氨基甲酸钠（aza-15-crown-5）二硫代氨基甲酸钠（1,4,7， 10-四氧杂十三-氮杂环戊二烯-13-碳二硫酸酯），（1）。4'-氨基苯并-15-冠-5（15-氨基苯并1,4,7,10,13-五氧杂环戊烷）形成相应的二硫代氨基甲酸酯（2）。化合物（1）的氧化二聚产生双（氮杂-15-冠-5）秋兰姆二硫化物[13,13'-（1,4-dithioxo-2,3-dithiabutane-1,4-diyl）di（1,4 ，（7，10-四氧杂十三-氮杂环戊烷）]，（3），相反（2）在相同条件下分解为4'-异硫氰酸根合苯并基-15-冠-5。绕S 2旋转的能量屏障化合物（3）的C–N键，ΔG ‡ = 65.3±0.5 kJ mol –1，由13 C-
• Cesium and Its Analogs, Rubidium and Potassium, in Rhombohedral [NaZr2(PO4)3 Type] and Cubic (Langbeinite Type) Phosphates: 1. Crystal-Chemical Studies
  作者：A. I. Orlova、V. A. Orlova、A. V. Buchirin、A. I. Beskrovnyi、V. S. Kurazhkovskaya

  DOI：10.1007/s11137-005-0078-6

  日期：2005.5

  The published crystallographic data on cesium, rubidium, and potassium phosphates crystallizing in the NaZr2(PO4)3 (NZP) and langbeinite structural types are summarized and correlated. The existence of new phosphates, analogs of langbeinite mineral, is predicted. The phosphates of the suggested compositions are prepared and studied by X-ray and neutron diffraction and by IR spectroscopy. Phosphates

  总结并关联了NaSr 2（PO 4）3（NZP）和兰贝石结构类型中结晶的铯，rub和磷酸钾的晶体学数据。预计会出现新的磷酸盐，这是蓝贝氏体矿物的类似物。通过X射线和中子衍射以及通过红外光谱法来制备和研究所建议的组合物的磷酸盐。式A 2 RM（PO 4）3，A 2 B 0.5 Zr 1.5（PO 4）3和ABR 2（PO 4）3的磷酸盐具有一个立方晶胞，空间群 P 2 1 3。在这些系列中，磷酸盐的晶胞参数仅随阳离子组成的变化而略有变化。根据结构研究的结果，可以估算出根据阳离子，兰贝纳石结构中键长和键角的变化。铯可以至多38wt％的量掺入立方骨架磷酸盐中。兰贝氏体结构的特征是同构取代的可能性很大，涉及大的碱金属和碱土金属阳离子排列在骨架空洞中，而小的 p，d 和 f 阳离子 处于氧化态2 +，3 +和4+的元素排列在骨架位置上。注意到镧系元素在兰贝尼特型骨架形成中的特定作用。
• The preparation of the 2,4-di(t-butyl)pentadienyl anion and its Ti(II), Cr(II), and Zn(II) complexes
  作者：Richard D. Ernst、Jeffrey W. Freeman、Paul N. Swepston、David R. Wilson

  DOI：10.1016/0022-328x(91)80077-w

  日期：1991.1

  The potassium of the 2,4-di(t-butyl)pentadienyl anion may be prepared by metallation of the corresponding 1,3-diene. This anion reacts readily with titanium, chromium, and zinc dichloride complexes to yield the appropriate M[2.4-(t-C4H9)2C5H5]2 species, which display significant differences relative to their 2,4-dimethylpentadienyl analogs.

  2，4-二（叔丁基）戊二烯基阴离子的钾可以通过相应的1，3-二烯的金属化来制备。该阴离子容易与钛，铬和二氯化锌络合物反应，生成适当的M [2.4-（tC 4 H 9）2 C 5 H 5 ] 2物种，相对于它们的2,4-二甲基戊二烯基类似物，它们显示出显着差异。

表征谱图