Caesium carbonate: Difference between revisions

| Watchedfields = changed

| verifiedrevid = 443031611

| Reference = <ref>{{RubberBible62nd | page=B-91}}.</ref>

| ImageFile = Cesium carbonate.svg

| ImageFile1 = Caesium-carbonate-3D-Balls.png

| ImageCaption1 = {{legend|rgb(64,16,96)|Caesium, Cs}}{{legend|black|Carbon, C}}{{legend|red|Oxygen, O}}

| ImageFile2 = Caesium carbonate.jpg

| PIN = Dicaesium carbonate

| OtherNames = {{ubl|Caesium carbonate|Cesium carbonate}}

|Section1={{Chembox Identifiers

| StdInChI_Ref = {{stdinchicite | correct | chemspider}}

| StdInChIKey_Ref = {{stdinchicite | correct | chemspider}}

| CASNo_Ref = {{cascite | correct | CAS}}

| UNII_Ref = {{fdacite | correct | FDA}}

| UNII = QQI20A14P4

| EC_number = 208-591-9

| ChemSpiderID_Ref = {{chemspidercite | correct | chemspider}}

|Section2={{Chembox Properties

| Formula = {{chem2|Cs2CO3}}

| Cs=2|C=1|O=3

| MeltingPtC = 610

| MeltingPt_notes = ([[Decomposition|decomposes]])

| Solubility2 = 119.6 g/L

| Solvent2 = dimethylformamide

| Solubility3 = 361.7 g/L

| Solvent3 = dimethyl sulfoxide

| Solubility4 = 394.2 g/L

| Solvent4 = sulfolane

| Solubility5 = 723.3 g/L

| Solvent5 = methylpyrrolidone

| MagSus = −103.6·10⁻⁶ cm³/mol

|Section7={{Chembox Hazards

| ExternalSDS =

| FlashPt = Non-flammable

|Section8={{Chembox Related

| OtherCations = {{ubl|[[Lithium carbonate]]|[[Sodium carbonate]]|[[Potassium carbonate]]|[[Rubidium carbonate]]}}

'''Caesium carbonate''' or '''cesium carbonate''' is a [[chemical compound]] with the [[chemical formula]] {{chem2|Cs2CO3|auto=1}}. It is white crystalline [[solid]]. [[Caesium]] [[carbonate]] has a high [[solubility]] in polar solvents such as [[water]], [[ethanol]] and [[dimethylformamide|DMF]]. Its [[solubility]] is higher in [[Organic compound|organic]] [[solvents]] compared to other carbonates like [[potassium carbonate]] and [[sodium carbonate]], although it remains quite insoluble in other organic solvents such as [[toluene]], [[p-xylene|''p''-xylene]], and [[chlorobenzene]]. This compound is used in organic synthesis as a [[Base (chemistry)|base]].<ref>{{cite book |doi=10.1002/047084289X.rc049.pub2|chapter=Cesium Carbonate |title=Encyclopedia of Reagents for Organic Synthesis |year=2001 |last1=Sivik |first1=Mark R. |last2=Ghosh |first2=Arun K. |last3=Sarkar |first3=Anindya |pages=1–12 |isbn=9780470842898}}</ref> It also appears to have applications in energy conversion.

==Preparation==

Caesium carbonate can be prepared by [[thermal decomposition]] of caesium oxalate.<ref name="simons">{{cite journal | author1=E. L. Simons | author2=E. J. Cairns | author3 = L. D. Sangermano | title=Purification and preparation of some caesium compounds | journal= Talanta | year=1966 | volume=13 | issue=2 | pages=199–204 | pmid=18959868 | doi = 10.1016/0039-9140(66)80026-7}}</ref> Upon heating, [[caesium oxalate]] is converted to caesium carbonate with emission of [[carbon monoxide]].

:{{chem2|Cs2C2O4 → Cs2CO3 + CO}}

It can also be synthesized by reacting [[caesium hydroxide]] with carbon dioxide.<ref name="simons"/>

:{{chem2|2 CsOH + CO2 → Cs2CO3 + H2O}}

==Chemical reactions==

Caesium carbonate facilitates the ''N''-alkylation of compounds such as [[sulfonamides]], [[amines]], [[Beta-lactam|β-lactams]], [[indoles]], [[heterocyclic compounds]], ''N''-substituted [[aromatic]] [[imides]], [[phthalimide]]s, and other similar compounds.<ref name="Escudero">{{cite journal | last=Mercedes | first=Escudero |author2=Lautaro D. Kremenchuzky |author3=a Isabel A. Perillo |author4=Hugo Cerecetto |author5=María Blanco | title=Efficient Cesium Carbonate Promoted N-Alkylations of Aromatic Cyclic Imides Under Microwave Irradiation | journal=Synthesis | year=2010 | volume=2011 | issue=4 | page=571 | doi=10.1055/s-0030-1258398}}</ref> Research on these compounds has focused on their synthesis and biological activity.<ref name="Babak">{{cite journal | last=Babak | first=Karimi |author2=Frahad Kabiri Estanhani | title=Gold nanoparticles supported on Cs₂CO₃ as recyclable catalyst system for selective aerobic oxidation of alcohols at room temperature | journal=Chemical Communications | year=2009 | volume=5556 | issue=55 | pages=5555–5557 | doi=10.1039/b908964k| pmid=19753355}}</ref> In the presence of [[sodium tetrachloroaurate]] ({{chem2|Na[AuCl4]}}), caesium carbonate is very efficient mechanism for [[Cellular respiration#Aerobic respiration|aerobic oxidation]] of different kinds of [[alcohols]] into [[ketones]] and [[aldehydes]] at room temperature without additional [[Polymer|polymeric compounds]]. There is no [[acid]] formation produced when [[primary alcohol]]s are used.<ref>{{cite journal | last=Lie | first=Liand | author2=Guodong Rao | author3=Hao-Ling Sun | author4=Jun-Long Zhang | title=Aerobic Oxidation of Primary Alcohols Catalyzed by Copper Salts and Catalytically Active m-Hydroxyl-Bridged Trinuclear Copper Intermediate | journal=Advanced Synthesis & Catalysis | year=2010 | volume=352 | issue=23 | pages=2371–2377 | doi=10.1002/adsc.201000456 | url=http://www.chem.pku.edu.cn/zhangjl/papers/adsc.201000456.pdf | format=reprint | access-date=2012-04-27 | archive-url=https://web.archive.org/web/20140201162136/http://www.chem.pku.edu.cn/zhangjl/papers/adsc.201000456.pdf | archive-date=2014-02-01 | url-status=dead}}</ref> The process of selective [[Redox|oxidation]] of alcohols to [[carbonyls]] had been quite difficult due to the [[nucleophilic]] character of the carbonyl [[Reaction intermediate|intermediate]].<ref name="Babak"/> In the past [[Chromium|Cr]](VI) and [[Manganese|Mn]](VII) reagents have been used to oxidize alcohols, however, these reagents are toxic and comparatively expensive. Caesium carbonate can also be used in [[Suzuki reaction|Suzuki]], [[Heck reaction|Heck]], and [[Sonogashira coupling|Sonogashira]] synthesis reactions. Caesium carbonate produces [[carbonylation]] of alcohols and [[carbamination]]{{cln|reason=What is carbamination???|date=December 2023}} of [[amines]] more efficiently than some of the mechanisms that have been introduced in the past.<ref name="Venka">{{cite journal | last=Rattan | first=Gujadhur |author2=D. Venkataraman |author3=Jeremy T. Kintigh | title=Formation of aryl–nitrogen bonds using a soluble copper(I) catalyst | journal=Tetrahedron Letters | year=2001 | volume=42 | issue=29 | pages=4791–4793 | url=http://people.umass.edu/dv/pdf/tetlet1.pdf|doi=10.1016/s0040-4039(01)00888-7}}</ref> Caesium carbonate can be used for sensitive synthesis when a balanced strong base is needed.

==For energy conversion==

Relatively effective polymer [[solar cells]] are built by [[thermal annealing]] of caesium carbonate. Caesium carbonate increases the energy [[effectiveness]] of the power conversion of solar cells and enhances the life times of the equipment.<ref name="Huang">{{cite journal|last=Jinsong |first=Huang |author2=Zheng Xu |author3=Yang Yang |title=Low-Work-Function Surface Formed by Solution-Processed and Thermally Deposited Nanoscale Layers of Cesium Carbonate |journal=Advanced Functional Materials |year=2007 |volume=17 |issue=19 |pages=1966–1973 |doi=10.1002/adfm.200700051 |s2cid=44557096 |url=http://yylab.seas.ucla.edu/papers/AFM%20Cs₂CO₃.pdf |accessdate=2012-03-31}}{{dead link|date=November 2016 |bot=InternetArchiveBot |fix-attempted=yes}}</ref> The studies done on UPS and XPS reveal that the system will do less work due to the thermal annealing of the {{chem2|Cs2CO3}} layer. Caesium carbonate breaks down into [[Caesium monoxide|{{chem2|Cs2O}}]] and [[Caesium peroxide|{{chem2|Cs2O2}}]] by thermal evaporation. It was suggested that, when {{chem2|Cs2O}} combines with {{chem2|Cs2O2}} they produce n-type dopes that supplies additional conducting electrons to the host devices. This produces a highly efficient inverted cell that can be used to further improve the efficiency of polymer solar cells or to design adequate multijunction photovoltaic cells.<ref>{{cite journal | last=Hua-Hstien | first=Liao |author2=Li-Min Chen |author3=Zheng Xu |author4=Gang Li |author5=Yang Yang | title=Highly efficient inverted polymer solar cell by low temperature annealing of Cs₂CO₃ interlayer | journal=Applied Physics Letters | year=2008 | volume=92 | issue=17 | page=173303 | doi=10.1063/1.2918983 | bibcode=2008ApPhL..92q3303L | url=http://yylab.seas.ucla.edu/papers/ApplPhysLett_92_173303.pdf}}</ref>

The [[nanostructure]] layers of {{chem2|Cs2CO3}} can be used as cathodes for organic electronic materials due to its capacity to increase the kinetic energy of the electrons. The nanostructure layers of caesium carbonate had been probed for various fields using different techniques. The fields include such as [[photovoltaic]] studies, current-voltage [[measurements]], UV [[photoelectron spectroscopy]], [[X-ray photoelectron spectroscopy]], and [[impedance spectroscopy]]. The [[n-type semiconductor]] produced by thermal [[evaporation]] of {{chem2|Cs2CO3}} reacts intensively with metals like Al, and Ca in the cathode. This reaction will cut down the work the cathode metals.<ref>{{cite journal | last=Jen-Chun | first=Wang |author2=Wei-Tse Weng |author3=Meng-Yen Tsai |author4=Ming-Kun Lee |author5=Sheng-Fu Horng |author6=Tsong-Pyng Perng |author7=Chi-Chung Kei |author8=Chih-Chieh Yuc |author9=Hsin-Fei Meng | title=Highly efficient flexible inverted organic solar cells using atomic layer deposited ZnO as electron selective layer | journal=Journal of Materials}}</ref> Polymer solar cells based on solution process are under extensive studies due to their advantage in producing low cost solar cells. [[Lithium fluoride]] has been used to raise the [[power conversion]] efficiency of polymer [[solar cells]]. However, it requires high temperatures (> 500 degree), and high vacuum states raise the cost of production. The devices with {{chem2|Cs2CO3}} layers have produced equivalent power conversion efficiency compared with the devices that use lithium fluoride.<ref name="Huang"/> Placing a {{chem2|Cs2CO3}} layer in between the cathode and the light-emitting polymer improves the efficiency of the white [[OLED]].

<references/>

*{{cite journal | last1 = Crich | first1 = David | last2 = Banerjee | first2 = Abhisek | title = Expedient Synthesis of syn-β-Hydroxy-α-amino acid derivatives: Phenylalanine, Tyrosine, Histidine and Tryptophan | journal = J. Org. Chem. | year = 2006 | volume = 71 | issue = 18 | pages = 7106–9 | doi = 10.1021/jo061159i | pmid = 16930077 | pmc = 2621330}}

* {{cite journal | last=Gerard | first=Dijkstra |author2=Wim H. Kruizinga |author3=Richard M. Kellogg | title=An Assessment of the Causes of the "Cesium Effect" | journal=J. Org. Chem. | year=1987 | volume=52 | issue=19 | page=4230 | doi=10.1021/jo00228a015}}

*{{OrgSynth preps | id=49137 | name=caesium carbonate}}

*[https://web.archive.org/web/20110708141716/http://www.specialmetals.chemetall.com/pdf/Cesium_Carbonate_999.pdf Caesium carbonate factsheet from Chemetall GmbH]

*[https://web.archive.org/web/20151123021127/http://www.muskingum.edu/dept/science/documents/cesiumcarbonate.pdf Material Safety Data Sheet Cesium Carbonate, 99.5%]

{{Carbonates}}

[[Category:Caesium compounds]]

[[Category:Carbonates]]

[[Category:Reagents for organic chemistry]]