Wikipedia:WikiProject Chemicals/Chembox validation/VerifiedDataSandbox and 1,10-Phenanthroline: Difference between pages

{{Short description|Heterocyclic organic compound}}

|Verifiedimages = changed

|Watchedfields = changed

|verifiedrevid = 464199880

|Name = Phenanthroline

|ImageFile_Ref = {{chemboximage|correct|??}}

|ImageFile = 1,10-phenanthroline.svg

|ImageName = 1,10-phenanthroline

|ImageFile1 = Sample of 1,10-Phenanthroline.jpg

|ImageName1 = Sample of 1,10-Phenanthroline

|PIN = 1,10-Phenanthroline<ref name=iupac2013>{{cite book | title = Nomenclature of Organic Chemistry : IUPAC Recommendations and Preferred Names 2013 (Blue Book) | publisher = [[Royal Society of Chemistry|The Royal Society of Chemistry]] | date = 2014 | location = Cambridge | page = 211 | doi = 10.1039/9781849733069-FP001 | isbn = 978-0-85404-182-4}}</ref>

|Section1={{Chembox Identifiers

|index1_label = monohydrate

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

|ChemSpiderID = 1278

|ChemSpiderID1 = 19955

|InChI = 1/C12H8N2/c1-3-9-5-6-10-4-2-8-14-12(10)11(9)13-7-1/h1-8H

|InChIKey = DGEZNRSVGBDHLK-UHFFFAOYAW

|ChEMBL_Ref = {{ebicite|correct|EBI}}

|ChEMBL = 415879

|PubChem = 1318

|PubChem1 = 21226

|EC_number = 200-629-2

|EC_number1 = 627-114-9

|ChEMBL1 = 1255788

|KEGG = C00604

|Beilstein = 126461

|Gmelin = 4040

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

|StdInChI = 1S/C12H8N2/c1-3-9-5-6-10-4-2-8-14-12(10)11(9)13-7-1/h1-8H

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

|StdInChIKey = DGEZNRSVGBDHLK-UHFFFAOYSA-N

|CASNo = 66-71-7

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

|CASNo1 = 5144-89-8

|CASNo1_Ref = {{cascite|correct|CAS}}

|CASNo1_Comment = (monohydrate)

|UNNumber = 2811

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

|UNII = W4X6ZO7939

|UNII1_Ref = {{fdacite|correct|FDA}}

|UNII1 = KSX215X00E

|DrugBank_Ref = {{drugbankcite|correct|drugbank}}

|DrugBank = DB02365

|ChEBI_Ref = {{ebicite|correct|EBI}}

|ChEBI = 44975

|SMILES = c1cc2ccc3cccnc3c2nc1

|SMILES1 = C1=CC2=C(C3=C(C=CC=N3)C=C2)N=C1.O

|RTECS = SF8300000

|Section2={{Chembox Properties

|Formula = C₁₂H₈N₂

|MolarMass = 180.21 g/mol

|Appearance = colourless crystals

|Density = 1.31 g/cm³

|Solubility = high<ref name=crc/>

|Solvent = other solvents

|SolubleOther = acetone, ethanol<ref name=crc/>

|MeltingPtC = 118.56

|MeltingPt_ref = <ref name=crc>{{cite book | editor= Haynes, William M. | date = 2016| title = [[CRC Handbook of Chemistry and Physics]] | edition = 97th | publisher = [[CRC Press]] | isbn = 978-1-4987-5429-3|page=3.444}}</ref>

|BoilingPt =409.2

|BoilingPt_ref = <ref name=crc/>

|pKa = 4.84 (phenH⁺)<ref name=crc/>

}}

|Section7={{Chembox Hazards

|MainHazards = mild neurotoxin, strong nephrotoxin, and powerful diuretic

|GHSPictograms = {{GHS06}}{{GHS09}}

|GHSSignalWord = Danger

|HPhrases = {{H-phrases|301|410}}

|PPhrases = {{P-phrases|264|270|273|301+310|321|330|391|405|501}}

}}

|Section8={{Chembox Related

|OtherCompounds = [[2,2'-bipyridine]]<br />[[ferroin]]<br />[[phenanthrene]]

}}

}}

'''1,10-Phenanthroline''' ('''phen''') is a [[heterocyclic]] [[organic compound]]. It is a white solid that is soluble in organic solvents. The 1,10 refer to the location of the nitrogen atoms that replace CH's in the hydrocarbon called [[phenanthrene]].

Abbreviated "phen", it is used as a [[ligand]] in [[coordination chemistry]], forming strong complexes with most metal ions.<ref name=Castellano>Luman, C.R. and Castellano, F.N. (2003) "Phenanthroline Ligands" in Comprehensive Coordination Chemistry II. Elsevier. {{ISBN|978-0-08-043748-4}}.</ref><ref>{{cite journal |doi=10.1039/cs9942300327|title=1,10-Phenanthroline: A versatile ligand|year=1994|last1=Sammes|first1=Peter G.|last2=Yahioglu|first2=Gokhan|journal=Chemical Society Reviews|volume=23|issue=5|page=327}}</ref> It is often sold as the monohydrate.

==Synthesis==

Phenanthroline may be prepared by two successive [[Skraup reaction]]s of [[glycerol]] with [[o-Phenylenediamine|''o''-phenylenediamine]], catalyzed by [[sulfuric acid]], and an oxidizing agent, traditionally [[Aqueous solution|aqueous]] [[arsenic acid]] or [[nitrobenzene]].<ref>{{cite journal | journal = [[J. Chem. Soc.]] | pages = 155–157 | year = 1946 |doi = 10.1039/jr9460000155 |pmid=20983293 | title = 43. Attempts to find new antimalarials. Part XXIV. Derivatives of o-phenanthroline (7 : 8 : 3{{prime}} : 2{{prime}}-pyridoquinoline)| last1 = Halcrow | first1 = Barbara E. | last2 = Kermack | first2 = William O. }}</ref> Dehydration of [[glycerol]] gives [[acrolein]] which condenses with the [[amine]] followed by a cyclization.

==Coordination chemistry==

In terms of its coordination properties, phenanthroline is similar to [[2,2'-bipyridine]] (bipy) with the advantage that the two nitrogen donors are preorganized for chelation. Phenanthroline is a stronger base than bipy. According to one ligand ranking scale, phen is a weaker donor than bipy.<ref>{{cite journal|last1=Teng|first1=Qiaoqiao|last2=Huynh|first2=Han Vinh|title=A Unified Ligand Electronic Parameter Based on C NMR Spectroscopy of N-Heterocyclic Carbene Complexes|journal=Dalton Transactions|date=2017|volume=46|issue=3|pages=614–627|doi=10.1039/C6DT04222H|pmid=27924321}}</ref>

Several homoleptic complexes are known of the type [M(phen)₃]²⁺. Particularly well studied is [Fe(phen)₃]²⁺, called "[[ferroin]]." It can be used for the [[spectrophotometry|photometric]] determination of Fe(II).<ref>{{cite journal | author = Belcher R | year = 1973 | title = Application of chelate Compounds in Analytical Chemistry | journal = Pure and Applied Chemistry | volume = 34 | pages = 13–27 | doi = 10.1351/pac197334010013 | s2cid = 44054260 | doi-access = free }}</ref> It is used as a [[redox indicator]] with [[standard potential]] +1.06 V. The reduced ferrous form has a deep red colour and the oxidised form is light-blue.<ref>{{cite journal

| last1 = Bellér | first1 = G. B.

| last2 = Lente | first2 = G. B.

| last3 = Fábián | first3 = I. N.

| title = Central Role of Phenanthroline Mono-N-oxide in the Decomposition Reactions of Tris(1,10-phenanthroline)iron(II) and -iron(III) Complexes

| journal = Inorganic Chemistry

| volume = 49

| issue = 9

| pages = 3968–3970

| year = 2010

| pmid = 20415494

| doi = 10.1021/ic902554b

}}</ref> The pink complex [Ni(phen)₃]²⁺ has been resolved into its Δ and Λ isomers.<ref>{{cite book | chapter = Resolution of the tris-(1,10-Phenanthroline)Nickel(II) Ion |author1=George B. Kauffman |author2=Lloyd T. Takahashi |title=Inorganic Syntheses | year = 1966 | volume = 5 | pages = 227–232|doi=10.1002/9780470132395.ch60 |isbn=978-0-470-13239-5 }}</ref> The complex [Ru(phen)₃]²⁺ is bioactive.<ref>{{cite journal | title = Biological Activity of Complex Ions | journal = [[Nature (journal)|Nature]] | volume = 170 | pages = 190–191 | year = 1952 | doi = 10.1038/170190a0 | pmid=12982853 | issue=4318|bibcode=1952Natur.170..190D | last1 = Dwyer | first1 = F. P. | last2 = Gyarfas | first2 = Eleonora C. | last3 = Rogers | first3 = W. P. | last4 = Koch | first4 = Judith H. | s2cid = 6483735 }}</ref>

Copper(I) forms [Cu(phen)₂]⁺, which is luminescent.<ref>{{cite journal | author = Armaroli N | year = 2001 | title = Photoactive Mono- and Polynuclear Cu(I)-Phenanthrolines. A Viable Alternative to Ru(Ii)-Polypyridines? | journal = Chemical Society Reviews | volume = 30 | issue = 2| pages = 113–124 | doi = 10.1039/b000703j }}</ref><ref name=Pallenberg/>

==Bioinorganic chemistry==

1,10-Phenanthroline is an [[enzyme inhibitor|inhibitor]] of [[metallopeptidase]]s, with one of the first observed instances reported in carboxypeptidase A.<ref>{{cite journal | doi = 10.1021/bi00908a006 | title = The mechanism of inhibition of carboxypeptidase A by 1,10-phenanthroline | journal = Biochemistry | year = 1962 | volume = 1 | pages = 231–238 | pmid = 13892106 | issue = 2| last1 = Felber | first1 = Jean-Pierre | last2 = Coombs | first2 = Thomas L. | last3 = Vallee | first3 = Bert L. }}</ref> Inhibition of the enzyme occurs by removal and chelation of the metal ion required for catalytic activity, leaving an inactive apoenzyme. 1,10-Phenanthroline targets mainly zinc metallopeptidases, with a much lower affinity for calcium.<ref>{{cite book |author1=Salvesen, GS |author2=Nagase, H |name-list-style=amp | chapter = Inhibition of proteolytic enzymes | title =Proteolytic Enzymes: A Practical Approach|edition = 2nd| year = 2001 | volume = 1 | pages = 105–130 |editor=Beynon, Rob |editor2=Bond, J S |isbn=978-0-19-963662-4|publisher=Oxford University Press}}</ref>

==Related phen ligands==

A variety of substituted derivatives of phen have been examined as ligands.<ref name=Pallenberg>{{cite journal |author=Pallenberg A. J. |author2=Koenig K. S. |author3=Barnhart D. M. | year = 1995 | title = Synthesis and Characterization of Some Copper(I) Phenanthroline Complexes | journal = Inorganic Chemistry | volume = 34 | issue = 11| pages = 2833–2840 | doi = 10.1021/ic00115a009 }}</ref><ref>{{cite journal |doi=10.1039/B806408N |title=1,10-Phenanthrolines: Versatile building blocks for luminescent molecules, materials and metal complexes |date=2009 |last1=Accorsi |first1=Gianluca |last2=Listorti |first2=Andrea |last3=Yoosaf |first3=K. |last4=Armaroli |first4=Nicola |journal=Chemical Society Reviews |volume=38 |issue=6 |pages=1690–2300 |pmid=19587962 }}</ref> Substituents at the 2,9 positions confer protection for the attached metal, inhibiting the binding of multiple equivalents of the phenanthroline. Such bulky ligands also favor trigonal or tetrahedral coordination at the metal.<ref name=Ruben/> Phen itself form complexes of the type [M(phen)₃]Cl₂ when treated with metal dihalides (M = Fe, Co, Ni). By contrast, [[neocuproine]] and [[bathocuproine]] form 1:1 complexes such as [Ni(neocuproine)Cl₂]₂.<ref>{{cite journal|author1=Preston, H. S. |author2=Kennard, C. H. L. |title=Crystal Structure of di-mu-Chloro-sym-''trans''-Dichloro-Bis-(2,9-Dimethyl-1,10-Phenanthroline)dinickel(II)-2-Chloroform|journal=J. Chem. Soc. A|year=1969|pages=2682–2685|doi=10.1039/J19690002682}}</ref>

{| class = "wikitable"

|+ Basicities of 1,10-Phenanthrolines and 2,2'-Bipyridine<ref name = pKa>{{cite journal

| title = Kinetics of the substitution of acetylacetone in acetylactonato-1,5-cyclooctadienerhodium(I) by derivatives of 1,10-phenantrholine and 2,2{{prime}}-dipyridyl

| journal = Journal of Organometallic Chemistry|author1 = Leipoldt, J.G.|author2 = Lamprecht, G.J.|author3 = Steynberg, E.C.

| year = 1991| volume = 402| issue = 2

| pages = 259–263

| doi = 10.1016/0022-328X(91)83069-G

}}</ref>

|-

! phen derivative

! pK_a

!comment/alt. name

! numbering scheme

|-

|1,10-phenanthroline ||4.86|| phen || rowspan="11" |[[File:Phenanthroline Numbering.png|frameless|150px|Numbering for 1,10-phenanthroline derivatives.]]

|-

| [[bipy|2,2'-bipyridine]] ||4.30|| bipy

|-

| 5-nitro-1,10-phenanthroline || 3.57

|-

| 2,9-dimethyl-1,10-phenanthroline || unknown ||[[neocuproine]]<ref name=Watson>{{cite journal |doi=10.1021/jacs.7b04312|title=Nickel-Catalyzed C-Alkylation of Nitroalkanes with Unactivated Alkyl Iodides |year=2017 |last1=Rezazadeh |first1=Sina |last2=Devannah |first2=Vijayarajan |last3=Watson |first3=Donald A. |journal=Journal of the American Chemical Society |volume=139 |issue=24 |pages=8110–8113 |pmid=28594543 |pmc=5531607 }}</ref><ref>{{cite book |doi=10.1002/047084289X.rn01440|chapter=Neocuproine |title=Encyclopedia of Reagents for Organic Synthesis |year=2012 |last1=Nilsson |first1=Peter |isbn=978-0-471-93623-7 }}</ref>

|-

|2,9-Dimethyl-4,7-diphenylphenanthroline||unknown||[[Bathocuproine]]<ref name=Watson/><ref>{{cite book |doi=10.1002/047084289X.rn01392|chapter=Bathocuproine |title=Encyclopedia of Reagents for Organic Synthesis |year=2012 |last1=Liu |first1=Guosheng |last2=Wu |first2=Yichen |isbn=978-0-471-93623-7 }}</ref>

|-

| 4,7-dimethyl-1,10-phenanthroline || 5.97

|-

| 4,7-diphenyl-1,10-phenanthroline || unknown ||bathophenanthroline<ref>{{cite book |doi=10.1002/047084289X.rn01319.pub2|chapter=Bathophenanthroline |title=Encyclopedia of Reagents for Organic Synthesis |year=2013 |last1=Vallée |first1=Frédéric |last2=Kühn |first2=Fritz E. |last3=Korinth |first3=Valentina A. |isbn=978-0-471-93623-7 }}</ref>

|-

| 5,6-dimethyl-1,10-phenanthroline || 5.20||5,6-Me₂phen

|-

|3,4,7,8-tetramethylphenanthroline || 6.31||3,4,7,8-Me₄phen<ref>{{cite book |doi=10.1002/047084289X.rn01515|chapter=3,4,7,8-Tetramethyl-1,10-phenanthroline (Tmphen) |title=Encyclopedia of Reagents for Organic Synthesis |year=2013 |last1=Zhu |first1=Lingui |last2=Altman |first2=Ryan A. |isbn=978-0-471-93623-7 }}</ref>

|-

|4,7-dimethoxy-1,10-phenanthroline || 6.45||4,7-(MeO)₂phen<ref>{{cite encyclopedia|encyclopedia=eEROS|title=Encyclopedia of Reagents for Organic Synthesis|author=Altman, Ryan A. |year=2008|doi=10.1002/047084289X.rn00918|chapter=1,10-Phenanthroline, 4,7-Dimethoxy|isbn=978-0-471-93623-7}}</ref>

|-

|2,6-dimesitylphenanthroline||unknown||HETPHEN<ref>{{cite journal |doi=10.1039/c6dt00324a|title=Synthesis, structure, ultrafast kinetics, and light-induced dynamics of CuHETPHEN chromophores|year=2016|last1=Kohler|first1=Lars|last2=Hayes|first2=Dugan|last3=Hong|first3=Jiyun|last4=Carter|first4=Tyler J.|last5=Shelby|first5=Megan L.|last6=Fransted|first6=Kelly A.|last7=Chen|first7=Lin X.|last8=Mulfort|first8=Karen L.|journal=Dalton Transactions|volume=45|issue=24|pages=9871–9883|pmid=26924711}}</ref><ref name=Ruben>{{cite journal |doi=10.1021/jacs.0c04695|title=Ni(I)–Alkyl Complexes Bearing Phenanthroline Ligands: Experimental Evidence for CO2 Insertion at Ni(I) Centers|year=2020|last1=Somerville|first1=Rosie J.|last2=Odena|first2=Carlota|last3=Obst|first3=Marc F.|last4=Hazari|first4=Nilay|last5=Hopmann|first5=Kathrin H.|last6=Martin|first6=Ruben|journal=Journal of the American Chemical Society|volume=142|issue=25|pages=10936–10941|pmid=32520556|pmc=7351122|bibcode=2020JAChS.14210936S }}</ref>

|}

==As an indicator for alkyllithium reagents==

Alkyllithium reagents form deeply colored derivatives with phenanthroline. The alkyllithium content of solutions can be determined by treatment of such reagents with small amounts of phenanthroline (ca. 1&nbsp;mg) followed by titration with alcohols to a colourless [[endpoint (chemistry)|endpoint]].<ref>{{OrgSynth | author1 = Fagan, Paul J. |author2 = Nugent, William A. | title = 1-Phenyl-2,3,4,5-Tetramethylphosphole| collvol = 9 | collvolpages = 653| year = 1998 | prep = CV9P0653}}</ref> [[Grignard reagents]] may be similarly titrated.<ref>{{cite journal | title = A Convenient Method for Determining the Concentration of Grignard Reagents|author1 = Lin, Ho-Shen |author2 = Paquette, Leo A. | journal = Synth. Commun. | volume = 24 | pages = 2503–2506 | year = 1994 | doi = 10.1080/00397919408010560 | issue =17}}</ref>

==See also==

* {{Annotated link|Ferroin}}

==References==

{{Reflist|30em}}

{{DEFAULTSORT:Phenanthroline, 1,10-}}

[[Category:Redox indicators]]

[[Category:Chelating agents]]

[[Category:Phenanthrolines| ]]