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Revision as of 16:26, 16 February 2012 editBeetstra (talk | contribs)Edit filter managers, Administrators172,055 edits Saving copy of the {{chembox}} taken from revid 443255630 of page 1,4,7-Triazacyclononane for the Chem/Drugbox validation project (updated: 'CASNo').  Latest revision as of 02:59, 20 June 2022 edit ByVarying (talk | contribs)Extended confirmed users1,567 edits →References: CategorizationTags: Mobile edit Mobile web edit Advanced mobile edit 
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{{ambox | text = This page contains a copy of the infobox ({{tl|chembox}}) taken from revid of page ] with values updated to verified values.}}
{{chembox {{chembox
| Verifiedfields = changed
| verifiedrevid = 443254341 | verifiedrevid = 477205742
| Name = 1,4,7-Triazacyclononane | Name = 1,4,7-Triazacyclononane
| ImageFile = 1,4,7-triazacyclononane.png | ImageFile = 1,4,7-triazacyclononane.svg
| ImageSize = 200px | ImageSize = 150px
| ImageName = 1,4,7-Triazacyclononane | ImageName = 1,4,7-Triazacyclononane
| IUPACName = 1,4,7-Triazacyclononane | ImageFile1 = 1,4,7-Triazacyclononane-3D-balls.png
| ImageSize1 = 160
| ImageAlt1 = TACN molecule
| PIN = 1,4,7-Triazonane
| Section1 = {{Chembox Identifiers | Section1 = {{Chembox Identifiers
⚫ | ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| ACXNumber = X1073996-5
⚫ | ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| ChEBI_Ref = {{ebicite|correct|EBI}} | ChEBI_Ref = {{ebicite|correct|EBI}}
| ChEBI = 37405 | ChEBI = 37405
| ChemSpiderID = 163681 | ChemSpiderID = 163681
| PubChem = 188318
| EINECS = 637-157-5
| ChEMBL = 1650628
| Beilstein = 773877
| Gmelin = 2614
| InChI = 1/C6H15N3/c1-2-8-5-6-9-4-3-7-1/h7-9H,1-6H2 | InChI = 1/C6H15N3/c1-2-8-5-6-9-4-3-7-1/h7-9H,1-6H2
| InChIKey = ITWBWJFEJCHKSN-UHFFFAOYAS | InChIKey = ITWBWJFEJCHKSN-UHFFFAOYAS
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} | StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
| StdInChIKey = ITWBWJFEJCHKSN-UHFFFAOYSA-N | StdInChIKey = ITWBWJFEJCHKSN-UHFFFAOYSA-N
| CASNo_Ref = {{cascite|correct|CAS}}
| CASNo = <!-- blanked - oldvalue: 4730-54-5 -->
| CASNo = 4730-54-5
⚫ }}
| UNII_Ref = {{fdacite|correct|FDA}}
| UNII = 2UIF93C5H3
}}
| Section2 = {{Chembox Properties | Section2 = {{Chembox Properties
| Formula = C<sub>6</sub>H<sub>15</sub>N<sub>3</sub> | Formula = C<sub>6</sub>H<sub>15</sub>N<sub>3</sub>
| MolarMass = 129.2046 g/mol | MolarMass = 129.2046 g/mol
}} }}
|Section7={{Chembox Hazards
| GHSPictograms = {{GHS05}}
| GHSSignalWord = Danger
| HPhrases = {{H-phrases|314}}
| PPhrases = {{P-phrases|260|264|280|301+330+331|303+361+353|304+340|305+351+338|310|321|363|405|501}}
⚫ }}
}} }}

'''1,4,7-Triazacyclononane''', known as "TACN" which is pronounced "tack-en," is an ] with the formula (C<sub>2</sub>H<sub>4</sub>NH)<sub>3</sub>.<ref>{{Cite book|last=Chaudhuri|first=P.|last2=Wieghardt|first2=K.|year=1987|editor-last=Lippard|editor-first=Stephen J.|chapter=The Chemistry of 1,4,7-Triazacyclononane and Related Tridentate Macrocyclic Compounds|title=Progress in Inorganic Chemistry|location=Hoboken, NJ, USA|publisher=John Wiley & Sons, Inc.|volume=35|pages=329–436|doi=10.1002/9780470166369.ch4|isbn=9780470166369}}</ref> TACN is derived, formally speaking, from cyclononane by replacing three equidistant CH<sub>2</sub> groups with NH groups. TACN is one of the oligomers derived from ], C<sub>2</sub>H<sub>4</sub>NH. Other members of the series include ], C<sub>4</sub>H<sub>8</sub>(NH)<sub>2</sub>, and the cyclic tetramer ].

==Synthesis==
The ligand is prepared from ] as follows by macrocyclization using ethyleneglycol ditosylate.<ref>{{Cite journal|last=Wieghardt|first=Karl|last2=Schmidt|first2=Wilfried|last3=Nuber|first3=Bernhard|last4=Weiss|first4=Johannes|year=1979|title=Darstellung und Struktur des trans-Diaqua-di-μ-hydroxo-bis-Kations; Kinetik und Mechanismus seiner Bildung|journal=]|language=de|volume=112|issue=6|pages=2220–2230|doi=10.1002/cber.19791120629}}</ref>
:H<sub>2</sub>NCH<sub>2</sub>CH<sub>2</sub>NHCH<sub>2</sub>CH<sub>2</sub>NH<sub>2</sub> + 3 TsCl → Ts(H)NCH<sub>2</sub>CH<sub>2</sub>N(Ts)CH<sub>2</sub>CHH<sub>2</sub>N(H)Ts + 3 HCl
:Ts(H)NCH<sub>2</sub>CH<sub>2</sub>N(Ts)CH<sub>2</sub>CH<sub>2</sub>N(H)Ts + 2 NaOEt → Ts(Na)NCH<sub>2</sub>CH<sub>2</sub>N(Ts)CH<sub>2</sub>CH<sub>2</sub>N(Na)Ts
:Ts(Na)NCHH<sub>2</sub>CH<sub>2</sub>N(Ts)CH<sub>2</sub>CH<sub>2</sub>N(Na)Ts + TsOCH<sub>2</sub>CH<sub>2</sub>OTs + → <sub>3</sub> + 2 NaOTs
:<sub>3</sub> + 3 H<sub>2</sub>O → <sub>3</sub> + 3 HOTs

==Coordination chemistry==
TACN is a popular tridentate ligand. It is threefold symmetric and binds to one face of an octahedron of metalloids and transition metals. The (TACN)M unit is kinetically inert, allowing further synthetic transformations on the other coordination sites. A bulky analogue of TACN, is the N,N',N"-trimethylated analogue ].

===Illustrative complexes===
*Although TACN characteristically coordinates to metals in mid- and high oxidation states, e.g. Ni(III), Mn(IV), Mo(III), W(III), exceptions occur. To illustrate, 1,4,7-triazacyclononane reacts readily with Mo(CO)<sub>6</sub> and W(CO)<sub>6</sub> to produce the respective air-stable tricarbonyl compounds, and . Both have an oxidation state of zero. After further reacting with 30% H<sub>2</sub>O<sub>2</sub>, the products are and . Both of these oxo complexes have an oxidation state of 6. The macrocyclic ligand does dissociate in the course of this dramatic change in formal oxidation state of the metal.
*The complex, , a catalyst for hydrolytic cleavage of phosphodiester bonds in DNA,<ref>{{Cite journal|last=Sibbons|first=Kevin F.|last2=Shastri|first2=Kirtida|last3=Watkinson|first3=Michael|year=2006|title=The application of manganese complexes of ligands derived from 1,4,7-triazacyclononane in oxidative catalysis|journal=Dalton Transactions|issue=5|pages=645–661|doi=10.1039/B511331H|pmid=16429167}}</ref> is prepared as follows from TACN trihydrochloride:

:TACN·3HCl + CuCl<sub>2</sub>·3H<sub>2</sub>O + 3 NaOH → + 6 H<sub>2</sub>O + 3 NaCl

*Mn-TACN complexes catalyze ] of ]s such as ] using H<sub>2</sub>O<sub>2</sub> as an oxidant in a carbonate buffered ] solution at a pH of 8.0.&nbsp; These reagents are considered environmentally benign,<ref>{{Cite journal|last=Deal|first=Kim A.|last2=Burstyn|first2=Judith N.|year=1996|title=Mechanistic Studies of Dichloro(1,4,7-triazacyclononane)copper(II)-Catalyzed Phosphate Diester Hydrolysis|journal=Inorg. Chem.|volume=35|issue=10|pages=2792–2798|doi=10.1021/ic951488l}}</ref>

: + H<sub>2</sub>O<sub>2</sub> + NaHCO<sub>3</sub> + (C<sub>6</sub>H<sub>5</sub>)C<sub>2</sub>H<sub>3</sub>→ + 2H<sub>2</sub>O + CO<sub>2</sub> +&nbsp; (C<sub>6</sub>H<sub>5</sub>)C<sub>2</sub>H<sub>2</sub>O

*Chromium (II) sources, e.g. created by heating CrCl<sub>3</sub><sup>.</sup>6H<sub>2</sub>O in DMSO react with TACN to form both 1:1 Cr:and 2:1 complexes,<ref>{{Cite journal|last=Wieghardt|first=Karl|last2=Schmidt|first2=Wilfried|last3=Endres|first3=Helmut|last4=Wolfe|first4=C. Robert|year=1979|title=Neue μ-Hydroxo-Übergangsmetallkomplexe, II. Darstellung mehrkerniger Komplexe des Chroms(III) mit dreizähnigen Amin-Liganden. Struktur des μ-di-μ-hydroxobis-Kations|journal=Chemische Berichte|language=de|volume=112|issue=8|pages=2837–2846|doi=10.1002/cber.19791120810}}</ref> e.g. yellow <sup>3+</sup>.<ref>{{Cite journal|last=Wieghardt|first=K.|last2=Schmidt|first2=W.|last3=Hermann|first3=W.|last4=Küppers|first4=H.-J.|year=1983|title=Redox potentials of bis(1,4,7-triazacyclononane complexes of some first transition series metals(II,III). Preparation of bis(1,4,7-triazacyclononane)nickel(III) perchlorate|journal=Inorg. Chem.|volume=22|issue=20|pages=2953|doi=10.1021/ic00162a037}}</ref>

==References==
{{reflist}}

{{DEFAULTSORT:Triazacyclononane, 1,4,7-}}
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