1,4,7-Triazacyclononane

1,4,7-Triazacyclononane
TACN molecule
Names
IUPAC name
1,4,7-Triazacyclononane
Identifiers
4730-54-5 N
ChEBI CHEBI:37405 YesY
ChemSpider 163681 YesY
Jmol interactive 3D Image
Properties
C6H15N3
Molar mass 129.2046 g/mol
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

1,4,7-Triazacyclononane, known as "TACN" which is pronounced "tack-en," is a cyclic organic compound with the formula C6H12(NH)3.[1] TACN is derived, formally speaking, from cyclononane by replacing three equidistant CH2 groups with NH groups. TACN is one of the oligomers derived from aziridine, C2H4NH. Other members of the series include piperazine, C4H8(NH)2, and the cyclic tetramer 1,4,7,10-tetraazacyclododecane.

Synthesis

The ligand is prepared from diethylene triamine as follows by macrocyclization using ethyleneglycol ditosylate.[2]

H2NCH2CH2NHCH2CH2NH2 + 3 TsCl → Ts(H)NCH2CH2N(Ts)CH2CHH2N(H)Ts + 3 HCl
Ts(H)NCH2CH2N(Ts)CH2CH2N(H)Ts + 2 NaOEt → Ts(Na)NCH2CH2N(Ts)CH2CH2N(Na)Ts
Ts(Na)NCHH2CH2N(Ts)CH2CH2N(Na)Ts + TsOCH2CH2OTs + → [(CH2CH2N(Ts)]3 + 2 NaOTs
[(CH2CH2N(Ts)]3 + 3 H2O → [CH2CH2NH]3 + 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.

Illustrative complexes

TACN·3HCl + CuCl2·3H2O + 3 NaOH → [(κ3-TACN)CuCl2] + 6 H2O + 3 NaCl
[(κ3-TACN)Mn] + H2O2 + NaHCO3 + (C6H5)C2H3→ [(κ3-TACN)Mn] + 2H2O + CO2 +  (C6H5)C2H2O

References

  1. Chaudhuri, P. and Wieghardt, K., "The Chemistry of 1,4,7-Triazacyclononane and Related Tridentate Macrocyclic Compounds", Progress in Inorganic Chemistry, 1987, volume 35, 329-436
  2. K. Wieghardt, W. Schmidt, B. Nuber, and J. Weiss, "Darstellung und Struktur des trans-Diaqua-di-μ-hydroxo-bis[(1,4,7-triazacyclononan)cobalt(III)]-Kations; Kinetik und Mechanismus seiner Bildung"Chem. Ber., 1979, 112, 2220-2230.
  3. K. Sibbons, K Shastri, and M Watkinson, "The application of manganese complexes of ligands derived from 1,4,7-triazacyclononane in oxidative catalysis", Dalton Transactions, 2006, 645-661.
  4. Deal, K. A.; Burstyn, J. N., "Mechanisitic Studies of Dichloro(1,4,7-triazacyclononane)copper(II)-Catalyzed Phosphate Diester Hydrolysis", Inorg. Chem. 1996, 35, 2792-2798
  5. K. Wieghardt, W. Schmidt, H. Endres and C.R. Wolfe, Chem. Ber., 1979, 112, 2837
  6. K. Wieghardt, W. Schmidt, W. Herrmann, and H.-J. Kuppers, Inorg. Chem., 1983, 22, 2953
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