Tetrakis(dimethylamino)ethylene explained

Tetrakis(dimethylamino)ethylene (TDAE) is an organic compound with the formula, It is a colorless liquid. It is classified as an enamine. Primary and secondary enamines tend to isomerize, but tertiary enamines are kinetically stable.[1] One unusual feature of TDAE is that it is a tetra-enamine. The pi-donating tendency of the amine groups strongly enhances the basicity of the molecule, which does exhibit properties of a typical alkene.[2]

Reactions

TDAE reacts with oxygen in a chemiluminescent reaction to give tetramethylurea.[3] The initial intermediate is (2+2) adduct, a 1,2-dioxetane. This species decomposes to electronically excited tetramethylurea. This returns to the ground state is accompanied by emission of green light with a maximum at 515 nm.[4]

TDAE is an electron donor with E = 1.06 V vs Fc+/0.[5]

TDAE has been examined as a reductant in coupling reactions.[6]

As one of many of examples of its redox behavior forms a charge-transfer salt with buckminsterfullerene:[7]

C2(N(CH3)2)4 + C60 → [C<sub>2</sub>(N(CH<sub>3</sub>)<sub>2</sub>)<sub>4</sub><sup>+</sup>][C<sub>60</sub><sup>−</sup>] Oxidation affords a dication.

Structure

Crystallographic analysis show that TDAE is a highly distorted alkene, the dihedral angle for the two N2C termini is 28°. The C=C distance is alkene-like, 135 pm. The nearly isostructural tetraisopropylethylene also has a C=C distance of 135 pm, but its C6 core is planar. In contrast, [TDAE]2+ is an alkane with multi-C-N bonds.

Synthesis

It is available by pyrolysis of tris(dimethylamino)methane by pyrolysis or from chlorotrifluoroethene and dimethylamine.[8]

Notes and References

  1. Encyclopedia of Reagents for Organic Synthesis (EROS). 1,1,2,2-Tetrakis(dimethylamino)ethene. Cédric. Spitz. Thierry. Terme. Patrice. Vanelle. 10.1002/047084289X. 2023. 978-0-471-93623-7 . 10261/236866. free.
  2. Book: Tetraaminoethylenes. 701–748. David M. Lemal. Saul Patai. The Amino Group. Patai's Chemistry of Functional Groups . 1968. 9780470771082 . 10.1002/9780470771082.
  3. Web site: Chemilumineszenz von TDAE. illumina-chemie.de. 2016-08-22. 2014-08-08. German.
  4. H.E. Winberg. J. R. Downing. D. D. Coffman. J. Am. Chem. Soc.. The Chemiluminescence of Tetrakis(dimethylamino)ethylene . 87. 2054–2055. 1965. 9. 10.1021/ja01087a039.
  5. Broggi . Julie . Terme . Thierry . Vanelle . Patrice . 2014-01-07 . Organic Electron Donors as Powerful Single-Electron Reducing Agents in Organic Synthesis . Angewandte Chemie International Edition . en . 53 . 2 . 384–413 . 10.1002/anie.201209060 . 24273111 .
  6. 10.1021/jo0207473. Palladium-Catalyzed Tetrakis(dimethylamino)ethylene-Promoted Reductive Coupling of Aryl Halides. 2003. Kuroboshi. Manabu. Waki. Yoko. Tanaka. Hideo. The Journal of Organic Chemistry. 68. 10. 3938–3942. 12737575.
  7. Allemand PM, Khemani KC, Koch A, Wudl F, Holczer K, Donovan S, GrÜner G, Thompson JD. 3. Organic Molecular Soft Ferromagnetism in a Fullerene. Science. 1991. 253. 5017. 301–302. 10.1126/science.253.5017.301. 17794696. 1991Sci...253..301A. 19561675.
  8. US. 3293299 . Process for making tetrakis(dimethylamino)ethylene . 1966-12-20 . 1965-10-4 . H. Boden . E.I. du Pont de Nemours and Co..

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