Tetrakis(dimethylamino)ethylene

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Tetrakis(dimethylamino)ethylene
C2(NMe2)4.png
Tetrakis(dimethylamino)ethylene-from-xtal-vertical-3D-bs-17.png
Tetrakis(dimethylamino)ethylene-from-xtal-end-on-3D-bs-17.png
Names
Preferred IUPAC name
N1,N1,N1,N1,N2,N2,N2,N2-Octamethylethene-1,1,2,2-tetramine
Other names
Octamethyl-ethenetetramine
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.012.398 Edit this at Wikidata
EC Number
  • 213-638-1
UNII
  • InChI=1S/C10H24N4/c1-11(2)9(12(3)4)10(13(5)6)14(7)8/h1-8H3
    Key: CBXRMKZFYQISIV-UHFFFAOYSA-N
  • CN(C)C(=C(N(C)C)N(C)C)N(C)C
Properties
C10H24N4
Molar mass 200.330 g·mol−1
Appearance colorless liquid
Density 0.861 g/cm3 (25 °C)
Melting point −4 °C (25 °F; 269 K)
Boiling point 59 °C (0.9 mm Hg)
Hazards
GHS labelling:
GHS02: FlammableGHS05: Corrosive
Danger
H226, H314
P210, P233, P240, P241, P242, P243, P260, P264, P280, P301+P330+P331, P303+P361+P353, P304+P340, P305+P351+P338, P310, P321, P363, P370+P378, P403+P235, P405, P501
Flash point 53 °C (127 °F; 326 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Tetrakis(dimethylamino)ethylene (TDAE) is an organic compound with the formula [C(NMe2)2]2 (where Me = CH3). A colorless liquid, this compound is classified as an enamine. Primary and secondary enamines tend to isomerize, but tertiary enamines are kinetically stable. The unusual feature of TDAE is that it is a tetra-enamine. The pi-donating tendency of the amine groups strongly modifies the properties of the molecule, which does exhibit properties of a typical alkene.[1]

Reactions[edit]

TDAE reacts with oxygen in a chemiluminescent reaction to give tetramethylurea[2][3]

Oxidation of TDAE (chemiluminescence).

TDAE is an electron donor with E = 1.06 V vs Fc+/0.[4][5] It forms a charge transfer salt with buckminsterfullerene:[6]

C2(N(CH3)2)4 + C60 → [C2(N(CH3)2)4+][C60]

Oxidation affords a dication.

Structure[edit]

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.

Structure of TDAE and its dication (distances in picometers).[7]

References[edit]

  1. ^ David M. Lemal (1968). "Tetraaminoethylenes". In Saul Patai (ed.). The Amino Group. pp. 701–748. doi:10.1002/9780470771082. ISBN 9780470771082.
  2. ^ H.E. Winberg; J. R. Downing; D. D. Coffman (1965). "The Chemiluminescence of Tetrakis(dimethylamino)ethylene". J. Am. Chem. Soc. 87 (9): 2054–2055. doi:10.1021/ja01087a039.
  3. ^ "Chemilumineszenz von TDAE" (in German). illumina-chemie.de. 2014-08-08. Retrieved 2016-08-22.
  4. ^ Broggi, Julie; Terme, Thierry; Vanelle, Patrice (2014-01-07). "Organic Electron Donors as Powerful Single-Electron Reducing Agents in Organic Synthesis" (PDF). Angewandte Chemie International Edition. 53 (2): 384–413. doi:10.1002/anie.201209060. PMID 24273111.
  5. ^ Kuroboshi, Manabu; Waki, Yoko; Tanaka, Hideo (2003). "Palladium-Catalyzed Tetrakis(dimethylamino)ethylene-Promoted Reductive Coupling of Aryl Halides". The Journal of Organic Chemistry. 68 (10): 3938–3942. doi:10.1021/jo0207473. PMID 12737575.
  6. ^ Allemand PM, Khemani KC, Koch A, et al. (1991). "Organic Molecular Soft Ferromagnetism in a Fullerene". Science. 253 (5017): 301–302. Bibcode:1991Sci...253..301A. doi:10.1126/science.253.5017.301. PMID 17794696. S2CID 19561675.
  7. ^ Bock, Hans; Borrmann, Horst; Havlas, Zdenek; et al. (1991). "Tetrakis(dimethylamino)ethene: An Extremely Electron-Rich Molecule with Unusual Structure both in the Crystal and in the Gas Phase". Angewandte Chemie International Edition in English. 30 (12): 1678–1681. doi:10.1002/anie.199116781.