Selenourea

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Selenourea
Structural formula Space-filling model
Identifiers
CAS number 630-10-4 YesY
ChemSpider 10293781
EC number 211-129-9
MeSH C081959
ChEBI CHEBI:36957
Jmol-3D images Image 1
Properties
Molecular formula CH4N2Se
Molar mass 123.02 g/mol
Appearance Pink/grey solid
Melting point 214 °C (417 °F; 487 K)
Boiling point 200 °C (392 °F; 473 K)
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
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Infobox references

Selenourea is the organoselenium compound with the formula SeC(NH2)2. It is a white solid. This compound features a rare example of a stable, unhindered carbon-selenium double bond. The compound is used in the synthesis of selenium heterocycles. Compared to urea, the oxo-analog of selenourea, few studies have been done on the compound due to the instability and toxicity of selenium compounds.[1]

Synthesis[edit]

The compound was first synthesized in 1884 by Auguste Verneuil by the reaction of hydrogen selenide and cyanamide:[2]

H2Se + NCNH2 → SeC(NH2)2

While this reaction has even found use in industrial synthesis of selenourea,[3] more modern methods concern themselves with synthesis of substituted selenoureas. These can be synthesized using organic isoselenocyanates and secondary amines:

RN=C=Se + NHR’R’’ → Se=C(NRH)(NR’R’’H)

Alternatively, a substituted carbodiimide could be used as follows:[1]

RN=C=NR’Reagents.gif Se=C(NRH)(NR’H)

Properties[edit]

X-ray crystallographic measurements on crystals at -100 °C give average C=Se bond lengths of 1.86 Å, and 1.37 Å for C-N. Both the Se-C-N and N-C-N angles were measured at 120°, as expected for an sp2 hybridized carbon. Through these same studies, the existence of Se-H hydrogen bonding in the crystal lattice—suggested from to the O-H and S-H hydrogen bonding found in crystals of oxo- and thiourea—was confirmed.[4]

Both the shortened length of the N-C bond and the longer Se=C bond suggest a delocalization of the lone pair on the amines; the Se=C π-bonding electrons are drawn towards the Se atom, while the N-lone pair is drawn towards the carbonyl carbon. A similar effect is observed in oxo- and thiourea analogs. In going from urea to thiourea to selenourea the double bond is more delocalized and longer, while the C-N σ bond is stronger and shorter. In terms of resonance structures, the selenol form (structures II, III) is more prevalent compared to oxo- and thione analogs; however, the lone pair the nitrogen of selenourea delocalizes only slightly more than the lone pair on thiourea (in contrast to a much greater delocalization in going from urea to thiourea).[5] These minor differences suggest that the properties emergent from the delocalized N-lone pair and destabilization C=S and C=Se π bond in thiourea and selenourea will also be similar.

Resonance.gif

Unlike urea and thiourea, which have both been researched extensively,[1] relatively few studies quantitatively characterize selenourea. While the selenone tautomer (I) has been shown to be the more stable form,[6] mainly qualitative and comparative information on selenourea’s tautomerization is available.

In comparable manner to ketones, selenones also tautomerize:

Selenourea Tautomers.gif

Since the greater delocalization of the lone pair electrons correlates with the selenone product, the equilibrium position of selenourea likely has an equilibrium position comparable to thiourea’s (which is lies more to the right that than urea’s). Thiourea has been shown to exist predominantly in its thione form at 42 °C in dilute methanol, with the thionol tautomer almost non-existent at neutral pH.[7]

Reactivity[edit]

An important class of reactions of selenourea is the formation of heterocycles. Some selenium-containing heterocycles exhibit anti-inflammatory and anti-tumor activity, among other medicinal uses. Using selenourea as a precursor is considered to be the most efficient means of selenium-containing heterocyclic synthesis.[8]

Another class of reactions is the complexation of selenourea with transition metals and metalloids. Its ability to act as an effective ligand is attributed to the electron-donating effect of the amino groups and consequent stabilization of the Se-M π-bond. In selenourea complexes only Se-M bonding has been observed, unlike in the oxo- and thiourea counterparts, which also bond through the nitrogen atom.[9]

References[edit]

  1. ^ a b c Koketsu, M. Ishihara, H. “Thiourea and Selenourea and Their Applications”. Curr. Org. Syn. 2006, 3, pp 439-455. doi:10.2174/157017906778699521
  2. ^ Hope, H. “Synthesis of Selenourea”. Acta Chem. Scand., 1964, 18, 1800. doi:10.3891/acta.chem.scand.18-1800
  3. ^ Suvorov, V. et al. “Production of selenourea of high purity”. Vysokochistye Veshchestva, 1996, 3, pp 17-23.
  4. ^ Rutherford, J. S., Calvo, C. “The Crystal Structure of Selenourea”. Zeitschrift für Kristallographie, 1969, 128, pp 229-258.
  5. ^ Hampson, P., Mathias, A. “Nitrogen-14 chemical shifts in ureas”. J. Chem. Soc. (B), 1968, pp 673-675. doi:10.1039/J29680000673.
  6. ^ Rostkowska, H., et al. “Proton transfer processes in selenourea: UV-induced selenone → selenol photoreaction and ground state selenol → selenone proton tunneling”. Chem. Phys., 2004, 298, pp 223-232. doi:10.1016/j.chemphys.2003.11.024
  7. ^ Pramanick, D.,Chatterjee, A. K. “Thiourea as a transfer agent in the radical polymerization of methyl methacrylate in aqueous solution at 42°”. Euro. Poly. J., 1980, 16, pp 895-899. doi:10.1016/0014-3057(80)90122-6
  8. ^ Ninomiya, M., et al. “Selenium-containing heterocycles using selenoamides, selenoureas, selenazadienes, and isoselenocyanates”. Heterocycles, 2010, 81, pp 2027-2055. doi:10.3987/REV-10-677
  9. ^ Jones, P. G., Thöne, C. “Preparation, Crystal Structures and Reactions of Phosphine(selenourea)gold (I) Complexes” Chemische Berichte 1991, 124, pp 2725-2729. doi:10.1002/cber.19911241213