Misplaced Pages

tert-Butyl isocyanide

Article snapshot taken from Wikipedia with creative commons attribution-sharealike license. Give it a read and then ask your questions in the chat. We can research this topic together.

This is an old revision of this page, as edited by Mowsala (talk | contribs) at 20:40, 20 March 2012 (→Safety: Removed inexplicable phrase about similarity to carbon monoxide). The present address (URL) is a permanent link to this revision, which may differ significantly from the current revision.

Revision as of 20:40, 20 March 2012 by Mowsala (talk | contribs) (→Safety: Removed inexplicable phrase about similarity to carbon monoxide)(diff) ← Previous revision | Latest revision (diff) | Newer revision → (diff)
tert-Butyl isocyanide
Names
Other names t-BuNC, propane, 2-isocyano-2-methyl
Identifiers
CAS Number
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.027.776 Edit this at Wikidata
PubChem CID
CompTox Dashboard (EPA)
InChI
  • InChI=1S/C5H9N/c1-5(2,3)6-4/h1-3H3Key: FAGLEPBREOXSAC-UHFFFAOYSA-N
  • InChI=1/C5H9N/c1-5(2,3)6-4/h1-3H3Key: FAGLEPBREOXSAC-UHFFFAOYAL
SMILES
  • CC(C)(C)#
Properties
Chemical formula C5H9N
Molar mass 83.13 g/mol
Appearance Colorless liquid
Density 0.735 g/cm³, liquid
Melting point ? °C
Boiling point 91 °C
Solubility in water N/A
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). checkY verify (what is  ?) Infobox references
Chemical compound

tert-Butyl isocyanide is an organic compound with the formula Me3CNC (Me = methyl, CH3). It is an isocyanide, commonly called isonitrile or carbylamine, as defined by the functional group C≡N-R. tert-Butyl isocyanide, like most alkyl isocyanides, is a reactive colorless liquid with an extremely unpleasant odor. It forms stable complexes with transition metals and can insert into metal-carbon bonds.

tert-Butyl isocyanide is prepared by a Hofmann carbylamine reaction. In this conversion, a dichloromethane solution of tert-butylamine is treated with chloroform and aqueous sodium hydroxide in the presence of catalytic amount of the phase transfer catalyst benzyltriethylammonium chloride.

Me3CNH2 + CHCl3 + 3 NaOH → Me3CNC + 3 NaCl + 3 H2O

tert-Butyl isocyanide is isomeric with pivalonitrile, also known as tert-butyl cyanide.

Coordination chemistry

By virtue of the lone electron pair on carbon, isocyanides serves as ligands in coordination chemistry, especially with metals in the 0, +1, and +2 oxidation states. tert-Butyl isocyanide has been shown to stabilize metals in unusual oxidation states, such as Pd(I).

Pd(dba)2 + PdCl2(C6H5CN)2 + 4 t-BuNC → 2 + 2 dba + 2 C6H5CN

tert-Butyl isocyanide can form hepta-coordinate homoleptic complexes, despite having a large t-Bu group, which is held far away from the metal center because of the linearity of the M-C≡N-C linkages.

Similarity to metal carbonyls

tert-Butyl isocycanide forms complexes that are stoichiometrically analogous to certain binary metal carbonyl complexes, such as Fe2(CO)9 and Fe2(tBuNC)9. Although structurally similar, the analogous carbonyls differ in several ways, mainly because t-BuNC is a better donor ligand than CO. Thus, Fe(tBuNC)5 is easily protonated, whereas its counterpart Fe(CO)5 is not.

Insertion into metal-carbon bonds

Under certain circumstances, tert-butyl isocyanide has been shown to insert into metal-carbon bonds to form iminoacyls. The insertion of isocyanides into metal-carbon bonds is of potential relevance in organic synthesis.

Safety

Tert-butyl isocyanide is toxic.

References

  1. Malatesta, L. Isocyanide Complexes of MetalsProgress in Inorganic Chemistry, 1959, volume 1, 284-291.
  2. Gokel, G.W.; Widera, R.P.; Weber, W.P. (1988). "Phase-transfer Hofmann carbylamine reaction: tert-butyl isocyanide". Organic Syntheses{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 6, p. 232.
  3. Rettig, M.F.; Maitlis, P.M.; Cotton, F.A.; Webb, T.R. Tetrakis(tert-butyl isocyanide)Di-μ-chloro-dipalladium(I). Inorganic Syntheses, 1990, 28, 110-113. ISBN 0-470-13259-0. doi:10.1002/9780470132593.ch29
  4. Carnahan, E.M.; Protasiewicz, J.D.; Lippard, S.J. 15 years of reductive coupling: what have we learned? Acc. Chem. Res. 1993, 26, 90-97
  5. Bassett, J.M.; Barker, G.K.; Green, M.; Howard, J.A.; Stone, G.A.; Wolsey, W.C. "Chemistry of low-valent metal isocyanide complexes" J.C.S. Dalton, 1981, 219-227.
  6. Bassett, J.M.; Farrugia, L.J.; Stone, G.A. "Protonation of pentakis(t-butyl isocyanide)iron" J.C.S. Dalton, 1980, 1789-1790.
  7. Vicente, J; Abad, J.A.; Fortsch, W.; Lopez-Saez, M.J. Reactivity of ortho-palladated phenol derivatives with unsaturated molecules. Organometallics, 2004, 23, 4414-4429. DOI 10.1021/om0496131.
Category: