Carbyne

In chemistry, a carbyne is a monovalent carbon radical species containing an electrically neutral univalent carbon atom with three non-bonded electrons.[1]

Gas phase/reactive intermediate

A carbyne can occur as a short-lived reactive intermediate. For instance, fluoromethylidyne (CF) can be detected in the gas phase by spectroscopy as an intermediate in the flash photolysis of CHFBr2.[2] The carbon atom was generally found to be an electronic doublet: the valence electrons are arranged as one radical (unpaired electron) and one electron pair, leaving a vacant atomic orbital, rather than being a tri-radical. The carbon atom is a complex hybridization, so the simple Hund's rule analysis of a simple atom containing 3 p orbitals (or 4 sp3 hybrids) is not correct.

Organometallic ligand

Carbynes are incorporated in Transition metal carbyne complexes[3][4] as a trivalent ligand. For example, in [WBr(CO)2(2,2'-bipyridine)C-Aryl] and [WBr(CO)2(PPh3)2C-NR2]. An example of how to make such a compound would be to react [W(CO)6] with Lithium diisopropylamide to form [(iPr2N)(OLi)C=W(CO)5]. This is then reacted with either oxalyl bromide or triphenylphosphine dibromide followed by triphenyl phosphine. Another method is to treat a methoxy metal carbene with a lewis acid.[5]

References

  1. ^ IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online corrected version:  (2006–) "carbynes".
  2. ^ Ruzsicska, B. P.; Jodhan, A.; Choi; H. K. J., Strausz, O. P.; Bell, T. N. (1983). "Chemistry of carbynes: reaction of CF, CCl, and CBr with alkenes". J. Am. Chem. Soc. 105: 2489–2490. doi:10.1021/ja00346a072. 
  3. ^ Furno, F.; Fox, T.; Berke, H.. "trans-W(CMes)(dmpe)2H: a W+ H ion pair". EURO-HYDRIDES 2000. http://www.u-bourgogne.fr/EuroH-2000/furno.pdf. 
  4. ^ Details of their reactivity and that of the related carbenes is shown at http://www.thieme-chemistry.com/thieme-chemistry/sos/info/include/pdf/sc02.pdf.
  5. ^ Jaeger, M.; Stumpf, R.; Troll, C.; Fischer, H. (2000). "Novel hepta-coordinated molybdenum(II) and tungsten(II) carbene complexes by oxidative decarbonylation of Mo(0) and W(0) carbene complexes". Chem. Commun.: 931–932. doi:10.1039/B002228O.