11/14/2017 Carbyne - Wikipedia

Carbyne
In organic chemistry, a carbyne is a general term for any compound whose
molecular structure includes an electrically neutral carbon atom with three
un-bonded electrons, connected to another atom by a single bond.[1] A
carbyne thus has the general formula R-C3, where R is any monovalent doublet (1
group and the superscript 3 indicates the three unbonded electrons. radical, 1 pair, 1 quartet (3
Carbynes are named after the simplest such compound, HC3, the vacant orbital) radicals)

methylidyne radical or unsubstituted carbyne.

Electronic configuration
Carbyne molecules are generally found to be in electronic doublet states: the non-bonding electrons on carbon are
arranged as one radical (unpaired electron) and one electron pair, leaving a vacant atomic orbital, rather than being a
tri-radical (the quartet state). The simplest case is the CH radical, which has an electron configuration 12 22 32
1.[2] Here the 1 molecular orbital is essentially the carbon 1s atomic orbital, and the 2 is the C-H bonding orbital
formed by overlap of a carbon s-p hybrid orbital with the hydrogen 1s orbital. The 3 is a carbon non-bonding orbital
pointing along the C-H axis away from the hydrogen, while there are two non-bonding 1 orbitals perpendicular to the
C-H axis. However the 3 is an s-p hybrid which has lower energy than the 1 orbital which is pure p, so the 3 is filled
before the 1. The CH radical is in fact isoelectronic with the nitrogen atom which does have three unpaired electrons
in accordance with Hund's rule of maximum multiplicity. However the nitrogen atom has three degenerate p orbitals,
in contrast to the CH radical where hybridization of one orbital (the 3) leads to an energy difference.

Occurrence
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]

Carbynes can act as trivalent ligands in many complexes with transition metals[3] connected to a metal by the three
non-bonded electrons in the -C3 group. Examples of such coordination compounds are Cl(CO)4WC-CH3,[4]
WBr(CO)2(2,2'-bipyridine)C-aryl and WBr(CO)2(PPh3)2C-NR2.[5] Such a compound can be obtained by the reaction
of tungsten hexacarbonyl W(CO)6 with lithium diisopropylamide to form (iPr2N)(OLi)C=W(CO)5. This salt is then
oxidized with either oxalyl bromide or triphenylphosphine dibromide, followed by addition of triphenylphosphine.
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 (http://g
oldbook.iupac.org/C00854.html)".
2. Ruzsicska, B. P.; Jodhan, A.; Choi,
H. K. J.; Strausz, O. P.; Bell, T. N. Structure of the C162- ligand spanning two [Pt(C6F5)(Ptol3)2]+
(1983). "Chemistry of carbynes: centers.[6]
reaction of CF, CCl, and CBr with
alkenes". J. Am. Chem. Soc. 105
(8): 24892490. doi:10.1021/ja00346a072 (https://doi.org/10.1021%2Fja00346a072).

https://en.wikipedia.org/wiki/Carbyne 1/2
11/14/2017 Carbyne - Wikipedia

3. Furno, F.; Fox, T.; Berke, H. trans-W(CMes)(dmpe)2H: a W+ H ion pair (https://web.archive.org/web/200709301

55033/http://www.u-bourgogne.fr/EuroH-2000/furno.pdf) (PDF). EURO-HYDRIDES 2000 (http://euroh-2000.u-bou
rgogne.fr). Archived from the original (http://www.u-bourgogne.fr/EuroH-2000/furno.pdf) (PDF) on 2007-09-30.
4. Fischer, Ernst Otto; Kreis, Gerhard; Kreiter, Cornelius G.; Mller, Jrn; Huttner, Gottfried; Lorenz, Hans (1973).
"Trans-Halogeno[alkyl(aryl)carbyne]tetracarbonyl Complexes of Chromium, Molybdenum, and Tungsten -A New
Class of Compounds Having a Transition Metal-Carbon Triple Bond". Angewandte Chemie International Edition in
English. 12 (7): 564. doi:10.1002/anie.197305641 (https://doi.org/10.1002%2Fanie.197305641).
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. (11):
931932. doi:10.1039/B002228O (https://doi.org/10.1039%2FB002228O).
6. Mohr, W.; Stahl, J.; Hampel, F.; Gladysz, J. A. (2003). "Synthesis, Structure, and Reactivity of sp Carbon Chains
with Bis(phosphine) Pentafluorophenylplatinum Endgroups: Butadiynediyl (C4) through Hexadecaoctaynediyl
(C16) Bridges, and Beyond". Chemistry A European Journal. 9: 33243340. doi:10.1002/chem.200204741 (http
s://doi.org/10.1002%2Fchem.200204741).

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