| Formula = 2•
| MolarMass = 14.0266 g mol−1
| Appearance = Colourless gas
| Solubility = Reacts
| DeltaHf = 386.39 kJ mol−1
| Entropy = 193.93 J K−1 mol−1
| OtherCompounds = Methyl (CH3) Methylidyne (CH) Carbide (C)
(systematically named methylidene
, and dihydridocarbon
), also called carbene
is an organic compound
with the chemical formula
(also written ). It is a colourless gas that fluoresces in the mid-infrared range, and only persists in dilution, or as an adduct
Methylene is the simplest carbene
.Roald Hoffman (2005), Molecular Orbitals of Transition Metal Complexes
. Oxford. It is usually detected only at very low pressures, very low temperatures
, or as a short-lived intermediate in chemical reaction
W. B. DeMore and S. W. Benson (1964), Preparation, properties, and reactivity of methylene
. In Advances in Photochemistry
, John Wiley & Sons, 453 pages.
The trivial name carbene
is the preferred IUPAC name
. The systematic names methylidene
, valid IUPAC
names, are constructed according to the substitutive and additive nomenclatures, respectively.
is viewed as methane
with two hydrogen atoms removed. By default, this name pays no regard to the radicality of the methylene. Although in a context where the radicality is considered, it can also name the non-radical excited state
, whereas the radical ground state
with two unpaired electrons is named methanediyl
is also used as the trivial name for the substituent
(), and methylidene
has an electron affinity of 0.65 eV http://webbook.nist.gov/cgi/cbook.cgi?ID=C2465567&Units=SI&Mask=20#Ion-Energetics
Discovery and preparation
The compound was first detected and studied around 1960, by infrared spectroscopy
in frozen gas matrix isolation
William B. DeMore, H. O. Pritchard, and Norman Davidson (1959), Photochemical experiments in rigid media at low temperatures. II. The reactions of methylene, cyclopentadienylene and diphenylmethylene
. Journal of the American Chemical Society, volume 81, issue 22, pages 5874–5879.
Marilyn E. Jacox and Dolphus E. Milligan (1963), ' Infrared study of the reactions of CH2 and NH with C2H2 and C2H4 in solid argon
''.Journal of the American Chemical Society, volume 85, issue 3, pages 278–282.
The first suggested use of methylene was by D. Duck
in 1944.Footnote 91 cites the relevant issue of Walt Disney's Comics and Stories
"If I mix CH2 with NH4 and boil the atoms in osmotic fog, I should get speckled nitrogen." Walt Disney's Comics and Stories
, issue 44, 1944
Methylene can be prepared, under suitable conditions, by decomposition of compounds with a methylidene or methanediyl group, such as ketene (ethenone)
(linear =), diazirine
) and diiodomethane
(I--I). The decomposition can be effected by photolysis
reagents (such as benzophenone
), or thermal decomposition.
Many of methylene's electronic states lie relatively close to each other, giving rise to varying degrees of radical chemistry. The ground state is a triplet radical with two unpaired electrons (X
Isaiah Shavitt (1985), Geometry and singlet-triplet energy gap in methylene: A critical review of experimental and theoretical determinations
. Tetrahedron, volume 41, issue 8, page 1531
and the first excited state is a singlet non-radical (ã
1). With the singlet non-radical only 38 kJ above the ground state, a sample of methylene exists as a mixture of electronic states even at room temperature, giving rise to complex reactions. For example, reactions of the triplet radical with non-radical species generally involves abstraction, whereas reactions of the singlet non-radical not only involves abstraction, but also insertion or addition.
1) + → • + HO
1) + → + or
The singlet state is also more sterospecific
than the triplet.
Unsolvated methylene will spontaneously autopolymerise to form various excited oligomers, the simplest of which, is the excited form of the alkene ethylene
. The excited oligomers, decompose rather than decay to a ground state. For example, the excited form of ethylene decomposes to acetylene and atomic hydrogen.
2 → → HCCH + 2 H
Unsolvated, excited methylene will form stable ground state oligomers.
The ground state of methylene has an ionisation energy
of 10.396 eV
. It has a bent configuration, with H-C-H angle of 133.84 °
, and is thus paramagnetic
. (The correct prediction of this angle was an early success of ab initio quantum chemistry
.) However conversion to a linear configuration requires only 5.5 kcal
This state has a slightly higher energy (by about 9 kcal/mol) than the triplet state, and its H-C-H angle is smaller, about 102°. In dilute mixtures with an inert gas, the two states will convert to each other until reaching an equilibrium.
Neutral methylene complexes undergo different chemical reactions
depending on the pi character of the coordinate bond to the carbon centre. A weak contribution, such as in diazomethane, yields mainly substitution reactions, whereas a strong contribution, such as in ethenone
, yields mainly addition reactions. Upon treatment with a standard base, complexes with a weak contribution convert to a metal methoxide. With strong acids (e.g., fluorosulfuric acid
), they can be protonated to give . Oxidation of these complexes yields formaldehyde, and reduction yields methane.
Free methylene undergoes the typical chemical reaction
s of a carbene. Addition reaction
s are very fast and exothermic.
Milan Lazár (1989), Free radicals in chemistry and biology
. CRC Press.
When the methylene molecule is in its state of lowest energy
, the unpaired valence electrons are in separate atomic orbital
s with independent spin
s, a configuration known as triplet state
Methylene may gain an electron yielding a monovalent anion methanidyl
(), which can be obtained as the trimethylammonium
()4 salt by the reaction of phenyl sodium
with trimethylammonium bromide
. The ion is bent too, with a H-C-H angle of about 103°.
Reactions with inorganic compounds
Methylene is also a common ligand
in coordination compound
s, such as copper methylene
Sou-Chan Chang, Zakya H. Kafafi, Robert H. Hauge, W. Edward Billups, and John L. Margrave (1987), Isolation and characterization of copper methylene (CuCH2) via FTIR matrix isolation spectroscopy
. Journal of the American Chemical Society, volume 109 pages 4508-4513. .
Methylene can bond as a terminal ligand, which is called methylidene
, or as a bridging ligand, which is called methanediyl