In chemistry, a nitrene (R–N:) is the nitrogen analogue of a carbene. The nitrogen atom has only 5 valence electrons and is therefore considered an electrophile. A nitrene is a reactive intermediate and is involved in many chemical reactions.
Electron configurationIn the most simple nitrene, the linear imidogen (:N–H), two of the 6 available electrons form a covalent bond with hydrogen, two others create a free electron pair and the two remaining electrons occupy two degenerate p orbitals. Consistent with Hund's rule the low energy form of imidogen is a triplet with one electron in each of the p orbitals and the high energy form is the singlet state with an electron pair filling one p orbital and the other one vacant. As with carbenes, a strong correlation exists between the spin density on the nitrogen atom which can be calculated in silico and the zero-field splitting parameter D which can be derived experimentally from electron spin resonance. Small nitrenes such as NH or CF3N have D values around 1.8 cm−1 with spin densities close to a maximum value of 2. At the lower end of the scale are molecules with low D (
FormationBecause nitrenes are so reactive, they are not isolated. Instead, they are formed as reactive intermediates during a reaction. There are two common ways to generate nitrenes:
- From azides by thermolysis or photolysis, with expulsion of nitrogen gas. This method is analogous to the formation of carbenes from diazo compounds.
- From isocyanates, with expulsion of carbon monoxide. This method is analogous to the formation of carbenes from ketenes.
ReactionsNitrene reactions include:
- Nitrene C–H insertion. A nitrene can easily insert into a carbon to hydrogen covalent bond yielding an amine or amide. A singlet nitrene reacts with retention of configuration. In one study a nitrene, formed by oxidation of a carbamate with potassium persulfate, gives an insertion reaction into the palladium to nitrogen bond of the reaction product of palladium(II) acetate with 2-phenylpyridine to methyl N-(2-pyridylphenyl)carbamate in a cascade reaction:
- Nitrene cycloaddition. With alkenes, nitrenes react to form aziridines, very often with nitrenoid precursors such as nosyl- or tosyl-substituted N-(phenylsulfonyl)iminophenyliodinane (PhI=NNs or PhI=NTs respectively)) but the reaction is known to work directly with the sulfonamide in presence of a transition metal based catalyst such as copper, palladium, or gold:Reactants cis- stilbene or trans-stilbene, nitrene precursor p-nitrosulfonamide or nosylamine which is oxidized by iodosobenzene diacetate. The gold catalyst is based on a terpyridine tridentate ligand.
- Arylnitrene ring-expansion and ring-contraction. Aryl nitrenes show ring expansion to 7-membered ring cumulenes, ring opening reactions and nitrile formations many times in complex reaction paths. For instance the azide 2 in the scheme below trapped in an argon matrix at 20 K on photolysis expels nitrogen to the triplet nitrene 4 (observed experimentally with ESR and ultraviolet-visible spectroscopy) which is in equilibrium with the ring-expansion product 6.