There exist several variants of the stable carbenes above where one of the nitrogen atoms adjacent to the carbene center (the α nitrogens) has been replaced by an alternative heteroatom, such as oxygen, sulfur, or phosphorus.
In particular, the formal substitution of sulfur for one of the nitrogens in imidazole would yield the aromatic heterocyclic compound thiazole. A thiazole based carbene (analogous to the carbene postulated by Breslow) has been prepared and characterised by X-ray crystallography. Other non-aromatic aminocarbenes with O, S and P atoms adjacent (i.e. alpha) to the carbene centre have been prepared, for example, thio- and oxyiminium based carbenes have been characterised by X-ray crystallography.
Since oxygen and sulfur are divalent, steric protection of the carbenic centre is limited especially when the N–C–X unit is part of a ring. These acyclic carbenes have diagnostic C NMR chemical shift values between 250 and 300 ppm for the carbenic carbon, further downfield than any other types of stable carbene. X-ray structures have shown N–C–X bond angles of around 104° and 109° respectively.
Carbenes that formally derive from imidazole-2-ylidenes by substitution of sulfur, oxygen, or other chalcogens for both α-nitrogens are expected to be unstable, as they have the potential to dissociate into an alkyne (RC≡CR) and a carbon dichalcogenide (X=C=X).