DFT studies of biarylcarbenes and the carbene-biradical continuum.

We use electronic structure modeling, mainly density functional methods, to characterize a variety of long-lived bisaryl triplet carbenes. The bisaryl systems have a triplet ground state, favored by a substantial delocalization of the spin into the aromatic rings. One can imagine two extreme cases of the bonding in these species, representable as valence isomers. In the first case, spin delocalization is minor and incidental; the spin is predominantly located on the central carbene carbon. In the second case, spins are separated by large distances and are found primarily on the aromatic rings; the rings are linked by an allenic bridge. The bisphenyl carbenes tend toward the first limit. They can be kinetically stabilized by ortho substituents which shield the reactive center and para substituents which protect that site which has substantial spin density. The bond angle at carbene is opened from about 142 degrees (the B3LYP/6-31G value for the parent bis(phenyl)carbene) to 160 degrees or more by these substituents. Bisanthryl carbenes illustrate the second extreme, favoring a D(2)(d)() structure and possessing a low-lying open shell singlet state. A hypothetical phenyl-9-anthrylcarbine lies between the carbine and diradical extemes. The same principle which guides the design of stabilized diphenylcarbene carbenes and substitution of reactive sites by bulky protective groups serves to stabilize the bis-9-anthrylcarbene biradical.