On the π-Electron Distribution in Biphenylene Analogues

Abstract

The bonding situation in a series of biphenylene analogues – benzo[b]biphenylene and its dication, 4,10-dibromobenzo[b]biphenylene, naphtho[2,3-b]biphenylene and its dianion, benzo[a]biphenylene, (biphenylene)tricarbonylchromium, benzo[3,4]cyclobuta[1,2-c]thiophene, benzo[3,4]cyclobuta[1,2-c]thiophene 2-oxide, benzo[3,4]cyclobuta[1,2-c]thiophene 2,2-dioxide, 4,10-diazabenzo[b]biphenylene, biphenylene-2,3-dione, benzo[3,4]cyclobuta[1,2-b]anthracene-6,11-dione, and 3,4-dihydro-2H-benzo[3,4]cyclobuta[1,2]cycloheptene – where one of the two benzo rings of biphenylene is replaced by a different π-system (B) was investigated on the basis of the NMR parameters of these systems. From the vicinal 1H,1H spin-spin coupling constants, the electronic structure of the remaining benzo ring (A) is derived via the Q-value method. It is found that increasing tendency of B to tolerate exocyclic double bonds at the central four-membered ring of these systems favors increased π-electron delocalization in the A ring. The analysis of the chemical shifts supports this conclusion. NICS (nucleus-independent chemical shift) values as well as C,C bond lengths derived from ab initio calculations are in excellent agreement with the experimental data. The charged systems benzo[b]biphenylene dication and naphtho[2,3-b]biphenylene dianion (72−) are also studied by 13C NMR measurements. The charge distribution found closely resembles the predictions of the simple HMO model and reveals that 72− can be regarded as a benzo[3,4]cyclobuta[1,2-b]-substituted anthracene dianion. It is shown that the orientation of the tricarbonylchromium group in complexes of benzenoid aromatics can be derived from the vicinal 1H,1H coupling constants.