Synthesis, Structures, and Properties of π-Extended Phosphindolizine Derivatives.

Dibenzo[b,g]phosphindolizine oxide and three types of benzo[e]naphthophosphindolizine oxides have been synthesized by the ring-closing metathesis of benzo[b]phosphole oxide and naphthophosphole oxides with two olefin tethers. Their molecular structures and properties were revealed by X-ray crystallographic analysis, UV-vis spectroscopy, and electrochemical analysis. The number and position of the benzene rings were found to alter the structural geometry and the HOMO/LUMO energy levels, and their effects were investigated by theoretical calculations. Among the phosphindolizine oxide derivatives investigated, only benzo[e]naphtho[2,3-b]phosphindolizine oxide with the naphthalene ring fused at 2,3-positions showed weak yellow fluorescence with a large Stokes shift.

Dibenzo[b,e]phosphindolizines synthesized by a ring-closing metathesis of benzo[b]phospholes with two vinyl tethers.

Dibenzo[b,e]phosphindolizines 1 were successfully synthesized by a ring-closing metathesis of benzo[b]phosphole chalcogenides 2a-2c with two vinyl tethers (for chalcogen analogs 1a-1c), and by a deselenization reaction (for lone-pair analog 1d). The structures, properties, and bowl inversion derived from a phosphorus atom were fully investigated.