Phenylnitrene Ring expansion, geometries

Our calculations on the ring expansion of the lowest singlet state of phenylnitrene ( A2-lb) to azacycloheptatetraene (3b) predict a two-step mechanism that is analogous to that for the rearrangement of la to 3a and which involves the bicyclic azirine intermediate 2b.61 The CASPT2 energetics are depicted in Fig. 5, and the CASSCF optimized geometries of the stationary points are shown in Fig. 6. 

Figure 6. CASSCF(8,8)/6-31G optimized geometries of stationary points in the ring expansion of singlet phenylnitrene ( Aj-lb).61 Bond lengths in angstroms, and bond angles in degrees. The ball-and-stick pictures are profiles that indicate the nonplanar nature of these species.

Fig. 8 CASPT2N/6-311G(2d,p) relative energies of species involved in the ring expansion of phenylnitrene (PN). Energies are for CASSCF/6-31G geometries and include ZPE corrections." ...

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See also in sourсe #XX -- [ ]

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