Photochemical reactions of the hydrogen atom transfer between arsines and triplet nitro compounds

We considered reactions of the hydrogen atom transfer between arsines and triplet nitro compounds such as

¹XAsH₂ + ³YNO₂ → ³[XAsH…H…ONOY] → ²XAsH^. + ²HONOY^.

in our case X = H, CH₃, Ph; Y = H, CH₃, Ph.

In the case of all arsine and nitro compounds we have obtained similar characteristics for example arsine - bond (As-H) =1.574 Å, bond (O-H) = 1.573 Å,  Angle (As-H-O) = 162,555-degree, atomic spin density (As) = 0.2931, atomic spin density (H) = -0.0425, atomic spin density (O) = -0.6895, activation energy = 4.79 kCal/mol. Methyl arsine and phenyl arsine have shorter bond between arsenic and hydrogen and longer one between oxygen and hydrogen in the case of arsine. We haven’t obtained any difference between HNO₂ and CH₃NO₂ geometries in the transitional states. Nitro phenyl has shorter bond between arsenic and hydrogen atoms and longer between oxygen and hydrogen atoms than in the case of arsine.

Spin density donor substituents at the arsenic atom makes bond (As-H) more long, but donor substituents at the nitrogen atom makes bond (O-H) shorter. If X or Y was Ph then, atomic spin density on hydrogen atom should be raised. X and Y made the same influence in the case of hydrogen atomic spin density.

Results were obtained by method ZOOM-NEB-TS wB97XD/def2-TZVP of the ORCA program.