Direct observation of a photoinduced nonstabilized nitrile imine structure in the solid state.
We report the direct observation of a bent geometry for a nonstabilized nitrile imine in a metal-coordination crystal. The photoinduced tetrazole ring rupture to release N(2) appears to depend on the size of voids around the N(3)-N(4) bond in the crystal lattice. We further observed the selective formation of the 1,3-addition product when a reactive nitrile imine was photogenerated in water. Overall, the bent nitrile imine geometry agrees with the 1,3-dipolar structure, a transient reactive species that mediates the photoinduced 1,3-dipolar cycloaddition in the aqueous medium.
Zheng
Shao-Liang
SL
Department of Chemistry, State University of New York at Buffalo, Buffalo, New York 14260, USA.
Wang
Yizhong
Y
Yu
Zhipeng
Z
Lin
Qing
Q
Coppens
Philip
P
D018360:Crystallography, X-Ray; D003500:Cyclization; D007097:Imines / Q000737:chemistry* / Q000528:radiation effects; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D008968:Molecular Conformation; D009570:Nitriles / Q000737:chemistry* / Q000528:radiation effects; D044367:Phase Transition; D055668:Photochemical Processes; D013777:Tetrazoles / Q000737:chemistry
D007097:Imines; D009570:Nitriles; D013777:Tetrazoles