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. 2009 Dec 23;131(50):18036-7.
doi: 10.1021/ja9094523.

Direct observation of a photoinduced nonstabilized nitrile imine structure in the solid state

Shao-Liang Zheng  1 , Yizhong Wang, Zhipeng Yu, Qing Lin, Philip Coppens
Affiliations

Direct observation of a photoinduced nonstabilized nitrile imine structure in the solid state

Shao-Liang Zheng et al. J Am Chem Soc. .

Abstract

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.

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Figures

Figure 1
Figure 1
Structures of the tetrazole compounds used in this study.
Figure 2
Figure 2
Crystal structures of Zn-tetrazole complexes: (a) Zn•12•(H2O)2; (b) Zn•22; (c) Zn•3•(H2O); (d) Zn•4•(NH3)2; (e) Zn•52•(H2O)4•(CH3OH)2; (f) Zn•62•(H2O)4•(NH4)2. Zn is shown in silver. The distances between N3–N4 and the nearest surrounding atoms are marked on the structures.
Figure 3
Figure 3
Photocrystallography of Zn-tetrazole 3 complex: (a) Color change of the crystal upon laser exposure. (b) Photodifference map based on the Fo,(after)-Fo (before). Blue, 2.0; light blue, 1.0; orange, −1.0; red, −2.0 e/A. Only one half of the map is shown because of the 2-fold symmetry. (c) ORTEP representation of the geometry-refined nitrile imine structure. (d) Packing of the nitrile imines and molecular N2 in the crystal lattice. The N≡N bonds are perpendicular to the plane of view.
Scheme 1
Scheme 1
Scheme 2
Scheme 2
See this image and copyright information in PMC

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