Access to Metal-Bridged Osmathiazine Derivatives by a Formal [4+2] Cyclization |
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Authors: | Jinhua Li Dr. Yu-Mei Lin Dr. Hong Zhang Yuan Chen Prof. Dr. Zhenyang Lin Prof. Dr. Haiping Xia |
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Affiliation: | 1. State Key Laboratory of Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005 P. R. China;2. Department of Chemistry, The Hong Kong University of Science &, Technology, Clear Water Bay, Kowloon, Hong Kong, P. R. China |
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Abstract: | Treatment of osmacyclopentadiene derivatives 1 with phenyl or isopropyl isothiocyanate gave the fused five and six-membered osmacycles 2 – 5 by a formal [4+2] cyclization. The facile protonation of the newly generated exocyclic imine in complexes 2 – 5 afforded conjugation-extended osmacycle derivatives 6 – 9 . Compounds 2 – 9 each contain two main-group heteroatoms (N and S) in the fused six-membered ring located at the ortho (for S) and para (for N) positions relative to the osmium centre; these species can be regarded as rare osma-1,3-thiazine derivatives and represent the first fused metallathiazine derivatives. In contrast to the non-planar organic 6H-1,3-thiazine, nearly coplanar metallathiazines 8 and 9 can be achieved by tuning the groups on the two nitrogen atoms. These unique metal-bridged osma-1,3-thiazine derivatives exhibit remarkable stabilities, broad spectral absorptions spanning the visible spectra, and considerable photothermal properties, which suggests their potential applications in material science. |
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Keywords: | [4+2] cyclization 1,3-thizaine heteroatoms metallacycles osmium |
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