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Access to Metal‐Bridged Osmathiazine Derivatives by a Formal [4+2] Cyclization
Author(s) -
Li Jinhua,
Lin YuMei,
Zhang Hong,
Chen Yuan,
Lin Zhenyang,
Xia Haiping
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201806354
Subject(s) - thiazine , heteroatom , chemistry , imine , ring (chemistry) , osmium , protonation , metal , stereochemistry , isopropyl , medicinal chemistry , ruthenium , organic chemistry , ion , catalysis
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 6 H ‐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.