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2005
Organo-chromium compounds
S 5500
Synthesis, Structure and Benzannulation of Chalcogen-Tethered Fischer Carbene
— The successful syntheses and structural assignments of chromium or
11- 181 Complexes.
tungsten α,β-unsaturated Fischer carbene complexes featuring a β-sulfur or β-selenium
substituent are reported. Either unseparable mixtures of (E)/(Z)-isomers like complexes
(IV)/(VI) or single (E)- and (Z)-isomers like complex (I) are obtained. By warming of
the mixture (IV)/(VI), pure (E)-isomer (VI) can be separated from cyclometalated product (V), which is formed by a chelation reaction of (Z)-isomer (IV). The (E)-isomers
of both selenium and sulfur complexes (I) and (VI) undergo with mono- and disubstituted acetylenes benzannulation reactions with elimination of the PhS- or PhSe-groups
to provide substituted phenols. In addition to these experiments, a variety of aminolysis
reactions are performed with the ethoxy-substituted Fischer carbenes to give the corresponding amino complexes either as geometrically pure isomers or as isomeric mixtures. — (SINHA-MAHAPATRA, D. K.; HAZRA, D.; PURANIK, V. G.; SARKAR*,
A.; J. Organomet. Chem. 689 (2004) 22, 3501-3512; Div. Org. Chem., Natl. Chem.
Lab., Pune 411 008, India; Eng.) — Klein
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