REACTIONS OF SOME IRON AND TUNGSTEN MERCAPTO-COMPLEXES WITH ELECTROPHILIC ACETYLENES LEADING TO NOVEL METALLACYCLES. THE CRYSTAL AND MOLECULAR STRUCTURE OF η2-VINYL COMPLEX 2-C(CF3)C(CF3)-C(O)SMe>(CO)2(η5-C5H5)>

DOI: 10.1039/DT9840002167

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2167 - 2176 (1984)

Update date:2022-08-05

Topics:

Authors:

Davidson, Jack L.

Shiralian, Mahmoud

Manojlovic-Muir, Ljubica

Muir, Kenneth W.

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Article abstract of DOI:10.1039/DT9840002167

Reactions of 5-C5H5)> with activated alkynes CF3C<*>CCF3 and MeO2CC<*>CCO2Me give heterocyclic complexes <*> (R' = alkyl or aryl, R = CF3 or CO2Me).Related derivatives <*> (R' = Me or Et) obtained from 5-C5H5)> and the alkynes in hexane at 20 deg C undergo a sequence of thermal isomerisations above 25 deg C involving initially a novel 1,3 shift of the SR' ligand across the eneone ligand to give the η²-vinyl complex 2-C(R)C(R)C(O)SR'>(CO)2(η⁵-C5H5)> (R = CF3 only) followed by S-bonded vinyl ketone complexes <*> and ultimately O-bonded vinyl ketone derivatives <*> and co-ordinatively unsaturated alkyne complexes CR)(η⁵-C5H5)> (R = CF3 only).An X-ray structure determination of the η² -vinyl complex 2-C(CF3)C(CF3)C(O)SMe>(CO)2(η⁵-C5H5)> reveals the first example of a vinyl group bonded to a metal via both carbon atoms and therefore acting as a three-electron donor ligand.The structure consists of an approximately octahedrally co-ordinated tungsten atom bonded to an η⁵-C5H5 ligand which occupies one face of the octahedron.Two carbonyl ligands occupy two octahedral sites while the third is occupied by the Η²-C(CF3)C(CF3)C(O)SMe ligand which adopts an orientation such that the vinylic C-C axis lies approximately parallel to one of the W-CO axes.

Full text of DOI:10.1039/DT9840002167

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