TY - JOUR
T1 - Reactions of some iron and tungsten mercapto-complexes with electrophilic acetylenes leading to novel metallacycles. The crystal and molecular structure of the η2-vinyl complex [W{η2-C(CF3)C(CF3)C(O)SMe}(CO)2 (η5-C5H5)]
AU - Davidson, Jack L.
AU - Shiralian, Mahmoud
AU - Manojlović-Muir, Ljubica
AU - Muir, Kenneth W.
PY - 1984
Y1 - 1984
N2 - Reactions of [Fe(SR')(CO)2(?5-C5H5)] with activated alkynes CF3C=CCF3 and MeO2CC=CCO2Me give heterocyclic complexes [Fe{C(O)C(R)=C(R)SR'}(CO)(?5-C5H5)] (R' = alkyl or aryl, R = CF3 or CO2Me). Related derivatives [W(C(O)C(R)=C(R)SR'}(CO)2(?5-C5H 5)](R' = Me or Et) obtained from [W(SR')(CO)3(?5-C5H5)] and the alkynes in hexane at 20 °C undergo a sequence of thermal isomerisations above 25 °C involving initially a novel 1,3 shift of the SR' ligand across the eneone ligand to give the ?2-vinyl complex [W{?2-C(R)C(R)C(O)SR'}(CO)2(? 5-C5H5)] (R = CF3 only) followed by S-bonded vinyl ketone complexes [W{C(R)=C(R)C(O)SR'}(CO)2(?5-C5H 5)] and ultimately O-bonded vinyl ketone derivatives [W{C(R)=C(R)C(SR')O}(CO)2(?5-C5H 5)] and co-ordinatively unsaturated alkyne complexes [W(SR')(CO)(RC=CR)(?5-C5H5)] (R = CF3 only). An X-ray structure determination of the ?2-vinyl complex [W{?2-C(CF3)C(CF3)C(O)SMe}(CO) 2(?5-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 ?5-C5H5 ligand which occupies one face of the octahedron. Two carbonyl ligands occupy two octahedral sites while the third is occupied by the ?2-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.
AB - Reactions of [Fe(SR')(CO)2(?5-C5H5)] with activated alkynes CF3C=CCF3 and MeO2CC=CCO2Me give heterocyclic complexes [Fe{C(O)C(R)=C(R)SR'}(CO)(?5-C5H5)] (R' = alkyl or aryl, R = CF3 or CO2Me). Related derivatives [W(C(O)C(R)=C(R)SR'}(CO)2(?5-C5H 5)](R' = Me or Et) obtained from [W(SR')(CO)3(?5-C5H5)] and the alkynes in hexane at 20 °C undergo a sequence of thermal isomerisations above 25 °C involving initially a novel 1,3 shift of the SR' ligand across the eneone ligand to give the ?2-vinyl complex [W{?2-C(R)C(R)C(O)SR'}(CO)2(? 5-C5H5)] (R = CF3 only) followed by S-bonded vinyl ketone complexes [W{C(R)=C(R)C(O)SR'}(CO)2(?5-C5H 5)] and ultimately O-bonded vinyl ketone derivatives [W{C(R)=C(R)C(SR')O}(CO)2(?5-C5H 5)] and co-ordinatively unsaturated alkyne complexes [W(SR')(CO)(RC=CR)(?5-C5H5)] (R = CF3 only). An X-ray structure determination of the ?2-vinyl complex [W{?2-C(CF3)C(CF3)C(O)SMe}(CO) 2(?5-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 ?5-C5H5 ligand which occupies one face of the octahedron. Two carbonyl ligands occupy two octahedral sites while the third is occupied by the ?2-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.
UR - http://www.scopus.com/inward/record.url?scp=37049097678&partnerID=8YFLogxK
U2 - 10.1039/DT9840002167
DO - 10.1039/DT9840002167
M3 - Article
SN - 1472-7773
SP - 2167
EP - 2176
JO - Journal of the Chemical Society, Dalton Transactions
JF - Journal of the Chemical Society, Dalton Transactions
IS - 10
ER -