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Activation of C−S Bonds in Organosulfur Compounds Containing α,β‐Unsaturated Ketone Systems by Carbonylruthenium and ‐iron Complexes
Author(s) -
AlvarezToledano Cecilio,
Delgado Esther,
Donnadieu Bruno,
Gómez M. Angeles,
Hernández Elisa,
Martín Gema,
OrtegaJiménez Fernando,
Zamora Félix
Publication year - 2003
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200390078
Subject(s) - chemistry , organosulfur compounds , substituent , crystal structure , ketone , stereochemistry , medicinal chemistry , crystallography , sulfur , organic chemistry
Vinylidenetetraruthenium clusters have been obtained from the reactions between [Ru 3 (CO) 12 ] and [CH 3 C(O)CH=C(SCH 3 ) 2 ] or [(C 5 H 5 )Fe{C 5 H 4 CH=CHC(O)CH=C(SCH 2 CH 2 S)}] by cleavage of the S−C sp 2 bonds in these ligands. An excess of [CH 3 C(O)CH=C(SCH 3 ) 2 ] afforded the dinuclear complex [Ru 2 (CO) 4 (μ‐SCH 3 ) 2 {η 2 :κ‐ C , O ‐C(SCH 3 )CHC(O)CH 3 } 2 ], which was then converted into the vinylidene cluster [Ru 4 (CO) 10 (μ‐SCH 3 ) 2 {μ 4 ,η 3 :κ‐ C , C , O ‐C=CHC(O)CH 3 }] in the presence of more of the carbonylruthenium complex. However, the carbonyliron complex led to the formation of the dinuclear compounds [Fe 2 (CO) 4 (μ‐SCH 3 ) 2 {η 2 :κ‐ C , O ‐C(SCH 3 )CHC(O)CH 3 } 2 ] and [Fe 2 (CO) 5 {μ,η 4 :κ‐ C , O , S , S ‐(SCH 2 CH 2 S)C=CHC(O)CH=CHC 5 H 4 }Fe(C 5 H 5 )]. All of the new complexes exhibit a pentametallacycle group as a consequence of the rupture of the S−C bonds, as well as the presence of the C(O)R substituent in these ligands. The compounds have been characterised by analytical and spectroscopic data and the crystal structures of some of them have been solved by X‐ray diffraction. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)