Carbonyl insertion into a C-S bond and complex dimerization during reaction of the dithioesters S=C(Me)SEt and S=C(Ph)SMe with iron carbonyl complexes

Article abstract of DOI:10.1016/0022-328X(87)80026-8

Dithioesters react with pentacarbonyliron or nonacarbonyldiiron under UV irradiation to give three classes of compounds.In the metal-metal-bonded complexes 1)SR²>> (R¹ = Me or Ph; R² = Et or Me) which belong to the first class, the iron atoms are doubly-bridged By a C-S unit and the original bicovalent sulphur atom of the intact dithioester unit.Similar metal links also exist in the complex 2-SC<*>S(CH2)2<*>S-S,S'>>(Fe-Fe) (I), formed from a trithiocarbonate (R¹R² = SCH2CH2) and , as confirmed by single-crystal X-ray diffraction.The nature of the bonding in the second class of compounds was established by determining the crystal structure of the dimeric compound >2 (V) in which there is no metal-metal bond but each coordinated ligand forms a non-symmetrical dative sulphur-metal bond on the other iron atom.An X-ray crystal structure of a member of the third type of compound 1)C(O)SR²>> (R¹ = Ph; R² = Me) (VI), shows that it is the result of carbonyl insertion into the C-SR² bond of the ligand.