DARSTERLLUNG UND EIGENSCHAFTEN VON UND REAKTIONEN MIT METALLHALTIGEN HETEROCYCLEN. XXXV. METALLZENTRIERTE C-C-VERKNUEPFUNG DURCH REDUKTIVE DIMERISIERUNG VON THIOAROYL-GRUPPEN; SYNTHESE, ABFANGREAKTIONEN UND KRISTALLSTRUKTUREN VON DITHIOLEN-KOMPLEXEN

Article abstract of DOI:10.1016/0022-328X(83)85161-4

The E- and Z-isomeric dithiolene complexes <(OC)5MnS>2(μ-CR¹=CR¹) (R' = C6H4X-4; X = H, F, Cl, CH3) are formed by the manganese-induced reductive dimerization of the thioaroyl chlorides S=C(R¹)Cl via a carbenoid intermediate which is not isolable.The Z-isomers stabilize by coordination of the free electron pairs of the sulphur on the manganese atoms under CO elimination, to give the cis-dithiolene compounds R2¹<η²-C(μ₂-S)=C(μ₂-S)>Mn2(CO)6.E-<(OC)5MnS>2(μ-CR¹=CR¹) (R¹ = C6H4F-4) and (C6H5)2<η²-C(μ₂-S)=C(μ₂-S)>Mn2(CO)6 crystallize in the monoclinic space group P2₁/n and P2₁/a with Z = 2 and 4, respectively.The E-dithiolene compounds react with activated alkynes R²C<*>CR² (R² = CO2C6H11, CO2CH(CH3)2, CO2C2H5) to form the trapping products , containing two thiamanganacyclobutene rings connected by a centre of symmetry.For R² = C6H4F-4 the compound crystallizes in the triclinic space group P<*> with Z = 1.