UEBERGANGSMETALLKOMPLEXE MIT SCHWEFELLIGANDEN. XXX. STRUCTUR, STEREOISOMERIE UND REACTIVITAET VON EISEN-, MOLYBDAEN- UND RUTHENIUM-KOMPLEXEN MIT DEN FUENFZAEHNIGEN THIOETHER-THIOLAT-LIGANDEN dpttd2- = 2,3,11,12-DIBENZO-1,4,7,10,13-PENTATHIATRIDECAN(-2) UND t-bu4-dpttd2- = 14,16,18...

Article abstract of DOI:10.1016/S0022-328X(00)99755-9

meso- (dpttd^2- = 2,3,11,12-dibenzo-1,4,7,10,13-pentathiatriatridecane(-2) can be isolated by fractional crystallization from a mixture of diastereomers of and was characterized by X-ray structure analysis.The Fe center in meso- is pseudo-octahedrally coordinated by one C and five S atoms and contains a mirror plane.The t-butyl derivative of dpttd-H2, the sterically demanding pentadentate thioether thiolate ^2- (=14,16,18,20-tetra-t-butyl-2,3,11,12-dibenzo-1,4,7,10,13-pentathiatridecane(-2)) coordinates to Fe, Ru and Mo centers yielding mixtures of diastereomeric complexes.Thus FeCl2.4H2O reacts with Na2 to give diastereomers of , which coordinate CO to give three diastereomers of , two of which could be separated.One of these was unambiguously identified by 1H NMR spectroscopy to be meso-. meso- reacts with NO⁺ retaining its configuration to yield meso-⁺; a reaction mechanism via thionitrosylation of a thiolate S atom of the t-bu4-dpttd^2- ligand is proposed.The reaction of with t-bu4-dpttd-H2 and H2O yields a mixture of diastereomers of , from which meso- is isolated by fractional crystallization.Reaction of RuCl3(NO).xH2O and with t-bu4-dpttd^2- yields mixtures of diastereomers of ⁺ and 2, respectively; the latter is reduced by Zn to give .