Reactivity of [H2Os3(CO)10] with six-membered heterocycles containing sulfur and/or nitrogen atoms. Cleavage of C–S, C–N and C–H bonds to yield linked clusters with S–C, and S–C–N bridging fragments

Abstract

The reactions of [H2Os3(CO)10] with hetero-cyclohexanes with positions 1, 3 and 5 substituted by nitrogen or sulfur atoms; 1,3,5-trimethyl-1,3,5-triazinane, 3,5-dimethyl-1,3,5-thiadiazinane, 5-methyl-1,3,5-dithiazinane and 1,3,5-trithiane; produce compounds where sulfur atoms and NCN fragments bridge metal–metal bonds as well as complexes containing trinuclear metal fragments linked by SCS and SCNCS units. Spectroscopic characterization of the products as well as the X-ray crystal structures of complexes {[(μ-H)Os3(CO)9(PMe3)]–[μ-(H2CCS2)]–[(μ-H)Os3(CO)10]}, {(μ-H)Os3(CO)10(μ-SCH2NMe2)}, {[(μ-H)Os3(CO)10]2[μ-S2(CH2)2NMe]} and [Os(S3(CH2)3)2Cl2(CO)2] are reported. A mechanistic proposal for all the reactions is made based in spectroscopic analysis of the reaction mixtures and theoretical calculations for the non-coordinated ligands.