83477-50-3Relevant academic research and scientific papers
Reactions of the SH- and S2- ligands in W(CO)5(SH)- and μ-S[W(CO)5]22- with organic electrophiles
Angelici, Robert J.,Gingerich, Richard G. W.
, p. 89 - 95 (2008/10/08)
The W(CO)5SH- complex reacts at room temperature with heterocumulenes to give products in which the S atom adds to the central carbon of the heterocumulene. Thus, W(CO)5SH- reacts with isocyanates (RN=C=O) to give monodentate thiocarbamate complexes (CO)5W[SC(=O)NHR]-, with the ketene Ph2C=C=O to give the thioacetate complex (CO)5W[SC(=O)CPh2H]-, with isothiocyanates (RN=C=S) to yield bidentate dithiocarbamate complexes (CO)4W(S2CNHR)- via the monodentate intermediate (CO)5W[SC(=S)NHR]-, with the ketenimine Ph2C=C=NPh to give the bidentate thioimidate complex (CO)4W[SC(=NPh)CPh2H]- which is transformed to the thioamide complex (CO)5W[S=C(NPhH)(CPh2H)] upon reaction with H+ and CO, and with carbodiimides (RN=C=NR) and H+ to yield thiourea complexes (CO)5W[S=C(NHR)2]. The reaction of W(CO)5SH- with perfluoroacetone and perfluorocyclohexene gives the F--substituted products (CO)5W[SCF2C(=O)CF3]- and (CO)5W[SC=CF(CF2)3CF2]-, respectively. With nitriles (MeCN, MeSCN, H2NCN) and H+, the SH- group is replaced to give (CO)5W(N≡CR) products. With PhOCN, the PhO- is displaced to give W(CO)5(NCS)-. Alkylation with MeOSO2F converts the SH- complex to W(CO)5(SMe2). The dinuclear complex with a bridging S2- ligand, μ-S[W(CO)5]22-, reacts with MeN=C=O to give the S-bridged monothiocarbamate complex [(CO)5W]2SC(=O)NMeH- and with Ph2C=C=O to yield the S-bridged acetate complex [(CO)5W]2SC(=O)CPh2H-. Results of several other attempted reactions of W(CO)5SH- with electrophiles are also reported. These studies indicate that the SH- and μ-S2- ligands in W(CO)5SH- and μ-S[W(CO)5]22- are very reactive toward organic electrophiles, while μ-HS[W(CO)5]2- is much less reactive.
