Although molecular thioamide complexes of late-transition metals have been prepared since 1979, the chemistry of primary thioamide complexes remains relatively unexplored. To shed light on this area, we have investigated synthesis, structures, and reactivities of simple rhodium organometallic complexes with a primary arenecarbothioamide ligand [Cp*RhCl 2 {SC(Ar)NH 2 -κ 1 S}] (Cp* = η 5 -C 5 Me 5 ). Intra-and intermolecular hydrogen bonding in the thioamide complexes is discussed on the basis of 1 H NMR spectroscopy and X-ray analysis. When these rhodium complexes were treated with a large excess amount of Et 3 N, desulfurization of the thioamide ligand took place to give arenecarbonitriles (ArCN) in high GC yield and the cubane-type cluster [(Cp*Rh) 4 (μ 3 -S) 4 ] (3) in good yield as the organometallic product. Use of a smaller amount (2.4 equiv) of Et 3 N followed by treatment with NaBAr F 4 (Ar F = 3,5-(CF 3 ) 2 C 6 H 3 ) led to the isolation of the cationic clusters [(Cp*Rh) 4 (μ 3 -S) 4 ](BAr F 4 ) or [(Cp*Rh) 4 (μ 3 -S) 4 ](BAr F 4 ) 2 in low yield. Reaction mechanisms of the desulfurization of the coordinated thioamides and the formation and oneor two-electron oxidation of 3 during the desulfurization are discussed.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.