Ruthenium(II) Thiol and H<sub>2</sub>S Complexes: Synthesis, Characterization, and Thermodynamic Properties
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The known, green, five-coordinate species trans-RuCl2(P–N)(PPh3) react with R′SH thiols to give yellow cis-RuCl2(P–N)(PPh3)(R′SH) products (P–N = o-diphenylphosphino-N,N′-dimethylaniline; R′ = alkyl). The MeSH and EtSH compounds are structurally characterized, with the former being the first reported for a transition metal–MeSH complex, while the thiol complexes with R′ = nPr, iPr, nPn (pentyl), nHx (hexyl), and Bn (benzyl) are synthesized in situ. Other trans-RuX2(P–N)(PR3) complexes (X = Br, I; R = Ph, p-tolyl) are synthesized, and their H2S adducts, of a type reported earlier by our group, are also prepared. Thermodynamic data are presented for the reversible formation of the MeSH and EtSH complexes and the H2S analogues. The RuIICl2(P–N)(PPh3) complex in solution decomposes under O2 to form [RuIIICl(P–N)]2(μ-O)(μ-Cl)2.
