ic3004118_si_002.cif (61.38 kB)

Ruthenium(II) Thiol and H2S Complexes: Synthesis, Characterization, and Thermodynamic Properties

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posted on 07.05.2012, 00:00 by Erin S. F. Ma, Steven J. Rettig, Brian O. Patrick, Brian R. James
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.