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

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• 作者：Erin S. F. Ma ; Steven J. Rettig ; Brian O. Patrick ; Brian R. James
• 刊名：Inorganic Chemistry
• 出版年：2012
• 出版时间：May 7, 2012
• 年：2012
• 卷：51
• 期：9
• 页码：5427-5434
• 全文大小：387K
• 年卷期：v.51,no.9(May 7, 2012)
• ISSN：1520-510X

文摘

The known, green, five-coordinate species trans-RuCl₂(P鈥揘)(PPh₃) react with R鈥睸H thiols to give yellow cis-RuCl₂(P鈥揘)(PPh₃)(R鈥睸H) products (P鈥揘 = o-diphenylphosphino-N,N鈥?dimethylaniline; R鈥?= alkyl). The MeSH and EtSH compounds are structurally characterized, with the former being the first reported for a transition metal鈥揗eSH complex, while the thiol complexes with R鈥?= ⁿPr, ⁱPr, ⁿPn (pentyl), ⁿHx (hexyl), and Bn (benzyl) are synthesized in situ. Other trans-RuX₂(P鈥揘)(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 Ru^IICl₂(P鈥揘)(PPh₃) complex in solution decomposes under O₂ to form [Ru^IIICl(P鈥揘)]₂(渭-O)(渭-Cl)₂.