Synthesis and characterization of osmium(II) compounds of stoichiometry (C5Me5)OsL2Br, (C5Me5)OsL2H, and (C5Me5)Os(NO)Br2

Christopher L. Gross, Gregory S. Girolami

Research output: Contribution to journalArticlepeer-review


The preparations of several new (pentamethylcyclopentadienyl)osmium(II) complexes from the osmium(III) compound (C5Me5)2Os2Br4 are described; among these are phosphine and alkene complexes of stoichiometry (C5Me5)OsL2Br and (C5Me5)OsL2H as well as the nitrosyl complex (C5Me5)Os(NO)Br2. Treatment of (C5Me5)2Os2Br4 with PPh3 in ethanol or PMe3 in dichloromethane affords the osmium(II) complexes (C5Me5)OsL2Br, where L = PPh3 or PMe3; the 1,5-cyclooctadiene complex (C5Me5)Os(cod)Br can be made similarly in ethanol. Treatment of either the PPh3 or cod complex with other tertiary phosphines in refluxing heptane affords several other compounds of this class: (C5Me5)OsL2Br, where L = PEt3, 1/2 Me2-PCH2PMe2, 1/2 Me2PCH2CH2PMe2, or 1/2 Ph2PCH2PPh2. These bromoosmium(II) species serve as excellent starting materials for the preparation of other osmium(II) complexes. For example, treatment with NaBH4 in ethanol or with NaOMe in methanol affords the hydrides (C5Me5)OsL2H, where L = PMe3, PEt3, PPh3, 1/2 cod, 1/2 Me2PCH2PMe2, 1/2 Me2PCH2CH2-PMe2, or 1/2 Ph2PCH2PPh2. Interestingly, treatment of (C5Me5)Os(PMe3)2Br with NaBH4 in refluxing ethanol affords the dihydride cation [(C5Me5)Os(PMe3)2H2 +], which can be deprotonated with methyllithium in tetrahydrofuran to afford the electrically neutral hydride (C5Me5)Os(PMe3)2H. This hydride complex is expected to be one of the most basic transition metal complexes known. Finally, treatment of (C5Me5)2Os2Br4 with nitric oxide in dichloromethane yields the osmium(II) complex (C5Me5)Os(NO)Br2. IR, NMR, and mass spectra of the new complexes are described. A secondary 13C/12C isotope effect on the 31P NMR chemical shifts of ca. 0.025 ppm is noted in several compounds. Comparisons of these osmium(II) compounds with analogous ruthenium species suggests that the former have stronger metal-ligand bonds, are slower to undergo nucleophilic substitution reactions, and are stronger reducing agents.

Original languageEnglish (US)
Pages (from-to)5359-5367
Number of pages9
Issue number25
StatePublished - Dec 10 1996

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry


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