Ruthenium(IV)-oxo complexes: the novel utilization of tertiary pnictogen ligands

Journal Article · Tue Mar 01 23:00:00 EST 1988 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00213a019· OSTI ID:7256247

Marmion, M E; Takeuchi, K J

The novel complexes ((bpy)/sub 2/(PnR/sub 3/)Ru/sup IV/(O))(ClO/sub 4/)/sub 2/ (where bpy = 2,2'-bipyridine and PnR/sub 3/ = tertiary phosphine or arsine) have been generated from the analogous ruthenium(II)-aquo species, through electrochemical means or by the addition of two equivalents of cerium(IV). Characterization of the ruthenium(II)-aquo and ruthenium(IV)-oxo complexes was accomplished through UV-vis spectroscopy, IR spectroscopy, /sup 18/O labeling experiments, NMR spectroscopy, cyclic voltammetry, coulometry, and conductivity measurements. These complexes are stable both in the solid state and in various solutions, where the phosphine and arsine ligands do not undergo oxidation by the ruthenium(IV)-oxo center. Cyclic voltammetric measurements of the ruthenium(II)-aquo complexes are consistent with the following redox couples: Ru/sup IV/ = ORu/sup III/ - OHRu/sup II/ - OH/sub 2/, which can be described as two sets of concomitant one-electron, one-proton transfers. The ruthenium(IV)-oxo complexes act as selective oxidation reagents toward organic substrates, where the nature of the pnictogen ligand greatly affects the rate of substrate oxidation. In addition, the use of a pnictogen ligand cis to the oxo moiety in these complexes simplifies the mechanism of substrate oxidation relative to other ruthenium-based oxidants. Finally, pnictogen ligands exert unusual effects on the redox chemistry of ruthenium(IV)-oxo complexes, including hydrophobic selectivity and aerobically driven substrate oxidation catalysis.

• Research Organization: State Univ. of New York, Buffalo (USA)
• OSTI ID: 7256247
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 110:5; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ABSORPTION SPECTROSCOPY
AROMATICS
AZINES
CARBON 13
CARBON ISOTOPES
CATALYSIS
CATALYSTS
CATALYTIC EFFECTS
CHEMICAL PREPARATION
CHLORINATED AROMATIC HYDROCARBONS
DATA
ELECTRIC CONDUCTIVITY
ELECTRICAL PROPERTIES
EVEN-EVEN NUCLEI
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
HALOGENATED AROMATIC HYDROCARBONS
HETEROCYCLIC COMPOUNDS
HYDROGEN 1
HYDROGEN ISOTOPES
INFORMATION
INFRARED SPECTRA
ISOTOPES
LABELLING
LIGANDS
LIGHT NUCLEI
MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXYGEN 18
OXYGEN ISOTOPES
PHOSPHINES
PHOSPHORUS COMPOUNDS
PHYSICAL PROPERTIES
PNICTIDES
PYRIDINES
REFRACTORY METAL COMPOUNDS
RESONANCE
RUTHENIUM COMPOUNDS
SPECTRA
SPECTROSCOPY
STABLE ISOTOPES
STRUCTURAL CHEMICAL ANALYSIS
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS
ULTRAVIOLET SPECTRA
VISIBLE SPECTRA
VOLTAMETRY