Isolation and characterization of a dimeric ruthenium(II) complex. An intermediate in the ruthenium-catalyzed oxygen oxidation of thioethers to sulfoxides
Complexes of the type Ru/sup II/X/sub 2/(MeSO)/sub 2 or 3/(PR/sub 3/) are excellent catalysts for the selective oxygen oxidation of thioethers to sulfoxides. The complex RuCl/sub 2/(Me/sub 2/SO)/sub 3/(PPh/sub 3/) is an example of such a catalyst, and its solution chemistry under simulated catalytic conditions reveals that only one detectable complex is present. This presumed catalytic complex has been isolated and characterized by /sup 1/H, /sup 13/C, and /sup 31/P NMR and by an x-ray structure determination to be the chlorotri-/mu/-chlorotris(dimethyl sulfoxide)bis(triphenylphosphine)diruthenium, 2. Single crystals of 2 are monoclinic with space group P/sub 2/sub 1//c/ with a = 16.662(3)/angstrom/, b = 16.576(3)/angstrom/, c = 19.282(3)/angstrom/, and /beta/ = 98.86(1)/degree/. Both Ru centers are coordinated in a distorted octahedral fashion having three /mu/-bridged chlorine atoms shared between them. Ru/sub 1/ possesses three terminal ligands, one chloride, one triphenylphosphine and a dimethyl sulfoxide. Ru/sub 2/ is terminally bonded to two Me/sub 2/SO centers and one triphenylphosphine. The /mu/-bridged chlorine atoms are bonded in an asymmetric fashion due to the differing trans-influences of the Cl/sup /minus//, (CH/sub 3/)/sub 2/SO and PPh/sub 3/ ligands bonded to the metal centers. Ru-/mu/Cl distances range from 2.436(2)/angstrom/ to 2.490(2)/angstrom/, and Ru-S distances from 2.205(2)/angstrom/ to 2.269(2)/angstrom/.
- Research Organization:
- Monsanto Company, St. Louis, MO (USA)
- OSTI ID:
- 5830773
- Journal Information:
- J. Coord. Chem.; (United States), Journal Name: J. Coord. Chem.; (United States) Vol. 19:1-3; ISSN JCCMB
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
CARBON 13
CARBON ISOTOPES
CATALYSIS
CATALYSTS
CATALYTIC EFFECTS
CHALCOGENIDES
CHEMICAL PREPARATION
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPLEXES
DATA
DIFFRACTION
DIMERS
ELEMENTS
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
HYDROGEN 1
HYDROGEN ISOTOPES
INFORMATION
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
NMR SPECTRA
NONMETALS
NUCLEAR MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
OXIDATION
OXYGEN
PHOSPHORUS 31
PHOSPHORUS ISOTOPES
REACTION INTERMEDIATES
RESONANCE
RUTHENIUM COMPLEXES
SCATTERING
SPACE GROUPS
SPECTRA
STABLE ISOTOPES
SULFIDES
SULFOXIDES
SULFUR COMPOUNDS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
X-RAY DIFFRACTION