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), Vol. 19:1-3
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
RUTHENIUM COMPLEXES
CATALYTIC EFFECTS
SULFIDES
OXIDATION
SULFOXIDES
CHEMICAL PREPARATION
CARBON 13
CATALYSIS
CATALYSTS
DIMERS
EXPERIMENTAL DATA
HYDROGEN 1
NMR SPECTRA
NUCLEAR MAGNETIC RESONANCE
OXYGEN
PHOSPHORUS 31
REACTION INTERMEDIATES
SPACE GROUPS
X-RAY DIFFRACTION
CARBON ISOTOPES
CHALCOGENIDES
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPLEXES
DATA
DIFFRACTION
ELEMENTS
EVEN-ODD NUCLEI
HYDROGEN ISOTOPES
INFORMATION
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
NONMETALS
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PHOSPHORUS ISOTOPES
RESONANCE
SCATTERING
SPECTRA
STABLE ISOTOPES
SULFUR COMPOUNDS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties