Ruthenium(II)-catalyzed thioether oxidation. 1. Synthesis of mixed sulfide and sulfoxide complexes
RuX/sub 2/(Me/sub 2/SO)/sub 4/ complexes are excellent catalysts for the selective oxygen oxidation of thioethers. Under conditions designed to mimic a catalytic situation, i.e. in methanol at 100/sup 0/C, but in the absence of oxygen, a variety of trans(X/sub 2/)-RuX/sub 2/(SR/sub 2/)/sub 4-n/(Me/sub 2/SO)/sub n/ complexes are formed; the value of n depends upon the steric bulk of the potential thioether donor, and SR/sub 2/ = S(CH/sub 2/)/sub 3/CH/sub 2/ (X = Br, n = 0 (7); X = Cl, n = 0 (8)), Me/sub 2/S (X = Cl, n = 0 (4), 1 (5), 2 (6); X = Br, n = 0 (1), 1 (2), 2 (3)), Et/sub 2/S (X = Br, n = 1 (10), 2 (11)), or t-Bu/sub 2/S (X = Br, n = 3 (9)). With multidentate thioether ligands the S-bound sulfoxide complexes trans(X/sub 2/)-RuX/sub 2/(EtSCH/sub 2/CH/sub 2/SEt)(Me/sub 2/SO)/sub 2/ (X = Cl (15), Br (12)), all-cis-RuCl/sub 2/-(EtSCH/sub 2/CH/sub 2/SEt)(Me/sub 2/SO)/sub 2/ (14), trans(X/sub 2/)-RuBr/sub 2/((EtSCH/sub 2/CH/sub 2/)/sub 2/S)(Me/sub 2/SO) (13), and cis-RuCl/sub 2/(CH/sub 3/C(CH/sub 2/SEt/sub 3/)/sub 3/)(Me/sub 2/SO) (16) were prepared, and the structure of complex 16 was confirmed by single-crystal X-ray analysis. Crystals of 16 are monoclinic, P2/sub 1//n, with a = 15.110 (2) A, b = 15.417 (3) A, c = 9.040 (1) A, ..beta.. = 104.33 (1)/sup 0/, and Z = 4. The octahedral Ru(II) complex has tridentate fac-thioether and cis-dichloro ligands. The Me/sub 2/SO ligand is coordinated to the Ru(II) ion through the S atom. The six-membered rings of the tridentate ligand assume twist-boat conformations. The Ru-S(thioether) bond lengths range from 2.312 (2) to 2.342 (2) A. The Ru-S bond length to the Me/sub 2/SO ligand is 2.277 (2) A. The Ru-Cl bond lengths are 2.423 (3) and 2.456 (3) A.
- Research Organization:
- Procter and Gamble Co., Cincinnati, OH
- OSTI ID:
- 5583306
- Journal Information:
- Inorg. Chem.; (United States), Vol. 25:11
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
BROMINE COMPLEXES
CHEMICAL PREPARATION
CRYSTAL STRUCTURE
X-RAY DIFFRACTION
CHLORINE COMPLEXES
ORGANIC COMPOUNDS
OXIDATION
CATALYSIS
RUTHENIUM COMPLEXES
CATALYTIC EFFECTS
SULFIDES
SULFOXIDES
BOND ANGLE
BOND LENGTHS
CATALYSTS
EXPERIMENTAL DATA
LATTICE PARAMETERS
CHALCOGENIDES
CHEMICAL REACTIONS
COHERENT SCATTERING
COMPLEXES
DATA
DIFFRACTION
DIMENSIONS
INFORMATION
LENGTH
NUMERICAL DATA
ORGANIC SULFUR COMPOUNDS
SCATTERING
SULFUR COMPOUNDS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
400301* - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)