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), Journal Name: Inorg. Chem.; (United States) Vol. 25:11; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
BOND ANGLE
BOND LENGTHS
BROMINE COMPLEXES
CATALYSIS
CATALYSTS
CATALYTIC EFFECTS
CHALCOGENIDES
CHEMICAL PREPARATION
CHEMICAL REACTIONS
CHLORINE COMPLEXES
COHERENT SCATTERING
COMPLEXES
CRYSTAL STRUCTURE
DATA
DIFFRACTION
DIMENSIONS
EXPERIMENTAL DATA
INFORMATION
LATTICE PARAMETERS
LENGTH
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
OXIDATION
RUTHENIUM COMPLEXES
SCATTERING
SULFIDES
SULFOXIDES
SULFUR COMPOUNDS
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
X-RAY DIFFRACTION