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Title: Ruthenium(II)-catalyzed thioether oxidation. 1. Synthesis of mixed sulfide and sulfoxide complexes

Abstract

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)more » 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.« less

Authors:
;
Publication Date:
Research Org.:
Procter and Gamble Co., Cincinnati, OH
OSTI Identifier:
5583306
Resource Type:
Journal Article
Journal Name:
Inorg. Chem.; (United States)
Additional Journal Information:
Journal Volume: 25:11
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, 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)

Citation Formats

Riley, D.P., and Oliver, J.D. Ruthenium(II)-catalyzed thioether oxidation. 1. Synthesis of mixed sulfide and sulfoxide complexes. United States: N. p., 1986. Web. doi:10.1021/ic00231a021.
Riley, D.P., & Oliver, J.D. Ruthenium(II)-catalyzed thioether oxidation. 1. Synthesis of mixed sulfide and sulfoxide complexes. United States. doi:10.1021/ic00231a021.
Riley, D.P., and Oliver, J.D. Wed . "Ruthenium(II)-catalyzed thioether oxidation. 1. Synthesis of mixed sulfide and sulfoxide complexes". United States. doi:10.1021/ic00231a021.
@article{osti_5583306,
title = {Ruthenium(II)-catalyzed thioether oxidation. 1. Synthesis of mixed sulfide and sulfoxide complexes},
author = {Riley, D.P. and Oliver, J.D.},
abstractNote = {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.},
doi = {10.1021/ic00231a021},
journal = {Inorg. Chem.; (United States)},
number = ,
volume = 25:11,
place = {United States},
year = {1986},
month = {5}
}