Oxidation of Ru-bound thiolate thioether and its NS4-ligand containing thiolate and thioether sulfur donors: synthesis, characterization, and X-ray structures
A ruthenium complex [Ru(H2O){Et2NpyS4(O3)2}] · (4) containing sulfinates, sulfenates S-donors, and water as co-ligand has been synthesized from oxidation of hydrazine complex [Ru(N2H4)(Et2NpyS4)] (3) and completely characterized with X-ray structural analysis [Et2Npy [image
omitted]= 4-(diethylamino)-2,6-bis[(2-mercaptophenyl)thiomethyl]pyridine(2-)]. Complex 4 exhibits distorted octahedral coordination of the ruthenium center and the d [Ru-Ssulfinates] and d [Ru-Ssulfenates] are almost equivalent. The average d[S-Osulfinate] at 148.0 pm is ca 10 pm longer than
the average d [S-Osulfenate] at 138.0 pm. The sulfinates IR(KBr) bands are located in the range 1132-1113 cm-1 as two band sets, ν(SO)asym and ν(SO)sym, whereas the sulfenates show a single absorbance at approximately 882 cm-1. The lower frequency of the ν(SO) stretches of the sulfenates
as compared to that of their sulfinate rivals indicates a weaker S-O bond in the sulfenates and is consistent with X-ray crystal structure data (vide infra). Oxidation of the dithiol ligand Et2NpyS4-H2 (1) under the same condition afforded the disulfide, in this case forming a macrocyclic
ligand S,S-Et2NpyS4 (2) as is evidenced by an X-ray crystal structure determination. Thus, the oxidation of 3 involves activation of either the oxygen or thiolate by the ruthenium center.
Keywords: Disulfide; Macrocycle; Ruthenium complexes; Sulfenates; Sulfinates; Sulfur oxidation
Document Type: Research Article
Affiliations: 1: Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich-Alexander University, D-91058 Erlangen, Germany,Faculty of Science, Department of Chemistry, Kafrelsheikh University, Kafrelsheikh 33516 Egypt 2: Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich-Alexander University, D-91058 Erlangen, Germany
Publication date: 01 July 2010
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