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Complex Formation between [(η 6 ‐ p ‐cymene)Ru(H 2 O) 3 ] 2+ and Hydroxycarboxylates or their Sulfur Analogues – The Role of Thiolate Groups in Metal Ion Binding
Author(s) -
Hüse Dániel,
Bíró Linda,
Patalenszki János,
Bényei Attila Csaba,
Buglyó Péter
Publication year - 2014
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201402559
Subject(s) - chemistry , protonation , carboxylate , tartaric acid , medicinal chemistry , nuclear magnetic resonance spectroscopy , alkoxide , stereochemistry , ruthenium , metal , hydrolysis , aqueous solution , alcohol , sulfur , inorganic chemistry , spectroscopy , crystallography , ion , organic chemistry , citric acid , catalysis , physics , quantum mechanics
The interactions between [(η 6 ‐ p ‐cymene)Ru(H 2 O) 3 ] 2+ and L ‐malic acid (H 2 mal), L ‐tartaric acid (H 2 tart), and their sulfur‐containing analogues dl ‐thiomalic acid (H 3 thiomal) and meso ‐2,3‐dimercaptosuccinic acid (H 4 dmsa) were studied by pH potentiometry, NMR spectroscopy, and ESI‐MS. The hydroxycarboxylates are potent metal ion binders and prevent hydrolysis at pH 7.4 in aqueous solution. Although H 2 mal forms mononuclear complexes with different degrees of protonation by the involvement of the alcohol/alkoxide group in addition to the carboxylate groups, the presence of binding isomers is detected for the H 2 tart system. The replacement of the alcohol group by a thiolate group results in the formation of dinuclear [Ru 2 A 2 ] complexes as the single species over a wide pH range. Complexes with identical binding modes with H 3 thiomal or polymeric species with H 4 dmsa are identified, and the X‐ray structure of [{(η 6 ‐ p ‐cym)Ru} 2 (Hthiomal) 2 ] is reported. The stereochemistry of the chiral‐at‐metal complexes was explored by NMR spectroscopy and is also discussed.