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Synthesis, Spectroscopic and Structural Characterization of New Ru II and Ru III Complexes Containing Triazole‐ and Thiadiazole‐Type Ligands
Author(s) -
Cingi Marina Biagini,
Lanfranchi Maurizio,
Pellinghelli Maria Angela,
Tegoni Matteo
Publication year - 2000
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/(sici)1099-0682(200004)2000:4<703::aid-ejic703>3.0.co;2-e
Subject(s) - chemistry , ruthenium , diastereomer , aqueous solution , triazole , medicinal chemistry , acetone , chelation , ligand (biochemistry) , stereochemistry , yield (engineering) , catalysis , organic chemistry , biochemistry , materials science , receptor , metallurgy
The chemical behavior of triazole, thiadiazole, and triazoline derivatives of thiocarbonohydrazide towards cis ‐[RuCl 2 (DMSO) 4 ] ( 2 ) was studied. Reaction of 4‐amino‐5‐methylthio‐3‐(2‐pyridyl)‐1,2,4‐triazole (L1) with 2 gave two diastereomeric complexes, trans,cis ‐[RuCl 2 (DMSO) 2 (L1)] ( 3 ) and chiral cis,cis ‐[RuCl 2 (DMSO) 2 (L1)] ( 4 ). Reaction of 2 with 2‐(2‐formylhydrazino)‐1,3,4‐thiadiazole in MeOH gave the complex trans,cis ‐[RuCl 2 (DMSO) 2 (L2)] ( 5 ) with concomitant deformylation of the starting ligand. The process was catalyzed by Ru II in very low yield. Synthesis of the Ru complexes of 4‐amino‐3‐methyl‐1,2,4‐Δ 2 ‐triazoline‐5‐thione (L3) and 4‐amino‐3‐ethyl‐1,2,4‐Δ 2 ‐triazoline‐5‐thione (L4) resulted in an interesting oxidation of the metal promoted by DMSO. Reaction of 2 with these ligands in a 6 N HCl solution led to the isolation of the complexes mer ‐[RuCl 3 (DMSO)(L3)] · 1/2 H 2 O ( 6 ) and mer ‐[RuCl 3 (DMSO)(L4)] · 1/2 H 2 O ( 7 ). The complex mer ‐[RuCl 3 (DMSO)(L4)] · CH 3 COOH · H 2 O ( 7′ ) was obtained by recrystallization of 7 from ethyl acetate. The complexes 6 , 7 , and 7′ were highly stable in HCl solutions and acetone but not in neutral aqueous solution. To the best of our knowledge this is the first report of Ru III complexes with an N–N–C–S chelating system.