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Synthesis, Properties, and Structural Characterization of Bromo‐ and Iodotetracarboxylatodiruthenium( II , III ) Compounds
Author(s) -
Barral M. Carmen,
GonzálezPrieto Rodrigo,
JiménezAparicio Reyes,
Priego J. Luis,
Torres M. Rosario,
Urbanos Francisco A.
Publication year - 2004
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.200400377
Subject(s) - chemistry , iodide , bromide , ligand (biochemistry) , solvatochromism , crystallography , stereochemistry , crystal structure , ruthenium , methyl iodide , bond length , molecule , medicinal chemistry , organic chemistry , catalysis , receptor , biochemistry
The synthesis and characterization of the compounds [Ru 2 X(μ‐O 2 CPh) 4 ] n [X = Br ( 1 ), I ( 2 )] and [Ru 2 X(μ‐O 2 CC 6 H 4 ‐ p ‐OMe) 4 (H 2 O)] [X = Br ( 3 ) and I ( 4 )] is described. The structures of these compounds were determined by single‐crystal X‐ray diffraction. The molecular structures of [Ru 2 Br(μ‐O 2 CCMePh 2 ) 4 (EtOH)·0.5EtOH] ( 5· 0.5EtOH) and [Ru 2 I(μ‐O 2 CCMePh 2 ) 4 (MeOH)·0.5H 2 O] ( 6· 0.5H 2 O) are also reported. Complexes 1 and 2 show a zigzag polymeric arrangement with the diruthenium units linked by bromide and iodide ligands, respectively. The molecular nature of compounds 3 and 4 shows the influence of the axial ligand in the arrangement in the solid state, which contrasts with the polymeric structure found in all chlorodiruthenium( II , III ) derivatives with arenecarboxylate bridging ligands. The Ru−Ru bond lengths for all complexes range from 2.2756(17) to 2.2906(7) and 2.273(3) to 2.2965(6) Å for the bromide and iodide derivatives, respectively. This study demonstrates that the nature of the axial ligand plays an important role in the arrangement in the solid state and in the electronic properties of the halotetracarboxylatodiruthenium( II , III ) complexes. Thus, the iodo derivatives show an intense solvatochromism, whereas the solvatochromism is slight in the bromo derivatives and is not observed in the chloro complexes. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)