Chemistry of a family of semiquinone monochelates of carbonyl ruthenium(II) generated by reacting quinones with hydridic species |
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| Authors: | Indranil Bhattacharyya Maya Shivakumar Animesh Chakravorty |
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| Affiliation: | 1. Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Kolkata 700 032, India;2. Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore 560 064, India;1. Department of Chemistry and Biochemistry, Waseda University, 3-4-1 Ohkubo, Shinjuku-ku, Tokyo 169-8555, Japan;2. Department of Applied Chemistry, Meiji University, 1-1-1 Higashimita, Tama-ku, Kawasaki 214-8571, Japan;1. Laboratory of Microbiology, Parasitology and Hygiene (LMPH), Faculty of Pharmaceutical, Biomedical and Veterinary Sciences, University of Antwerp, Universiteitsplein 1, B-2610, Wilrijk, Belgium;2. Department of Green Chemistry and Technology, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, B-9000, Ghent, Belgium;3. Institut de Pharmacologie et de Biologie Structurale (IPBS), Université de Toulouse, CNRS, Université Paul Sabatier, F-31077, Toulouse, France;1. Institute of Physical and Organic Chemistry at Southern Federal University, Stachka Avenue 194/2, Rostov-on-Don, Russia;2. Department of Chemistry and Biochemistry, Utah State University, Old Main Hill 300, Logan, UT 84322, USA |
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| Abstract: | The reactions of [Ru(H)(Cl)(CO)(PPh3)3] with 3,5-di-tert-butyl-o-benzoquinone (dbq) and 3,4,5,6-tetrachloro-o-benzoquinone (tcq) have afforded the corresponding semiquinone complexes [RuII(dbsq)(Cl)(CO)(PPh3)2] and [RuII(tcsq)(Cl)(CO)(PPh3)2], respectively. The reaction of [Ru(H)2(CO)(PPh3)3] with tcq has furnished [RuII(tcsq)(H)(CO)(PPh3)2]. Structure determination of [Ru(dbsq)(Cl)(CO)(PPh3)2] has revealed that it is a model semiquinonoid chelate with two equal C---O lengths ( 1.291(6) and 1.296(6) Å). The complexes are one-electron paramagnetic (1.85μB) and their EPR spectra in fluid media display a triplet structure (g2.00) due to superhyperfine coupling with two trans-31P atoms (Aiso17 G). The stretching frequency of the CO ligand increases by 20 cm−1 in going from [Ru(dbsq)(Cl)(CO)(PPh3)2] to [Ru(tcsq)(Cl)(CO)(PPh3)2] consistent with electron withdrawal by chloro substituents. For the same reason the E1/2 values of the cyclic voltammetric quinone/semiquinone and semiquinone/catechol couples undergo a shift of 500 mV to higher potentials between [Ru(dbsq)(Cl)(CO)(PPh3)2] and [Ru(tcsq)(Cl)(CO)(PPh3)2]. |
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| Keywords: | Ruthenium(II) complexes Semiquinone monochelates Homolytic hydride cleavage |
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