Acrylonitrile and Cyanoacetic Acid Complexes of RuIII and RuII Amines: An Analysis of The σ- And π-Component Relevance in The RuII-NCR Bond

The complexes [Ru(NH3)5L](PF6)n (n = 2,3), L = NCCHCH2, NCCH2COOH, have been isolated and characterized by elemental analysis, electronic and vibrational spectroscopies, and cyclic voltammetry. In aqueous medium, the RuII species undergoes hydrolysis yielding the corresponding tetramine aquocomplex...

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Published in:Polyhedron 1996-06, Vol.15 (19), p.3299-3307
Main Authors: Jane Fernandes Alves, Janete, Wagner Franco, Douglas
Format: Article
Language:English
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Summary:The complexes [Ru(NH3)5L](PF6)n (n = 2,3), L = NCCHCH2, NCCH2COOH, have been isolated and characterized by elemental analysis, electronic and vibrational spectroscopies, and cyclic voltammetry. In aqueous medium, the RuII species undergoes hydrolysis yielding the corresponding tetramine aquocomplex ; whereas the hydrolysis of the RuII species occurs at the coordinated nitrile ligand with the formation of the corresponding amide ligand. The substitution reaction: trans- [Ru(NH3)4NCR(H2O)]2++pz trans-[Ru(NH3) 4NCR(pz)]2+ + H2O has been investigated and the formation of an outer-sphere complex trans-[Ru(NH3)4NCR(H2O)… pz]2+ has been postulated. From the kinetic data for these substitution reactions the position of nitriles in the trans-effect and trans-influence series is proposed. The electrochemical, spectroscopic and reactivity experimental results and related data obtained for analogous systems are interpreted in terms of the relative extension of the σ- and π-RuII-NCR bond components. Copyright © 1996 Elsevier Science Ltd
ISSN:0277-5387
DOI:10.1016/0277-5387(96)00046-0