Trichlorostannyl complexes of Ruthenium(II): Synthesis, structure, reactivity and computational studies
| Autor: | Jorge Bravo, Gabriele Albertin, Gianluigi Zanardo, Nuria Álvarez-Pazos, Stefano Antoniutti, Jose M. Hermida-Ramón, Soledad García-Fontán |
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| Jazyk: | angličtina |
| Rok vydání: | 2018 |
| Předmět: |
Settore CHIM/03 - Chimica Generale e Inorganica
Ruthenium complexes 010405 organic chemistry Chemistry Organic Chemistry DFT Diphosphinite ligand NBO Trichlorostannyl ligand chemistry.chemical_element Crystal structure Structure reactivity Optically active 010402 general chemistry 01 natural sciences Biochemistry 0104 chemical sciences Ruthenium Inorganic Chemistry Crystallography Distortion Materials Chemistry Physical and Theoretical Chemistry |
| Popis: | Trichlorostannyl complexes [Ru(SnCl3) (Cp')L] (2a-c) were prepared by treatment of optically active half-sandwich chlorocomplexes [RuCl(Cp')L] (1a-c) with an excess of SnCl2.2H2O in ethanol. Treatment of trichlorostannyl complexes 2a-c with NaBH4 afforded trihydridostannyl derivatives [Ru(SnH3) (Cp')L] (3a-c) in moderated yields. Treatment of 2a-c with MgBrMe gave the trimethylstannyl complexes Ru(SnMe3) (Cp')L (4a-c). Alkynylstannyl derivatives [Ru{Sn(C≡CPh)3}(Cp')L] (5a-c) were prepared by treatment of trichlorostannyl compounds 2a-c with an excess of LiC≡CPh in thf. All the complexes present optical activity. The complexes were characterized spectroscopically and by X-ray crystal structure determination of [RuCl(η5-C5Me5)L] (1b), [Ru(SnCl3) (η5-C5Me5)L] (2b), and [Ru(SnCl3) (η5-C9H7)L] (2c). The influence of different ligands on the Ru P interaction in several complexes 1a-c, 2a-c and 3a-c was evaluated by DFT calculations. These calculations indicate that [SnCl3]- has a stronger stabilization effect than [Cl]- and the same occurs between C9H7 and C5Me5. These relative stabilities combined with the distortion energies of the fragments produce a stabilizing effect in the Ru P bonds of complex 2c that is twice as strong as in the 1b complex. |
| Databáze: | OpenAIRE |
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