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(Reference retrieved automatically from Web of Science through information on FAPESP grant and its corresponding number as mentioned in the publication by the authors.)

Structural and reactivity changes in ruthenium ammines induced by the NO ligand

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Silva, Welter C. ; Castellano, Eduardo E. [2] ; Franco, Douglas W.
Total Authors: 3
Document type: Journal article
Source: Polyhedron; v. 23, n. 6, p. 1063-1067, mar. 2004.
Field of knowledge: Physical Sciences and Mathematics - Chemistry

The crystal structure of [Ru(NH3)(5)(OH2)](2)(S2O6)(3) . 2H(2)O has been solved by X-ray diffraction techniques. The relevant average interatomic distances are Ru-(NH3)(eq) = 2.09 Angstrom, Ru-(NH3)(ax) = 2.08 Angstrom and Ru-(OH2)(ax) = 2.11 Angstrom. The aquation rate (k(H2O)) and the activation parameters for the reaction trans-[RuNO(NH3)(5)Cl](2+) + H2O (kH2O)--> trans-[RuNO(NH3)(4)(H2O)](3+) + Cl- have been calculated as 8.4 x 10(-6) s(-1) (0.10 mol L-1 CF3COOH, mu = 0.10 mot L-1, 40 degreesC), DeltaH(-1)(not equal), = 2.3 kcal mol(-1), DeltaS(-1)(not equal) = 24.0 cal deg(-1) mot and DeltaG(-1)(not equal) = 8.6 kcal mol(-1). A comparison between the structural data, kinetic and thermodynamic reactivities of [Ru(NH3)(5)(OH2)](3+) and trans-[RuNO(NH3)(4)(OH2)](3+) ions strongly suggests that the substitution of the trans NH3 ligand in the coordination sphere of [Ru(NH3)(5)(OH2)](2+) by NO confers a character of Ru(111) to the formally Ru(II) center. (AU)

FAPESP's process: 99/07109-9 - Thermal and photochemical reactivity of ruthenium nitrosyl complexes: knowledge and control of the nitric oxide coordinated reactivity
Grantee:Douglas Wagner Franco
Support type: Research Projects - Thematic Grants