Influence of ligands on the fac (hv)reversible arrow mer isomerization in [RuCl3(NO)(P-P)] complexes, [P-P (Delta)= R2P(CH2)(n)PR2 (n=1-3) and R2P(CH2)POR2, PR2-CH=CH-PR2, R=Ph and (C6H11)(2)P-(CH2)(2)-P(C6H11)(2)]

摘要

[RuCl3(NO)(P-P)], [P-P = R2P(CH2)(n)PR2 (n = 1-3) and R2P(CH2)POR2, PR2-CH=CH-PR2, R = Ph and (C6H11)(2)P-(CH2)(2)-P(C6H11 )(2)] were obtained and characterized by P-31 {H-1} NMR, IR spectroscopies and cyclic voltammetry. The structures of fac-[RuCl3(NO)(P-P)], P-P = dppm (1), dppe (2), c-dppen (3) and dppp (4), mer-[RuCl3(NO)(dcpe)] (6a) and mer-[RuCl3(NO)(dppmO)] (7) have been determined by X-ray diffraction. Photochemical isomerization of fac- to mer-[RUCl3(NO)(P-P)] was observed under white light in a CH2Cl2 solution and in solid state. The isomerization processes were followed by IR and P-31 {H-1} spectra. The mer-[RUCl3((NO)-N-15)- (dppb)] isomer was used for the definition of the phosphorus atoms in the structure of the complex in solution. The electrochemical study shows that the oxidation/reduction processes observed in these complexes are dependent on both the isomer (fac or mer) and the solvent. In CH2Cl2, the NO+ reduction potentials are less negative for the mer-isomers than for the fac ones, while in CH3CN solvent these potentials are, in general, very close for both isomers. (c) 2005 Elsevier B.V. All rights reserved.