| Popis: |
[n-Bu4N][[Ph3SiO]2VO2] reacts with H2O2 to yield an oxoperoxo complex which crystallizes as a mixed-crystal compound, [P(C6H5)4][[(C6H5)3 SiO]2VO2]x[[(C6H5)3 SiO]2VO(O2)](1-x), 1(x = 0.57). It has been characterized by elemental analysis and spectroscopy (51V NMR, UV-visible and IR). The X-ray structure analysis reveals the presence of two interrelated anions: [[Ph3SiO]2VVO2]-, 1a, and [[Ph3SiO]2VVO(O2)]-, 1b with a cisoid geometry of the [VO(O2)]+ moiety. The two structures differ only slightly: anion 1a exhibits unusual tetrahedral coordination around the vanadium centre found in the precursor, whereas the geometry at the metal ion in 1b can be described as a trapezoidal pyramid. Steric constraints due to Ph3SiO- ligands and PPh4+ cations are responsible for this geometry. The reactivity of 1 in the C-C bond cleavage of 2-methylcyclohexanone under anaerobic conditions has been studied. The results suggest that peroxygen species are involved in the oxidative cleavage of C-C bonds of cycloalkanones. |
