Activation of water and of dioxygen by a bis(diphenylphosphinopropyl)silyl(biPSi) complex of ruthenium(II): Formation of bis(diphenylphosphinopropyl)siloxo cage complexes. Concomitant oxygen atom insertion into a silicon-carbon bond

The coordinatively saturated hydrido complex RuH(biPSi)(CO)(2) (1), biPSi = -Si(Me)(CH2CH2CH2PPh2)(2), reacts slowly with either water/piperidine or d ioxygen to afford the novel "anchored" siloxo complexes RuH[OSiMe(CH2CH2CH2 PPh2)(2)](CO)L (3, L = CO) and RuH[OSi(OMe)(CH2CH2CH2PPh2)(2)](CO)L (6, L = CO), respectively, which undergo carbonyl displacement to yield, analogues in which L = P(OMe)(3) that are crystalline (5 or 7, respectively) and for which anti stereochemistry (i.e., H at Ru vs Me or OMe at Si) has been ide ntified by using X-ray crystallography (i.e., products 5-a, 7-a respectivel y). Complex 1 catalyzes autoxidation of cyclohexene (mainly to cyclohexenon e, cyclohexenol: TTO approximate to 300, 4 h).