The photochemistry of Ru(CO)3(dmpe) (II; dmpe = Me2PCH2CH2PMe2), has been studied by matrix isolation at 12 K and laser flash photolysis with UV - visible and IR detection at ambient temperature. UV photolysis in a matrix results in the formation of Ru(CO)2(dmpe)·S (S = matrix host), which shows two distinctive UV-visible bands with λmax dependent on S (Ar, 410, 600 nm; CH4, 357, 500 nm; Xe, 345, 457 nm). These shifts are the largest yet observed for any matrix-solvated species. The reactions are partially reversed by long-wavelength (λ > 420 nm) photolysis. Laser flash photolysis in heptane solution (λexe = 266 or 308 nm) with IR or UV - visible detection reveals that Ru(CO)2(dmpe)·heptane is a short-lived fragment which decays rapidly by reaction with Ru(CO)3(dmpe) (k2 ≈ 1 × 109 dm3 mol-1 s-1). Steady-state photolysis of II in heptane in the presence of hydrogen or triethylsilane yields Ru(CO)2(dmpe)H2 and Ru(CO)2(dmpe)(SiEt3)H, respectively, which have been characterized by IR and NMR spectroscopy.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry