MATRIX PHOTOCHEMISTRY OF RU(CO)(2)(PME(3))(2)H-2 AND RU(CO)(3)(PME(3))(2) - FORMATION OF O)(2)(PME(3))(2)CENTER-DOT-CENTER-DOT-CENTER-DOT-S(S=AR, CH4, XE)
Rj. Mawby et al., MATRIX PHOTOCHEMISTRY OF RU(CO)(2)(PME(3))(2)H-2 AND RU(CO)(3)(PME(3))(2) - FORMATION OF O)(2)(PME(3))(2)CENTER-DOT-CENTER-DOT-CENTER-DOT-S(S=AR, CH4, XE), Organometallics, 14(7), 1995, pp. 3268-3274
The photochemical reactions of Ru(CO)(2)(PMe(3))(2)H-2 (I) and Ru(CO)(
3)(PMe(3))(2) (II) have been studied in low-temperature Ar, CH4, and X
e matrices by IR and UV-visible spectroscopy. UV photolysis (lambda >
200 nm) of I and II results in the formation of Ru(CO)(2)(PMe(3))(2)..
.S (S = matrix host), which shows a distinctive UV-visible absorption
band with lambda(max) dependent on S (Ar, 423 nm; CH4, 385 nm; Xe, 352
nm). The reactions are partially reversed by irradiation with lambda
> 360 nm. (CO)-C-13 isotopic labeling studies and trapping experiments
in H-2-doped and N-2-doped Ar and CO matrices prove that the intermed
iate is a dicarbonyl species. In the structure proposed for RU(CO)(2)(
PMe(3))(2)...S, the C-Ru-C bond angle must exceed 130 degrees.