Association Reactions of Manganese, Iron, and Ruthenium with Nitric Oxide
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Abstract
The gas-phase association reactions of ground-state manganese, iron, and ruthenium atoms with nitric oxide are reported. The transition metal atoms were produced by the 248 nm photodissociation of 2-methylcyclopentadienylmanganese tricarbonyl, ferrocene, and ruthenocene. Detection of these transition metal atoms was by laser-induced fluorescence. Manganese was found to be the least reactive with nitric oxide of the transition metals in this work. The limiting low-pressure third-order rate constant, ko, of Mn + NO + Ar can be expressed as (9.5 ± 2.5) × 10-33 exp[−1.5 ± 0.4 kcal mol-1/(RT)] cm6 molecule-2 s-1. ko for Fe + NO + N2 at 296 K is (2.3 ± 0.5) × 10-32 cm6 molecule-2 s-1; this reaction is independent of temperature over the range 296−622 K. Ruthenium was found to be the most reactive toward NO. In Ar buffer, ko = (7.3 ± 1.0) × 10-30 cm6 molecule-2 s-1 and the limiting high-pressure rate constant k∞ = (3.8 ± 0.8) × 10-11 cm3 molecule-1 s-1 for a fixed broadening factor of Fc = 0.6. The uncertainties here represent precision. Recent density functional theory calculations on transition metal mononitrosyls were combined with RRKM calculations to estimate the binding energies of the Mn−NO and Fe−NO adducts.
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