A study of the mechanism of iron carbonyl-catalyzed isomerization of 1-pentene in the gas phase using time-resolved infrared spectroscopy

After generation of Fe(CO)(3) by 308-nm gas-phase photolysis of Fe(CO)(5), 1-pentene adds to Fe-(CO)(3) to form Fe(CO)(3)(eta(2)-1-pentene) with a bim olecular rate constant of k(a) = (4 +/- 1) x 10(-10) cm(3) molecule(-1) (-1 ). Rapid beta-hydrogen transfer, by way of intramolecular C-H bond insertio n to form HFe(CO)(3)(eta(3)-C5H9), follows rate-limiting addition of 1-pent ene to Fe(CO)(3) and proceeds with a lower bound of k(1) greater than or eq ual to 10(9) s(-1) Under experimental conditions, HFe(CO)(3)(eta(3)-C5H9) d ecays on a millisecond time scale with concurrent formation of Fe(CO)(3)(et a(2)-pentene)(2) by addition of 1-pentene to an Fe(CO)(3)(eta(2)-pentene) i ntermediate. It is Fe(CO)(3)(eta(2)-pentene) that is in equilibrium with HF e(CO)(3)(eta(3)-C5H9) that adds 1-pentene to form Fe(CO)(3)(eta(2)-pentene) , which may contain an isomerized olefin. CO may add to Fe(CO)(3)(eta(2)-pe ntene) that is in equilibrium with HFe(CO)(3)(eta(3)-C5H9) to form Fe(CO)(4 )(eta(2)-pentene). Fe(CO)(4)(eta(2)-pentene) remains stable on the time sca le of catalytic turnover and its formation serves as a termination pathway for thermal catalysis. This system is compared to the analogous propene sys tem (Long, G. T.; Wang, W.; Weitz, E. J. Am. Chern. Sec. 1995, 117, 12810). The major difference in behavior between these systems is attributed to an similar to 3 orders of magnitude shift in the equilibrium constant toward HFe(CO)(3)(pi-allyl) relative to Fe(CO)(3)(olefin) when the starting olefin is l-pentene instead of propene. The magnitude of the equilibrium constant s indicates that there is an similar to 4 kcal mol(-1) greater enthalpy dif ference between HFe(CO)(3)(eta(3)-C5H9) and Fe(CO)(3)(eta(2)-pentene) than for the corresponding species in the propene system.