Co(+)-assisted decomposition of h6-acetone and d6-acetone: acquisition of reaction rate constants and dynamics of the dissociative mechanism.

Reaction rate constants have been acquired for the gaseous unimolecular decomposition reaction of the Co(+)(OC(CH(3))(2)) cluster ion and its deuterium labeled analog. Each rate constant is measured at a well resolved cluster internal energy within the range 12,300-16,100 cm(-1). The weighted, averaged kinetic isotope effect (KIE), k(H)/k(D) = 1.54 ± 0.05, is about three times smaller than the KIE measured for the rate-determining rate constants in the similar Ni(+)(OC(CH(3))(2)) decomposition reaction. These reactions likely follow the same oxidative addition-reductive elimination mechanism. Thus, this unexpected change in the KIE magnitudes is not due to differences in the dissociative reaction coordinates. Rather, we propose that the unique dissociation dynamics of these two similar systems is due to differences in the low-lying electronic structure of each transition metal ion.

Reaction rate constants and mechanistic detail of the Ni+ + butanone reaction.

The unimolecular decomposition kinetics of the jet-cooled Ni(+)-butanone cluster ion has been monitored over a range of internal energies (16000-18800 cm⁻¹). First-order rate constants are acquired for the precursor ion dissociation into three product channels. The temporal growth of each fragment ion is selectively monitored in a custom instrument and yields similar valued rate constants at a common ion internal energy. The decomposition reaction is proposed to proceed along two parallel reaction coordinates. Each dissociative pathway is rate-limited by the initial Ni(+) oxidative addition into either the C-CH3 or C-C2H5 σ-bond in the butanone molecule. Ratios of integrated product ion intensities as well as the measured rate constants are used to determine values for each σ-bond activation rate constant. The lowest energy measurement presented in this study occurs when the binary complex ion possesses an internal energy of 16000 cm⁻¹. Under this condition, the Ni(+) assisted decomposition of the butanone molecule is rate limited by k(act)(C-C2H5) = (0.92 ± 0.08) × 105 s⁻¹ and k(act)(C-CH3) = (0.37 ± 0.03) × 105 s⁻¹. The relative magnitudes of the two rate constants reflect the greater probability for reaction to occur along the C-C2H5 σ-bond insertion pathway, consistent with thermodynamic arguments. DFT calculations at the B3LYP/6-311++G(d,p) level of theory suggest the most likely geometries and relative energies of the reactants, intermediates, and products.

Low-energy reaction rate constants for the Ni+-assisted decomposition of acetaldehyde: observation of C-H and C-C activation.

Rate constants for the low-energy Ni(+)-assisted dissociative reaction of acetaldehyde have been measured under jet-cooled conditions in the gas phase. The rate constants are acquired through monitoring the time dependence of fragment Ni(+)CO formation. The decomposition of the precursor Ni(+)-acetaldehyde cluster ion proceeds via consecutive, parallel reaction coordinates that originate with the Ni(+)-assisted cleavage of either a C-C or an aldehyde C-H bond. The energies used to initiate these reactions are well below that required to cleave sigma-bonds in the isolated acetaldehyde molecule. Direct measurement of the reaction kinetics over a range of energies indicates that the rate-limiting step in the dissociative mechanism changes at cluster ion internal energies = 17,200 +/- 400 cm(-1). Arguments are presented that this energy marks the closure of the dissociative coordinate that initiates with C-H sigma-bond activation and thus provides a measure of the activation energy of this dissociative pathway.

Rate-limiting step in the low-energy unimolecular decomposition reaction of Ni+* acetone into Ni+CO + ethane.

Rate constants for the low-energy Ni(+)-assisted C-C bond cleavage reaction of deuterium-labeled acetone have been acquired under jet-cooled conditions in the gas phase. The energies used to initiate the dissociative reactions of the precursor complex ion Ni(+)(d(6)-Ac) are well below that required to cleave C-C sigma-bonds in isolated organic molecules. The rate constants are compared to those acquired previously for the lighter Ni(+)(h(6)-Ac) isotope and result in a substantial kinetic isotope effect (k(H)/k(D) approximately 5.5). Arguments are made that implicate isomerization leading to C-C bond coupling as the rate-limiting step (not C-C sigma-bond activation) in the dissociative reaction.

The low-energy unimolecular reaction rate constants for the gas phase, Ni+-mediated dissociation of the C-C sigma bond in acetone.

The time dependence of the gaseous unimolecular decomposition of the jet-cooled adduct ion, Ni+-OC(CH3)2, was monitored through selective detection of the Ni+CO fragment ion. Various resolved amounts of energy in the range 15600-18800 cm(-1) were supplied to initiate the dissociation reaction through absorption of laser photons by the title molecular complex. First-order rate constants, k(E), ranged from 113000 to 55000 s(-1) and decreased with decreasing amounts of internal excitation. The energy used to initiate the reaction is well below that required to fragment C-C sigma bonds and indicates the necessity of the Ni+ cation to induce bond activation and fragmentation. These measurements are carried out in a unique apparatus and represent the first direct kinetic study of such catalytic type reactions.