Journal of the American Chemical Society, Vol.124, No.20, 5843-5849, 2002
Dissociation kinetics of energy-selected Cp2Mn+ ions studied by threshold photoelectron-photoion coincidence spectroscopy
Threshold photoelectron-photoion coincidence spectroscopy has been used to investigate the dissociation kinetics of the manganocene ion, Cp2Mn+ (Cp = eta(5)-cyclopentadienyl). The Cp loss reaction was found to be extremely slow over a large ion internal energy range. By simulating the measured asymmetric time-of-flight peak shapes and breakdown diagram, the 0 K thermochemical dissociation limit for CpMn+ production was determined to be 9.5 +/- 50.15 eV. A CpMn+-Cp bond energy of 3.43 eV was obtained by combining this CpMn+ + Cp dissociation limit with the Cp2Mn adiabatic ionization energy of 6.12 +/-0.07 eV. Combining the measured onset with known heats of formation of Cp and Mn+, the CpMn+ bond energy was determined to be 3.38 +/- 0.15 eV. These results lead to 298 K heats of formation Of Cp2Mn+ and CpMn+ of 863 +/- 7 and 935 +/- 16 kJ/mol, respectively. Finally, by combining these results with a previous measurement of the CpMn(CO)(3) --> CpMn+ + 3CO + e(-) dissociation limit, we arrive at a new value for Delta(f)Hdegrees(298K)(CpMn(CO)(3)) of -424 +/- 17 kJ/mol.