Threshold photoelectron spectroscopy of trimethylborane and its pyrolysis products

Abstract

Trimethylborane (TMB) and its chemistry upon pyrolysis have been investigated by threshold photoelectron spectroscopy. TMB shows an unstructured spectrum and its adiabatic ionization energy (IE_ad) has been determined to be 9.93 ± 0.1 eV. Dissociative photoionization induces a methyl radical loss in TMB and the barrier to dissociation in the cation is measured to be 0.65 ± 0.1 eV. Upon pyrolysis methane loss dominates, leading to C₂H₅B, which can exist in five different isomeric structures. Quantum chemical calculations were used to investigate possible methane loss mechanisms as well as the isomerization pathways on the C₂H₅B potential energy surface. Through isomer-selective photoion mass-selected threshold photoelectron spectroscopy (ms-TPES) the two isomers CH₃BCH₂ and CH₃CHBH were identified by their ms-TPE spectra and IE_ad values of 8.55 ± 0.02 eV and 8.73 ± 0.02 eV were determined, respectively. A second channel leading to the loss of ethene from TMB forms CH₂BH, which exhibits an IE_ad value of 9.37 ± 0.03 eV. The reaction mechanism in the literature needs to be expanded by an additional methane loss from the intermediately formed ethyl methyl borane.