Molecular near zero oxidation state clusters of metals are of interest as fuel additives. In this work high heating rate decomposition of the Al(I) tetrameric cluster, [AlBr(NEt3)](4) (Et = C2H5), was studied at heating rates of up to 5 x 10(5) K/s using temperature-jump time-of-flight mass spectrometry (T-jump TOFMS). Gas phase Al and AIH(X) species were rapidly released during decomposition of the cluster, at similar to 220 degrees C. The activation energy for decomposition was determined to be similar to 43 kJ/mol. Addition of an oxidizer, KIO4, increased Al, AlO, and HBr signal intensities, showing direct oxidation of the cluster with gas phase oxygen. (C) 2016 Elsevier B.V. All rights reserved.