  Knowledge of the relative stabilities of alane (AlH3) complexes with electron
donors is essential for identifying hydrogen storage materials for vehicular
applications that can be regenerated by off-board methods; however, almost no
thermodynamic data are available to make this assessment. To fill this gap, we
employed the G4(MP2) method to determine heats of formation, entropies, and
Gibbs free energies of formation for thirty-eight alane complexes with NH3-nRn
(R = Me, Et; n = 0-3), pyridine, pyrazine, triethylenediamine (TEDA),
quinuclidine, OH2-nRn (R = Me, Et; n = 0-2), dioxane, and tetrahydrofuran
(THF). Monomer, bis, and selected dimer complex geometries were considered.
Using these data, we computed the thermodynamics of the key formation and
dehydrogenation reactions that would occur during hydrogen delivery and alane
regeneration, from which trends in complex stability were identified. These
predictions were tested by synthesizing six amine-alane complexes involving
trimethylamine, triethylamine, dimethylethylamine, TEDA, quinuclidine, and
hexamine, and obtaining upper limits of delta G for their formation from
metallic aluminum. Combining these computational and experimental results, we
establish a criterion for complex stability relevant to hydrogen storage that
can be used to assess potential ligands prior to attempting synthesis of the
alane complex. Based on this, we conclude that only a subset of the tertiary
amine complexes considered and none of the ether complexes can be successfully
formed by direct reaction with aluminum and regenerated in an alane-based
hydrogen storage system.

Chemical Physics;Materials Science;Atomic and Molecular Clusters