The desorption of dihydrogen from magnesium(II) hydride, MgH2 (containing 7.6 wt% H), is reversible. MgH2 therefore holds promise as a hydrogen storage material in devices powered by fuel cells. We believed that dimeric magnesium(I) dimers (LMgMgL, L=β-diketiminate) could find use as soluble models to aid the study of the mechanisms and/or kinetics of the hydrogenation of magnesium and its alloys. Here, we show that LMgMgL can be readily hydrogenated to yield LMg(µ-H)2MgL by treatment with aluminium(III) hydride complexes. In one case, hydrogenation was reversed by treating LMg(µ-H)2MgL with potassium metal. The hydrogenation by-products are the first thermally stable, neutral aluminium(II) hydride complexes to be produced, one of which, [{(IPr)(H)2Al}2] (IPr=:C[{(C6H3-i-Pr(2)-2,6)NCH}2]), is an N-heterocyclic carbene adduct of the elusive parent dialane4 (Al2H4). A computational analysis of this compound is presented.