Salt metathesis has been exploited in the synthesis of M-Al bonds, stabilized by a variety of chelating N-donor substituents at aluminium and including the first examples of such systems featuring ancillary guanidinato frameworks. Importantly, this synthetic approach can be extended to the synthesis of σ-alane complexes through the use of hydride-containing transition metal nucleophiles. Cp'Mn(CO)(2)-[H(Cl)Al{(N(i)Pr)(2)CPh}] synthesized via this route features an alane ligand bound in a more 'side-on' fashion than other alane complexes, although DFT calculations imply that the potential energy surface associated with variation in the Mn-H-Al angle is a very soft one.