Reaction of [Ru(C 6H 4PPh 2) 2(Ph 2PC 6H 4AlMe(THF))H] with CO results in clean conversion to the Ru-Al heterobimetallic complex [Ru(AlMePhos)(CO) 3] (1), where AlMePhos is the novel P-Al(Me)-P pincer ligand (o-Ph 2PC 6H 4) 2AlMe. Under photolytic conditions, 1 reacts with H 2to give [Ru(AlMePhos)(CO) 2(μ-H)H] (2) that is characterized by multinuclear NMR and IR spectroscopies. DFT calculations indicate that 2 features one terminal and one bridging hydride that are respectively anti and syn to the AlMe group. Calculations also define a mechanism for H 2addition to 1 and predict facile hydride exchange in 2 that is also observed experimentally. Reaction of 1 with B(C 6F 5) 3results in Me abstraction to form the ion pair [Ru(AlPhos)(CO) 3][MeB(C 6F 5) 3] (4) featuring a cationic [(o-Ph 2PC 6H 4) 2Al] +ligand, [AlPhos] +. The Ru-Al distance in 4 (2.5334(16) Å) is significantly shorter than that in 1 (2.6578(6) Å), consistent with an enhanced Lewis acidity of the [AlPhos] +ligand. This is corroborated by a blue shift in both the observed and computed ν COstretching frequencies upon Me abstraction. Electronic structure analyses (QTAIM and EDA-ETS) comparing 1, 4, and the previously reported [Ru(ZnPhos)(CO) 3] analogue (ZnPhos = (o-Ph 2PC 6H 4) 2Zn) indicate that the Lewis acidity of these pincer ligands increases along the series ZnPhos < AlMePhos < [AlPhos] +. copy; 2022 American Chemical Society.