The complexes cis, trans, cis-[Rh(H)(2)(PPh3)(2)(NH2CH2Ph)(2)]PF6 (1) and cis-[Rh(PPh3)(2)(NH2CH2Ph)(2)]PF6 (2) are characterized by X-ray crystallography; the structures are maintained in CH2Cl2 where the species are in equilibrium under H-2. In MeOH and in acetone, loss of amine and/or H-2 can occur. Traces of 1 and 2 are present after a Rh-catalyzed H-2-hydrogenation of PhCH=NCH2Ph in MeOH, where the amine is generated by hydrolysis of the imine substrate through adventitious water. The findings are relevant to catalyst poisoning in the catalytic process.