Reaction of the dimeric species [(eta(3)-Ind) Pd(A-Cl)] 2 (1) (Ind) indenyl) with NEt3 gives the complex (eta(3-5)-Ind) Pd(NEt3) Cl (3), whereas the analogous reactions with BnNH2 (Bn) PhCH2) or pyridine (py) afford the complexes trans-L2Pd(eta(1)-Ind) Cl ( L) BnNH2 ( 4), py ( 5)). Similarly, the one-pot reaction of 1 with a mixture of BnNH2 and the phosphine ligands PR3' gives the mixed-ligand, amino and phosphine species (PR3)( BnNH2) Pd(eta(1)-Ind) Cl (R = Cy (6a), Ph (6b)); the latter complexes can also be prepared by addition of BnNH2 to (A(3-5)-Ind) Pd(PR3) Cl (R) Cy (2a), Ph (2b)). Complexes 6 undergo a gradual decomposition in solution to generate the dinuclear Pd-I compounds (mu,eta(3)-Ind)(mu-Cl) Pd-2(PR3)(2) (R = Cy (7a), Ph (7b)) and the Pd-II compounds (BnNH2)(PR3) PdCl2 (R) Cy (8a), Ph (8b)), along with 1,1'-biindene. The formation of 7 is proposed to proceed by a comproportionation reaction between in situ-generated Pd-II and Pd-0 intermediates. Interestingly, the reverse of this reaction, disproportionation, also occurs spontaneously to give 2. All new compounds have been characterized by NMR spectroscopy and, in the case of 3, 4, 5, 6a, 7a, 7b, and 8a, by X-ray crystallography.