The dimeric cyclometalated complexes [Pd-2{kappa C-2,N-C6H4CH2CH2C(R)(Me)NH2-2}(2)(mu-Cl)(2)] (R = Me (1a), H (1b)) are prepared by reacting 1,1-dimethyl-3-phenylpropylammonium or 1- methyl-3-phenylpropylammonium triflate with Pd(OAc)(2) in a 1:1 molar ratio and subsequent treatment with excess NaCl. The mononuclear derivatives [Pd{kappa C-2,N-C6H4CH2CH2C(R)(Me)NH2-2}Cl(L)] (L = PPh3, R = Me (3a), H (3b); L = 4-picoline (4-pic), R = Me (4a), H (4b)) were prepared from la,b by splitting the chloro bridges with the neutral ligands L. A conformational analysis of the mononuclear palladacycles in solution has been carried out. Insertion of CO takes place into the Pd-C bond of complexes la,b, affording Pd(0) and the tetrahydro-benzazepinone Sa or 513, which possesses potential pharmacological interest. Additionally, the triflate salt A or B undergoes catalytic carbonylation with CO to afford the corresponding N,N'-dialkylurea, using Pd(OAc)(2)/Cu(OAc)(2), in boiling acetonitrile. The crystal structures of 3a.(1)/2H2O, 3b, 4b center dot CHCl3, and 5a were determined by X-ray diffraction studies.