cis-[Pd(ONO(2))(2)(PPh(3))(2)] (1) reacts under mild conditions with CO in methanol (MeOH) in the presence of pyridine (py), yielding trans-[Pd(COOMe)(ONO(2))(PPh(3))(2)] (1a). The use of NEt(3) instead of py leads to a mixture of 1a, trans-[Pd(COOMe)(2)(PPh(3))(2)] (2), and [Pd(CO)(PPh(3))(3)]. Pure 2 was prepared by reacting cis-[Pd(OTs)(2)(PPh(3))(2)] with CO in MeOH and subsequently adding NEt(3). The nitro complex trans-[Pd(COOMe)(NO(2))(PPh(3))(2)] (3a) was prepared by reacting trans-[Pd(COOMe)Cl(PPh(3))(2)] with AgNO(2) or with AgOTs and NaNO(2). New syntheses for 1 and trans-[Pd(NO(2))(2)(PPh(3))(2)] (3) are also reported. All complexes have been characterized by IR and (1)H and (31)P{(1)H} NMR spectroscopies. Complexes 1 and 2 exchange irreversibly and quantitatively one nitrato with one carbomethoxy ligand, yielding 1a. 2 in CD(2)Cl(2) at 40 degrees C decomposes with the formation of dimethyl carbonate (DMC), whereas under 4 atm of CO, DMC and dimethyl oxalate (DMO) are formed, ca. 12% each; in the presence of PPh(3) and in the absence of CO, decomposition occurs at 60 degrees C with the formation of DMC only, suggesting that decarbonylation involves a five-coordinate intermediate or predissociation of a PPh(3) ligand. The oxidative carbonylation of MeOH does not occur when using NaNO(2) or NaNO(3) as the oxidant and 1, 1a, 3, or 3a as the catalyst precursor. On the contrary, when using benzoquinone (BQ) as the oxidant, these complexes, 2, or [Pd(COOMe)(2-n)X(n)(PPh(3))(2)] (X = Cl, OAc, OTs; n = 1, 2) promote selective catalysis to DMO. After catalysis the precursors are transformed into [Pd(BQ)(PPh(3))(2)](2).H(2)BQ, [Pd(CO)(PPh(3))](3) and [Pd(CO)(PPh(3))(3)]. Also the last with BQ gives selective catalysis to DMO. The solid-state structures of 1.CH(2)Cl(2) and 1a have been determined by means of single-crystal X-ray diffraction.