Mononuclear palladium hydroxo complexes of the type [Pd(N-N)(C6F5)(OH)] [(N-N = 2,2'-bipyridine (bipy), 4,4'-dimethyl-2,2'-bipyridine (Me(2)bipy), 1,10-phenanthroline (phen), or N,N,N',N'-tetramethylethylenediamine (tmeda)] have been prepared by reaction of [Pd(N-N)(C6F5)(acetone)]ClO4 with KOH in methanol. These hydroxo complexes react, in methanol, with CO (1 atm, room temperature) to yield the corresponding methoxycarbonyl complexes [Pd(N-N)(C6F5)(CO2Me)]. Similar alkoxycarbonyl complexes [Pd(N-N)(C6F5)(CO2R)] (N-N = bis(3,5-dimethylpyrazol-1-yl)methane); R = Me, Et, or Pr-i) are obtained when [Pd(N-N)(C6F5)Cl] is treated with KOH in the corresponding alcohol ROH and CO is bubbled through the solution. The reactions of [Pd(N-N)(C6F5)(OH)] (N-N = bipy or Me2bipy) with CO2, in tetrahydrofuran, lead to the formation of the binuclear carbonate complexes [(N-N)(C6F5)-Pd(mu-eta(2)- CO3)Pd(C6F5)(N-N)]. Complexes [Pd(N-N)(C6F5)(OH)] react in alcohol with PhNCS to yield the corresponding N-phenyl-O-alkylthiocarbamate complexes [Pd(N-N)(C6F5){SC(OR)NPh}]. Similarly, the reaction of [Pd(biPY)(C6F5)(OH)] with PhNCO in methanol gives the N-phenyl-O-methylcarbamate complex [Pd(bipy)(C6F5){NPhC(O)OR}]. The reactions of [(N-N)Pd(C6F5)(OH)] with PhNCS in the presence of Et2NH yield the corresponding thioureidometal complexes [Pd(N-N)(C6F5){NPhCSNR2}]. The crystal structures of [Pd(tmeda)(C6F5)(CO2Me)], [Pd-2(Me(2)bipy)(2)(C6F5)(2)-(mu-eta(2)-CO3)].2CH(2)Cl(2), and [Pd(tmeda)(C6F5){SC(OMe)NPh}] have been determined.