Insertion Reactions into Pd−O and Pd−N Bonds: Preparation of Alkoxycarbonyl, Carbonato, Carbamato, Thiocarbamate, and Thioureide Complexes of Palladium(II)

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Abstract
Mononuclear palladium hydroxo complexes of the type [Pd(N−N)(C6F5)(OH)] [(N−N = 2,2‘-bipyridine (bipy), 4,4‘-dimethyl-2,2‘-bipyridine (Me2bipy), 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 iPr) 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(μ-η2-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)], [Pd2(Me2bipy)2(C6F5)2(μ-η2-CO3)]·2CH2Cl2, and [Pd(tmeda)(C6F5){SC(OMe)NPh}] have been determined.

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