The complex [HgR2] (R = C6(NO2)2-2,6-(OMe)3-3,4,5-C1 (2)), obtained by thermal decomposition of [Hg(O2CR)2] (1), reacts with Q2[Pd2Cl4(μ-Cl)2] to give [Hg(R)Cl] (3) and Q2[Pd(R)Cl(μ-Cl)]2 (Q = (PhCH2)Ph3P (4a), Me4N (4b)), which react (i) with Tl(acac) (1:2, acac = acetylacetonate) to give Q[Pd(R)Cl(O,O-acac)] (Q = (PhCH2)Ph3P (5a), Me4N (5b)) or (ii) with AgClO4 (1:2) to give [Pd(κ3-R)Cl] (κ3-R = κ3-C6(NO2)2-2,6-(OMe)3-3,4,5-C1,O,O‘ (6)), which can also be obtained by reacting 5a with HBF4. Complex 6 reacts with p-toluidine (1:1, L) to give [Pd(R)(μ-Cl)L]2 (7). Complex 5b decomposes in a mixture of acetone/water to give [Pd(κ2-R)(O,O-acac)] (κ2-R = κ2-C6(NO2)2-2,6-(OMe)3-3,4,5-C1,O (8)), which reacts (i) with neutral monodentate ligands to give [Pd(R)(O,O-acac)L] (L = PPh3 (9), pyridine (py) (10), tetrahydrothiophene (11)), (ii) with bis(diphenylphosphino)methane (dppm) to give a complex that readily oxidizes to give [Pd(R)(O,O-acac)(dppmO)] (dppmO = monoxide of bis(diphenylphosphino)methane (12)), (iii) with 1,10-phenanthroline (phen) to give [Pd(R)(C-acac)(phen)] (13), and (iv) with protonated ligands (HL)ClO4 to give 10 (L = py) or cis-[Pd(R)(H2O)2(PPh3)]·H2O (L = PPh3 (14)). Trifluoromethanesulfonic acid (HOSO2CF3) reacts with 9 and PPh3 or with 13 to give trans-[Pd(R)(OSO2CF3)(PPh3)2] (15) or [Pd(R)(OSO2CF3)(phen)] (16), respectively. The X-ray crystal structures of 7·2CH 2 Cl 2 , 8, 10, and 14·H 2 O have been determined.

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