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Methyl iodide, benzyl bromide, and benzyl iodide react with PdMePh(bpy) (bpy = 2,2'-\udbipyridyl) in acetone at 0 °C to form the isolable fuc-triorganopalladium(1V) complexes PdIMez-\udPh(bpy) (3) and PdXMePh(CHzPh)(bpy) [X = Br (4), I (5)l. Complex 3 occurs as a mixture\udof isomers in a cu. 1:l ratio, involving the phenyl group in a position trans either to bpy (3a)\udor to iodine (3b), while complexes 4 and 5 are obtained as one isomer which, most likely, has\udthe benzyl group trans to the halogen. The selectivity of reductive elimination from a metal\udbonded to three different groups could be studied for the first time. The complexes undergo\udfacile reductive elimination in (CD3)zCO at 0 °C, in which PdIMezPh(bpy) gives a mixture of\udethane and toluene in a 4:l molar ratio together with PdIR(bpy) (R = Ph, Me), whereas PdXMePh-\ud(CHzPh)(bpy) (X = Br, I) gives exclusively toluene and PdX(CHZPh)(bpy). The analogous\udtmeda complex, PdMePh(tmeda) (tmeda = N,N,N',N'-tetramethylethylenediamine), reacts\udmore slowly than PdMePh(bpy1 with alkyl halides. Methyl iodide reacts cleanly with PdMePh-\ud(tmeda) at 0 °C in (CD3)zC0 to form ethane and PdIPh(tmeda), but the expected palladium(1V)\udintermediate could not be detected. Benzyl bromide does not react with PdMePh(tmeda)\udbelow the decomposition temperature of the latter under these conditions (50 °C, (CD&CO),\udwhile benzyl iodide reacts at 40 °C to give a complicated mixture of products of which ethane,\uddiphenylmethane, ethylbenzene, toluene, and PdIR(tmeda) (R = Me, Ph) could be identified.\udBenzyl iodide reacts with PdMez(tmeda) at -30 °C in (CD3)zCO to form PdIMez(CHzPh)-\ud(tmeda), for which lH NMR spectra showed the benzyl group to be trans to one of the N-donor\udatoms. However, PdIMez(CHzPh) (tmeda) is unstable and undergoes facile reductive elimination\udto form ethane and PdI(CH2Ph)(tmeda). Transfer of alkyl and halide groups from palladium-\ud(IV) to palladium(I1) complexes occurs in (CD3)zCO at low temperatures for several reaction\udsystems in which the resulting palladium(1V) complex is known to be more stable than the\udpalladium(1V) reagent. There is a strong preference for benzyl group transfer from PdXMePh-\ud(CHZPh)(bpy) to PdMez(L2) (X = Br, I; LZ = bpy, phen). The mechanism of the transfer\udreactions is discussed in terms of the mechanism suggested earlier for alkyl halide transfer from\udpalladium(1V) to platinum(II), palladium(I1) to palladium(O), cobalt(II1) to cobalt(I), and\udrhodium(II1) to rhodium(1). These reaction systems involve nucleophilic attack by the lower\udoxidation state reagent at an alkyl group attached to the higher oxidation state reagent

organometallics

Phenylpalladium(IV) Chemistry: Selectivity in Reductive Elimination from Palladium(IV) Complexes and Alkyl Halide Transfer from Palladium(IV) to Palladium(II)