The palladium complexes
[Pd(PPh3)(aryl)LOR]
(aryl = Ph, p-tolyl;
LOR¯ =
[(C5H5)Co{P(OR)2O}3]¯,
R = Me, Pri) have been prepared by reaction of
[PdI(aryl)(tmeda)] (tmeda =
N,N,N′,N′-tetramethyl-ethylenediamine)
with the silver salts AgLOR in the presence of
PPh3. The complexes
[Pd(PPh3)(aryl)LOR]
rapidly and reversibly insert carbon monoxide to yield the aroyl palladium
complexes [Pd(PPh3)(C(O)-
p-tolyl)LOR] (R = Me,
Pri ). The palladium iodide complex
[PdI(p-tolyl)(tmeda)] and the silver salt
AgLOR in the absence of PPh3 form
an unusual adduct
[(p-tolyl)(tmeda)Pd(µ2-I)AgLOMe]
that contains a short silver-iodide bond (Ag-I 2 · 703(1) Å). The
silver-palladium bond is bridged by iodine (Pd-Ag 3 · 011(1), Pd{I
2 · 5934(9) Å) and the silver atom is coordinated by the
tris-chelating oxygen ligand LOMe.
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