Synthesis and characterization of neutral and cationic organopalladiumcomplexes containing an imidazolylphosphine P,N-ligand and their carbonylationreactions
2001
Several new neutral and cationic organopalladium complexes containing
a P–N chelating ligand, 2-(diisopropylphosphinomethyl)-1-methylimidazole,
have been synthesized and characterized. The neutral complexes [PdPh(I)(P–N)] 1 and [PdMe(I)(P–N)] 2
have been synthesized by oxidative addition of PhI and MeI, respectively to
Pd(dba)2 (dba = dibenzylideneacetone) in the
presence of the P–N ligand. The cationic complexes [PdPh(PPh3)(P–N)]BF4 3 and [PdMe(PPh3)(P–N)]BF4 4 were obtained by adding
an acetone solution of AgBF4/PPh3 to the corresponding
neutral precursors 1 and 2, respectively. A cationic allyl complex, [Pd(η3-C3H5)(P–N)]Br 5, has also been prepared by oxidative addition
of 3-bromopropene to Pd(dba)2 in presence of the P–N ligand.
Single crystal structure determinations have been carried out for 1, 4
and 5. Carbonylation of the metal–carbon
bond in these new complexes was also studied. The neutral complexes 1 and 2
react smoothly with CO to give carbonylated products [Pd(C(O)Ph)I(P–N)] 6 and [Pd(C(O)Me)I(P–N)] 7,
respectively. The methyl complex 2
reacted much faster than the phenyl complex 1.
The cationic complexes 3 and 4 are inert and do not give any carbonylated
product. However, in the case of the reaction of 3,
evidence has been obtained for the formation of a CO-coordinated complex [PdPh(PPh3)(CO)(P–N)]BF4 8 in which the P–N
ligand temporarily acts as a monodentate phosphorus-bonded ligand. On the
other hand, a cationic complex containing a weakly coordinating acetone molecule,
[PdMe{(CD3)2CO}(P–N)]BF4 9, showed an enhanced
reactivity toward CO and gave [Pd{MeC(O)}(CO)(P–N)]BF4 10.
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