Elsevier, Journal of Organometallic Chemistry, 14(692), p. 3070-3080
DOI: 10.1016/j.jorganchem.2007.03.035
Full text: Unavailable
(R)-1-Phenylethyl-benzylidene-amine (1) reacted with Pd(OAc)2 in acetic acid at 60°C under nitrogen affording the acetato-bridged dinuclear endo five-membered ortho-cyclopalladated compound (μ-OAc)2[Pd(κ2-C,N-(R)-C6H4-CHN-CHMe-Ph)]2 (2) in 65% yield. Compound 2 was converted by a metathesis reaction with LiCl into the corresponding chloro-bridged dinuclear cyclopalladated compound (μ-Cl)2[Pd(κ2-C,N-(R)-C6H4-CHN-CHMe-Ph)]2 (3). 1H NMR of CDCl3 solutions of compounds 2 and 3 treated separately with py-d5, (R)-1-phenylethylamine and racemic 1-phenylethylamine were consistent with the endo cyclopalladated structure and the R absolute configuration of the chiral carbon atoms of compounds 2 and 3. Compounds 2 and 3 reacted with carbon monoxide in methanol affording, as major compounds, methyl 2-formylbenzoate (91% chemical yield) and the epimers of 3-methoxy-2-[(R)-1-phenylethyl]isoindolin-1-one (64% chemical yield) in ca. 20% diastereomeric excess, respectively. The trans isomer of compound 3 crystallized in the P21 monoclinic space group with a=10.430(4)Å, b=12.082(8)Å, c=11.168(4)Å and β=95.20(3)° and presented C–H⋯Cl intramolecular and C–H⋯Pd intermolecular non-conventional hydrogen bonds.