Article
Organometallics, Vol. 28, No. 15, 2009 4359
appearance of its NMR resonance signals is temperature-
dependent. Such temperature dependence of the signals is
therefore indicative of a facile exchange process occurring
between the isomers present in solution in equilibrium. These
four peaks reflect the existence of the dimer as a mixture of
six possible isomers in solution, which are the chiral anti-(R,
R), anti-(S,S), syn-(R,R), and syn-(S,S) as well as the achiral
anti-(R,S) and syn-(R,S) isomers, in which both isomers of
the first two pairs are enantiomeric and cannot be distin-
guished from each other by routine NMR spectroscopy.
Optical Resolution of the Dimeric Complex (()-3. The
optical resolution of the racemic complex (()-3 was per-
formed using sodium (S)-prolinate as the resolving reagent,
as shown in Scheme 2. After treating complex (()-3 with 2
Figure 1. Molecular design for complexes (S)-1, (S)-2, and (S)-3.
Preparation of the racemic dimeric palladacycle (()-3 is
shown in Scheme 1. Treatment of the alkyl chloride (()-46
and sodium diphenylphosphide in THF afforded the highly
air-sensitive racemic phosphine (()-5 as a brown-colored oil
in 74.3% yield, δ 5.0 in the 31P NMR spectrum (CDCl3). The
ortho-palladation of compound (()-5 was carried out by the
treatment of the racemic phosphine with Pd(OAc)2 in tol-
uene, followed by the in situ chloride metathesis with LiCl in
methanol with 79.2% isolated yield.10c
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