The asymmetric bidentate ligand
(±)-(2-aminophenyl)(2-chlorophenyl)methylphosphine has been
prepared via chemoselective cleavage of the phenyl group from
(±)-(2-aminophenyl)methylphenylphosphine using lithium in
tetrahydrofuran (thf), to give (2-aminophenyl)methylphosphine upon
hydrolysis, followed by deprotonation of the secondary phosphine with
sodium in thf and subsequent reaction with 1,2-dichlorobenzene. The
chlorophenyl-substituted tertiary phosphine has been resolved by the
method of metal complexation. The absolute configuration of the
R enantiomer of the ligand has been assigned by a crystal
structure determination of the diastereomeric palladium(
II)
complex
[(S
P
),(R)]-[(2-aminophenyl)(2-
chlorophenyl)methylphosphine-N,P]{1-[1-
(dimethylamino)ethyl]naphthyl-C
2
,N}
palladium(
II) hexafluorophosphate. Reaction of
(±)-(2-aminophenyl)(2-chlorophenyl)methylphosphine with an
equimolar quantity of sodium (2-dimethylarsinophenyl)methylarsenide in
thf at -20 ± 5 °C gave a
1
:
1 diastereomeric mixture of the chiral pentadentate
ligands
(R
As
*,R
As
*,S
P
*)-(±)- and
(R
As
*,S
As
*,S
P
*)-(±)-{2-[(2-dimethylarsinophenyl)
methylarsinophenyl}{2-[(2-dimethylarsinophenyl)
methylarsinoamino]phenyl}methylphosphine. The chiral quadridentate
ligand
(R
As
*,S
P
*)-(±)-1-[(2-
aminophenyl)methylphosphino]-2-[(2-dimethylarsinophenyl)methylarsino]
benzene can be isolated, however, when the coupling reaction is
performed at 50 ± 5 °C. The chiral
multidentate ligands have been isolated by complexation to
cobalt(
III) and the structures of the three complexes
determined by X-ray analyses. It is clear from the structural data that
the quadridentate ligand has formed a single
dichlorocobalt(
III) complex with cis-α
stereochemistry and in which the stereogenic arsenic and phosphorus
atoms of the ligand have opposite relative configurations. Two other
complexes have also been isolated from the coupling reaction:
trans-dichlorobis[1,2-phenylenebis(dimethylarsine)]cobalt(
III) chloride and
bis[(2-aminophenyl)methylphenylphosphine]dichlorocobalt(
III)
chloride. The latter is isolated as an isomeric mixture. The formation
of asymmetric bidentate (±)-(2-aminophenyl)methylphenylphosphine
is believed to result from reduction of the chloro group in the tertiary
phosphine precursor by the sodium arsenide reagent. Metal-assisted
methylation of a (2-dimethylarsinophenyl)methylarsino moiety by methanol
is postulated to account for the formation of
1,2-phenylenebis(dimethylarsine) in the reaction. Optically active
analogues of the three multidentate ligands have also been synthesized
by reaction of
(R)-(2-aminophenyl)(2-chlorophenyl)methylphosphine with sodium
(2-dimethylarsinophenyl)methylarsenide in thf and similarly isolated by
complexation to cobalt(
III).