CuI Complexes Containing Phenylaminobis(phosphonite)
properties.7 Among the various bis(phosphine) ligands, bis-
(diphenylphosphino)methane (dppm) is an important bridging
ligand for making polynuclear species with most metals and
particularly with copper(I).8 Similar types of bis(phosphines),
with an “RN<” spacer in place of the methylene group, are
known as acyclic diphosphazanes.
As a part of our interest in phosphorus-based ligands and
their catalytic applications,12 we describe here the copper(I)
chemistry of aminobis(phosphonite) PhN(P(OC6H4OMe-o)2)2
(PNP; 1). The crystal and molecular structures of several
di- and tetranuclear complexes including a novel coordination
polymer are also described.
The transition-metal chemistry of acyclic diphosphazanes
and their bis(chalcogenide) derivatives have attracted con-
siderable attention in recent years because of the versatile
coordination behavior of the former, because it is similar to
dppm,9 and the potential application of the latter as single-
source precursors of various metal-, nonmetal-, and met-
alloid-telluride thin films and nanoparticles.10 Although
several groups have studied the coordination behavior of
aminobis(phosphines) and related phosphonite derivatives,
the copper(I) chemistry of this class of ligands is scant despite
their ability to form interesting complexes through their
versatile coordination behavior.8c,11
Results and Discussion
Reactions with Copper(I) Halides. Treatment of the
aminobis(phosphonite) 1 with 2 equiv of CuI in acetonitrile
leads to the formation of a dinuclear complex Cu2(µ2-I)2-
(NCCH3)2(µ-PNP) (2) in good yield (Scheme 1). In contrast,
the reactions of 1 with 2 equiv of CuX (X ) Cl, Br) in
acetonitrile afforded tetranuclear complexes Cu4(µ2-X)2(µ3-
X)2(µ-PNP)2 (3, X ) Cl; 4, X ) Br) in quantitative yield.
The 31P NMR spectra of complexes 2-4 show single
resonances at 88.5, 101.3, and 98.2 ppm, respectively. The
1H NMR spectrum of 2 shows single resonances at 1.94 and
3.57 ppm, respectively, for coordinated CH3CN and o-
1
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