Synthesis and crystal structure of some phosphite, thiophosphite, and amidophosphite copper(I) halide complexes

Article abstract of DOI:10.1002/hc.20459

Some Cu(I) halides complexes based on P(III) acid esters, {[(RE) ₃PCuBr] (where E = O, N, S); R = n-Pr, i-Pr, Et₂N} were obtained and characterized using IR, ³¹P NMR spectroscopy, and single crystal X-ray diffraction. The comparative structural characteristics of complexes with various donor atoms (E = O, N, S) are analyzed.

Full text of DOI:10.1002/hc.20459

Heteroatom Chemistry
Volume 19, Number 5, 2008
Synthesis and Crystal Structure of Some
Phosphite, Thiophosphite, and
Amidophosphite Copper(I) Halide Complexes
Lidiya I. Kursheva, Olga N. Kataeva, Dmitry B. Krivolapov,
Aidar T. Gubaidullin, Elvira S. Batyeva, and Oleg G. Sinyashin
A. E. Arbuzov Institute of Organic and Physical Chemistry, Russian Academy of Sciences,
Arbuzov Str. 8, 420088 Kazan, Russia
Received 1 June 2007; revised 24 March 2008
acyclic and cyclic diphophine ligands [2–5]. As for
ABSTRACT: Some Cu(I) halides complexes based
the Cu(I) halide complexes with the esters of P(III)
on P(III) acid esters,{[(RE)3PCuBr] (where E = O, N,
acids, there are relatively few structural data in the
S); R = n-Pr, i-Pr, Et2N} were obtained and charac-
literature [6–15], although the complexation of the
terized using IR, 31P NMR spectroscopy, and single
esters of P(III) acids, especially phosphites and ami-
crystal X-ray diffraction. The comparative structural
dophosphites, with Cu(I) halides has been widely
characteristics of complexes with various donor atoms
investigated. Phosphorus ligands P(ERn)3 (n= 1 or
ꢀ
C
(E = O, N, S) are analyzed.
2008 Wiley Periodicals,
2) containing several donor atoms such as E = O,
N, S are potentially polydentate ligands, which may
form a variety of complexes with different coordina-
tion modes. Owing to unusual donor properties of
the ambident system P-E, such ligands are of great
interest in organometallic chemistry and catalysis
[6–9,15].
Inc. Heteroatom Chem 19:483–489, 2008; Published on-
line in Wiley InterScience (www.interscience.wiley.com).
DOI 10.1002/hc.20459
INTRODUCTION
However, to date, the X-ray data have been
reported for Cu(I) halide complexes mainly with
bulky and chiral P N, P O ligands, e.g., for
the 6-membered cyclic P–N ligand [6] or bulky
chiral P O ligands [7,8,10–12,15], which have
the cubane-like structure. It is shown that the
bulky ligands are essential but insufficient for
the formation of tetramers [7,8,10–12]. The con-
ditions of realization of the bond between tran-
sition metal atoms and ligand are also essential.
If in [11] the structure of Cu(I)Cl and Cu(I)Br
complexes with triphenyl phosphite was found to
be a cubane tetrameric one, the authors [13,14]
have observed the dimeric structure for Cu(I)Cl and
Cu(I)I complexes with the same ligand. In several
cases, cubane-like structure was observed in the
The diversity in structural chemistry of copper(I) is
well illustrated in complexes of copper(I) halides es-
pecially with the monodentate tertiary phosphines
[1]. The tetrameric “cubane” structure was found
to be the most common for such complexes, al-
though an open “chair” (or “step’) structure was
also observed in several cases. The polymeric chain
and monomeric structure was observed for some
Correspondence to: Lidiya I. Kursheva; e-mail: kursheva@
iopc.knc.ru.
Contract grant sponsor: Russian Fund for Basic Research, Divi-
sion of Chemistry and Material Science of the Russian Academy
of Sciences (Program 7).
Contract grant number: 06-03-32180.
2008 Wiley Periodicals, Inc.
c
ꢀ
483

484 Kursheva et al.
equilibrium with a dimeric or tetrameric–dimeric
forms in solution, as for the Cu(I) chloride
complex with phosphite P(odag)3(odag = 1,2:5,6-di-
O-isopropylidene-α-D-glucofuranoside) [8] or for
the Cu(I) halides with the caged phosphites 4-
2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane and its
4-nitro-derivative [12]. The structure of Cu(I) chlo-
ride complex with triisopropylphosphite ligand is
shown to be a centrosymmetric dimer [9]. The search
of phosphite and amidophosphite complexes with
Cu(I) halides in the Cambridge Crystallographic
Database [5] yielded only compounds with mon-
odentate coordination of metal by phosphorus atom;
no compounds with bidentate coordination of cop-
per(I) by phosphorus and oxygen or nitrogen are be-
ing found. In total, considerations cited above are
limited to the structures for Cu(I) complexes with
P(III) esters with such characteristics as the steric
hindrance, in which the monodentate type of coor-
dination of Cu(I) via P atom is realized, whereas the
binding ability of such ligands for copper(I) halides
depending on a second donor atom (O, N, S) is not
considered. Earlier we have reported our studies on
the coordination properties of thioesters of P(III)
acids. The series of complexes of trialkyltrithiophos-
phites with Cu(I) halides were synthesized, and the
structure of most of these complexes in solid state
has been studied [16,18–21]. It was found that the
thiophosphite ligands have significantly different co-
ordination properties as compared with phosphite or
amidophosphite ligands. The major difference refers
to the participation in coordination of the second
donor center–the sulfur atom. Thiophosphites form
the Cu(I) complexes of various structures: dimeric,
tetrameric cubane-like, and step-like structure as
well as polymeric and cluster structure [16–24] and
exhibit the variety of coordination modes: “classical”
monodentate coordination via phosphorus, biden-
tate coordination with participation of both donor
atoms phosphorus and sulfur, both types of coordi-
nation in one complex and tridentate coordination
via phosphorus and two sulfur atoms.
The ligands, excluding the commercial triiso-
propylphosphite and triamidophosphite, were syn-
thesized by reacting PCl3 with the equimolecular
amount of alcohol (propanol) or thiol (isopropyl
mercaptan) [25]. All ligands are colorless liquids and
extremely soluble in hydrocarbons and other non-
polar and polar solvents. The single peaks in the 31
P
NMR spectra at δ + 138, 137, 118, 104 ppm are in
the expected ranges for appropriate esters of P(III)
acids.
These esters have been treated with Cu(I) halides
to give the complexes CuXLn 1–5. Complexes 2–5
are white crystalline compounds. There is the simi-
lar 1:1 stoichiometry (ligand : metal) for complexes
1, 2, 4, 5, the different 2:1 stoichiometry being only
observed for the compound 3. The complexation re-
sults in the significant high-frequency shifts of the
PO3, PN3, or PS3 stretching vibrations in the IR spec-
tra of complexes 1–5 as compared with the spectra
of respective free ligands. The 31P NMR spectra of
all complexes show a single peak at δ + 114.9 (1),
114.6 (2), 105.2 (3), 91.1(4), and 103.9(5), respec-
tively, the high-field shifts (ꢀδp ∼15–30 ppm) of
the phosphorus signal are being observed for com-
plexes in comparison with free P(III) esters. The
crystal and molecular structures of complexes 2–5
were determined by single crystal X-ray diffraction
(Figs. 1–3). Crystals of complexes suitable for X-
ray analysis were grown from benzene (complexes
2, 3, 5) and chloroform (complex 4). Unfortunately,
our attempts to obtain single crystals of complex 1
with tris(n-propyl)phosphite ligand suitable for
X-ray diffraction study failed.
According to the X-ray data, in the Cu(I)Br
complexes the monodentate type of coordination
via the P atom is realized regardless of the P O ,
P N , and P S ligands (Figs. 1–3). However, dif-
ferent types of self-assembly are observed: tetrahe-
dral monomeric structure CuBrL3, L = (i-PrO)3P 2
and CuBrL2, L = (Et2 N)3P 3; tetrameric [CuXL]4,
L = (i-PrS)3P; X = Br 4; L = (Et2 N)3 P, X = Cl 5.
A
complex of the Cu(I)Br with tris(iso-
propyl)phosphite 2 has the monomeric structure,
two molecules in asymmetric part of unit cell in this
structure are being revealed (Fig. 1). It should be
mentioned that in the case of Cu(I)Cl complex with
the same ligand, authors [9] have observed the cen-
trosymmetric dimeric structure.
The monomeric structure is also re-
vealed for the complex of Cu(I)bromide with
tris(diethylamido)phosphite, 3; however, as men-
tioned above, this complex has the ligand:metal
stoichiometry, 2:1, and the copper(I) atom has the
planar-trigonal configuration (Fig. 2), unlike the
complexes 2 and 4 with a tetrahedral copper atom.
RESULTS AND DISCUSSION
In a course of our studies of new complexes based
on the esters of P(III) acids, we have synthesized sev-
eral complexes with Cu(I) halides, namely tripropyl-
1, tri-isopropyl-2, tris(diethylamido)-3, tris(iso-
propylthio)-4 phosphites, with Cu(I)Br, and complex
of tris(diethylamido)phosphite with Cu(I)Cl 5. Com-
plexes 2–5 were investigated by single crystal X-ray
diffraction, and their structures being reported here
to compare the structural characteristics for P O ,
P N , P S ligands.
Heteroatom Chemistry DOI 10.1002/hc

Synthesis and Crystal Structure of some Phosphite, Thiophosphite and Amidophosphite Copper(I) Halide Complexes 485
FIGURE 1 Molecular structure of complex (i-PrO)3P•CuBr 2.
FIGURE 2 Molecular structure of complex {[(Et2N)3P]2•CuBr} 3.
Meanwhile, complex 5 of Cu(I) chloride with the
same P N ligand, tris(diethylamido)-phosphite,
has the 1:1 stoichiometry and the cubane-like
structure with tetrahedral configuration of copper
atom. The tetrameric core consisting of copper
and chlorine atoms as well as the monodentate
(via P) coordination mode was determined. More
detailed consideration of the geometrical parame-
ters of complex 5 is impossible because of the low
accuracy due to poor quality of the crystals and
their instability, which did not allow us to localize
all of the terminal carbon atoms. It is reasonable
to suppose that differences, which are observed in
the structure of Cu(I) complex described in [9] and
complex 2 discussed here, as well as 3 and 5 ones,
may be due to the volume of halogen and also the
conditions of crystal growth.
For the Cu(I) complexes with trialkyltrithiophos-
phite ligands, the cyclic chain polymeric structure
and the bidentate type of copper coordination (via
P and S) are found to be the most common ones
[16–22]. However, for the complex 4 of Cu(I)Br with
tris(iso-propylthio)phosphite, steric factors exclude
the participation of sulfur in coordination bond with
copper; thus, monodentate type of Cu coordination
via P-atom and the tetrameric cubane structure were
Heteroatom Chemistry DOI 10.1002/hc

486 Kursheva et al.
EXPERIMENTAL
All manipulations involving P(III) acid esters were
carried out under argon using dry solvents. The IR
spectra were recorded as Nujol mulls on a Specord
UR-20 and M-80 spectrometers in the range 400–
4000 cm−1. The 31P NMR spectra: Bruker MSL-400,
(162 MHz); CXP-100 (36.47 MHz), standard: exter-
nal 85% H3PO4); solvents: C6H6 or CHCl3. The melt-
ing points were determined on a Boetius apparatus
and are uncorrected. All commercial reagents were
used without further purification. The P-ligands, tri-
isopropyl phosphite, and tri(diethylamido)- phos-
phite were purchased from Alfa Aesar (a Johnson
Matthey Company: UK, Heysham, Lancashire LA3
2XY).
The P-ligands, tri-n-propyl-, and tri(isopropyl-
thio)phosphites were obtained according to the
method described in [25].
Tri-n-propyl Phosphite
A solution of PCl3 (6.86 g, 0.05 mol) in dry ether (40
mL) was added dropwise to a stirred solution con-
taining 9 g (0.15 mol ) of dry n-propanol and 15.1 g
(0.15 mol ) dry triethylamine in dry ether (80 mL) for
2 h at −10◦C. The reaction mixture was then heated
with the vigorous stirring for 2 h at 35◦C to form the
precipitate of ammonium hydrochloride. The latter
was filtered off and washed with two portions of the
ether (2 × 20 mL). After concentration filtrate, the
residue was distillated to give ∼7 g (60%) of tri-n-
propyl phosphite, bp 90–95◦C (15 mm/Hg); δp 138.
Anal. Calcd for C9H21O3P [208]: C, 51.92; H, 10.09;
P, 14.9. Found: C, 51.31; H, 10.2; P, 15.10.
FIGURE
PrS)3P•CuBr]4 4.
3 Molecular structure of complex [(i-
found (Fig. 3). Each copper(I) atom is in a dis-
torted tetrahedral coordination environment being
linked to one ligand molecule and to three bridg-
ing bromine atoms, because such tetrameric cubane
Cu4Br4 core is much distorted and strained. The dis-
torted “cubane-like” structure is also observed for
the complex of Cu(I)I [23], whereas for the complex
of Cu(I)Cl a unique cluster structure and tridentate
type of coordination via P and two S atoms were re-
alized with the same ligand [23]. It should be noted
that “cubane-like” structure was often observed for
the complexes with bulky phosphite and amidophos-
phite ligands [6–8,10–12,15].
Triisopropylthiophosphite
PCl3 (9.2 g, 0.07 mol) was added dropwise to the
solution of isopropyl mercaptan (15 g, 0.2 mol) in
dry ether (100 mL) at 0◦C for 1.5 h. After complete
addition, the ether was removed; the residue was
distillated to give 13.3 g (55%) of triisopropylthio-
phosphite, bp 90–100◦C (10 mm/Hg); δp104. Anal.
Calcd for C9H21S3P [256]: C, 42.2; H, 8.2; P, 12.2; S,
37,5. Found: C, 41.8; H, 8.3; P, 12.35; S, 36.85.
In all studied crystals the Cu· · · P distances range
˚
from ∼2.212 (8) A in tetrameric complex 4 to 2.238
˚
(1) Cu–P(2)–2.245 (2) Cu–P(1) A in dimer [9] and
˚
˚
2.267(3) A as well as 2.2484 (8) A in monomeric com-
plexes 2 and 3, respectively (Table 1).
These results have shown that Cu(I) displays a
wide structural diversity in studied complexes of
Cu(I) halides with the P(III) acid esters with a dif-
ferent stoichiometry, configuration, and structure in
such complexes regardless of the nature of second
donor atom at phosphorus. Structure of Cu(I) halide
complexes with phosphites, amidophosphites, and
thiophosphites are generally determined by the vol-
ume and nature of ligand, the binding ability of such
ligands, the conditions of crystal growth, the solvent
used and the volume of halogen atom as well.
[Tri(n-propyl)phosphite]copper(I) Bromide (1)
and [Tri(iso-propyl)phosphite]copper(I)
Bromide (2)
CuBr (2.8 g, 0.02 mol) was added by portions at the
stirring to 4 g (0.02 mol) of corresponding phosphite.
The temperature increasing of the reaction mixture
from 18 to 40◦C was observed. Then C6H6(7 mL)
was added to the reaction mixture with its following
Heteroatom Chemistry DOI 10.1002/hc

Synthesis and Crystal Structure of some Phosphite, Thiophosphite and Amidophosphite Copper(I) Halide Complexes 487
◦
˚
TABLE 1 Selected Bond Distances (A), and Bond Angles ( ) for Complexes 2–4
Complex 2
˚
˚
Bond
d (A)
Bond
d (A)
Cu(1A)–Br(1A)
Cu(1B)–Br(1B)
P(1A)–Cu(1A)
2.4748(14)
2.4670(15)
2.278(3)
P(2A)–Cu(1A)
P(1B)–Cu(1B)
P(3B)–Cu(1B)
2.269(3)
2.265(3)
2.258(3)
ω (◦)
Bond angles
ω (◦)
Bond angles
P(3A)–Cu(1A)–P(2A)
P(3A)–Cu(1A)–P(1A)
P(2A)–Cu(1A)–P(1A)
P(3A)–Cu(1A)–Br(1A)
P(2A)–Cu(1A)–Br(1A)
P(1A)–Cu(1A)–Br(1A)
114.51(10)
116.46(10)
112.38(10)
101.41(8)
101.14(8)
108.93(8)
P(3B)–Cu(1B)–P(2B)
P(3B)–Cu(1B)–P(1B)
P(2B)–Cu(1B)–P(1B)
P(3B)–Cu(1B)–Br(1B)
P(2B)–Cu(1B)–Br(1B)
P(1B)–Cu(1B)–Br(1B)
114.64(10)
117.08(11)
110.72(11)
101.65(8)
103.09(8)
108.00(8)
Complex 3
˚
˚
Bond
d (A)
Bond
d (A)
Cu(1A)–P(1A)a
Cu(1A)–P(1A)
Cu(1A)–Br(1A)
2.2513(9)
2.2513(9)
2.4115(8)
Cu(1B)–P(1B)b
Cu(1B)–P(1B)
Cu(1B)–Br(1B)
2.2456(8)
2.2456(8)
2.4151(8)
Bond angles
ω (◦)
Bond angles
ω (◦)
P(1A)a–Cu(1A)–P(1A)
P(1A)a–Cu(1A)–Br(1A)
P(1A)–Cu(1A)–Br(1A)
142.20(5)
108.90(3)
108.90(3)
P(1B)b–Cu(1B)–P(1B)
P(1B)b–Cu(1B)–Br(1B)
P(1B)–Cu(1B)–Br(1B)
142.67(5)
108.67(2)
108.67(2)
Complex 4
˚
˚
Bond
d (A)
Bond
d (A)
Br(1D)–Cu(1A)
Br(1D)–Cu(1D)
Br(1D)–Cu(1B)
Br(1C)–Cu(1B)
Br(1C)–Cu(1C)
Br(1C)–Cu(1A)
Br(1A)–Cu(1C)
Br(1A)–Cu(1A)
2.492(4)
2.515(5)
2.590(4)
2.502(4)
2.527(4)
2.551(4)
2.483(4)
2.499(4)
Br(1A)–Cu(1D)
Br(1B)–Cu(1D)
Br(1B)–Cu(1B)
Br(1B)–Cu(1C)
Cu(1A)–P(1A)
Cu(1B)–P(1B)
Cu(1C)–P(1C)
Cu(1D)–P(1D)
2.554(4)
2.458(4)
2.523(4)
2.559(4)
2.203(8)
2.222(7)
2.211(8)
2.213(8)
Bond angles
ω (◦)
Bond angles
ω (◦)
Cu(1A)–Br(1D)–Cu(1D)
Cu(1A)–Br(1D)–Cu(1B)
Cu(1D)–Br(1D)–Cu(1B)
Cu(1B)–Br(1C)–Cu(1C)
Cu(1B)–Br(1C)–Cu(1A)
Cu(1B)–Br(1B)–Cu(1C)
P(1A)–Cu(1A)–Br(1D)
P(1A)–Cu(1A)–Br(1A)
Br(1C)–Cu(1B)–Br(1B)
P(1B)–Cu(1B)–Br(1D)
Br(1C)–Cu(1B)–Br(1D)
Br(1B)–Cu(1B)–Br(1D)
P(1C)–Cu(1C)–Br(1A)
P(1C)–Cu(1C)–Br(1C)
Br(1A)–Cu(1C)–Br(1C)
P(1D)–Cu(1D)–Br(1D)
Br(1B)–Cu(1D)–Br(1D)
77.42(13)
78.87(12)
75.86(12)
81.36(13)
79.46(12)
80.34(13)
118.7(3)
116.4(2)
98.62(14)
107.7(2)
98.68(13)
100.53(13)
123.7(2)
113.2(3)
103.75(15)
111.4(3)
Cu(1C)–Br(1C)–Cu(1A)
Cu(1C)–Br(1A)–Cu(1A)
Cu(1C)–Br(1A)–Cu(1D)
Cu(1A)–Br(1A)–Cu(1D)
Cu(1D)–Br(1B)–Cu(1B)
Cu(1D)–Br(1B)–Cu(1C)
Br(1D)–Cu(1A)–Br(1A)
P(1A)–Cu(1A)–Br(1C)
Br(1D)–Cu(1A)–Br(1C)
Br(1A)–Cu(1A)–Br(1C)
P(1B)–Cu(1B)–Br(1C)
P(1B)–Cu(1B)–Br(1B)
P(1C)–Cu(1C)–Br(1B)
Br(1A)–Cu(1C)–Br(1B)
Br(1C)–Cu(1C)–Br(1B)
P(1D)–Cu(1D)–Br(1B)
Br(1B)–Cu(1D)–Br(1A)
75.41(12)
77.12(13)
78.41(12)
76.59(13)
78.11(13)
78.75(12)
102.32(15)
114.3(3)
99.98(13)
102.62(15)
123.1(3)
123.6(3)
115.7(3)
99.52(15)
97.00(13)
126.2(3)
104.46(14)
100.33(15)
aSymmetry code, –x + 3/2, y,– z+ 1/2
bSymmetry code, –x + 3/2, y, – z+ 3/2
Heteroatom Chemistry DOI 10.1002/hc

488 Kursheva et al.
TABLE 2 Crystal Data, Data Collection, and Refinement Details for Complexes 2–4
2
3
4
Empirical formula
Formula weight
Space group
(i-PrO)3P•CuBr
768.13
P21/a (two independent
molecules)
[(Et2N)3P]2•CuBr
638.17
P2/n (two independent
molecules)
[(i-PrS)3P•CuBr]4
1599.43
P212121
˚
a (A)
19.975(3)
20.906(4)
19.246(3)
9.2150(10)
13.872(2)
19.649(3)
˚
b (A)
˚
c (A)
20.838(4)
90
104.35(3)
90
8430(3)
8
1.21
19.479(3)
90
101.42(2)
90
3386.2(8)
4
25.402(2)
α (◦)
β (◦)
γ (◦)
90
90
90
3
˚
V (A )
6923.8(2)
4
1.53
3232
Z
Dcalc (mg m−3
F(000)
)
1.25
1360
3248
Crystal color
Crystal form
Crystal size (mm)
Colorless
Prismatic
0.3 × 0.3 × 0.2
Colorless
Prismatic
0.3 × 0.2 × 0.2
Colorless
Prismatic
0.3 × 0.2 × 0.1
˚
Radiation (A)
0.71073
293
Temperature (K)
Scan mode
293
ω/2θ
2.31–22.77
293
ω
2.17–24.98
39.98
ω/2θ
2.45–26.29
19.41
Variable, 1–16.4
7,063
Recording range θ
(◦)
max
Absorption correction µ (cm−1
)
16.18
Scan speed (deg · min−1
)
Number of recorded reflections
10,313
9,617
4485
8,608
7,905
2,884
Number of independent reflections
6,857
3,916
Number of independent reflections
with F2 ≥ 2σ (F2)
R (%)
Rw (%)
S
0.0552
0.1310
0.988
0.0361
0.0755
0.974
0.0812
0.1814
0.903
heating for 2–2.5 h at 40–45◦C. The mixture was
cooled to room temperature and then concentrated
under reduced pressure to give complexes. Complex
1 (370 mg, 57%) was obtained as a colorless viscous
liquid. 31P NMR, δ: 114.9; ꢀδ 23. IR (ν/cm−1): 560
(CO), 745–840 (PO). Anal. Calcd for C9H21CuBrO3P
(351.76): C 30.72, H 6.02, Cu 18.18, Br 22.72; P 8.81.
Found: C 31.67; H 6.03; Cu 17.79; Br 22.01, P 8.37.
Complex 2 was crystallized to give colorless crys-
tals of (350 mg, 51.5%); mp 155–158◦C. 31P NMR, δ:
114.6; ꢀδ 26. IR (ν/cm−1): 545 (CO), 750–770 (PO).
Anal. Calcd for C9H21CuBrO3P (351.76): C 30.72, H
6.02, Cu 18.18, P 8.81. Found: C 30.66; H 6.01; Cu
18.14; P 8.85.
105.2; ꢀδ 12.0. IR (ν/cm−1): 930 (PN). Anal. Calcd for
C24H60BrCu N6P2 (638.22): C 45.16, H 9.47, P 9.71.
Found: C 45.40; H 9.82; P 10.0.
[Triisopropylthio phosphite]copper(I)
Bromide (4)
CuBr (1.5 g, 0.01 mol) was added to a stirred solu-
tion of triisopropylthio phosphite (3.5 g, 0.01 mol)
in 10 mL CHCl3. The temperature of the reaction
mixture increased from 14 to 22◦C. After refluxing
for 1 h and following cooling to room tempera-
ture, unreacted salt was filtered off from the reac-
tion mixture. The filtrate was evaporated, and the
residue was recrystallized from CHCl3, to give com-
plex 4 (3.3 g, 66%); mp 88–92◦C. 31P NMR, δ: 91.1;
ꢀδ 14.1. IR (ν/cm−1): 630 (CS), 500 (PS). Anal. Calcd
for C9H21BrCuS3P (399.94): C 27.03, H 5.29, P 7.75.
Found: C 27.58; H 5.21; P 8.0.
[Tri(diethylamido)phosphite]copper(I)
Bromide (3)
CuBr (0.59 g, 0.004 mol) was added to a stirred solu-
tion of tri(diethylamido) phosphite (1 g, 0.004 mol)
in 5 mL of C6H6. The reaction mixture was stirred
for 1.5–2 h without heating and then was allowed to
stay for crystallization during 2 weeks. After that, the
solvent was removed to give the complex 3 (87 mg,
67%) of the 2:1 ratio; mp 116–118◦C. 31P NMR, δ:
[Tri(diethylamido)phosphite]copper(I)
Chloride (5)
In a similar manner to that described above, from
CuCl (0.4 g, 0.004 mol) and tri(diethylamido) phos-
phite (1 g, 0.004 mol), the complex 5 (0.8 g, 57%)
Heteroatom Chemistry DOI 10.1002/hc

Synthesis and Crystal Structure of some Phosphite, Thiophosphite and Amidophosphite Copper(I) Halide Complexes 489
was obtained, m.p. .97–100◦C. 31P NMR, δ: 103.9; ꢀδ
[6] Nifant’ev, E. Eug.; Teleshev, A. T.; Blokhin, Yu. I.;
15.4. IR (ν/cm−1): 928 (PN). Anal. Calcd for C12H30
ClCuN3P (346.36): C 41.61, H 8.73, P 8.95. Found: C
41.04; H 8.69; P 8.87.
Antipin, M. Yu.; Struchkov, Yu. T. Zh Obshch Khim
1985, 55(6), 1265.
[7] Nifant’ev, E. Eug.; Koroteev, M. P.; Koroteev, A. M.;
Antipin, M. Yu.; Lysenko, K. A.; Bel’ski, V. K. Tsao L.
Dokl Ak Nauk 1997, 353(4), 508.
[8] Stolmar, M.; Floriani, C.; Gervasio, G.; Viterbo, D. J
Chem Soc, Dalton Trans 1997, (7), 1119–1121.
[9] Lobkovsky, E. B.; Antipin, M. Yu.; Makhaev, V. D.;
Borisov, A. P.; Semenenko, K. N.; Struchkov, Yu. T.
Koord Khim 1981, 7(1), 141.
[10] Arkhireeva, T. M.; Bulychev, B. M.; Sizov, A. I.;
Sokolova, T. A.; Belsky, V. K.; Soloveichik, G. L Inorg
Chim Acta 1990, 169(1), 109–118.
[11] Pike, R. D.; Starnes Ynr, W. H.; Carpenter, G. B. Acta
Crystallogr, Sec C 1999, 55, 162–165.
[12] Cole, J. R.; Dellinger, M. E., Johnson, T. J.; Reinecke,
B. A.; Pike, R. D.; Pennington, W. T.; Krawiec, M.;
Rheingold, A. L. J Chem Cryst 2003, 33, 341.
[13] Na¨ther, Ch.; Steinhoff, T.; Jeß, I. Acta Crystallogr, Sec
E 2003, 59, m1041–m1043.
[14] Jian, F-F.; Wang, K-F.; Xiao, H-L.; Qiao, Y-B. Acta
Crystallogr, Sec E 2005, 61, m1324–1325.
[15] Pfretzschner, T.; Kleemann, L.; Janza, B.; Harms, K.;
Schrader, Th. Chem-Eur J 2004, 10(23), 6048–6057.
[16] Kataeva, O. N.; Litvinov, I. A.; Naumov, V. A.;
Kursheva, L. I.; Batyeva, E. S. Inorg Chem 1995,
34(21), 5171–5174.
[17] Jones, P. G.; Fisher, A. K.; Frolova, L.; Schmutzler,
R. Acta Crystallogr, Sec C 1998, 54, 1842–1854.
[18] Kursheva, L. I.; Il’in, A. M.; Batyeva, E. S. Russ J Gen
Chem 1998, 68(1), 157–158.
[19] Kursheva, L. I.; Il’in, A. M.; Gidzalova, Yu. G.;
Batyeva, E. S. Zh Obshch Khim 1999, 69(6), 916–919.
[20] Kursheva, L. I.; Il’in, A. M.; Batyeva, E. S.; Kataeva,
O. N.; Gubaidullin, A. T. Russ J Gen Chem 2001,
71(3), 521.
X-Ray Crystallographic Study
The X-ray diffraction data for the crystals of 2–4
were collected on a CAD4 Enraf-Nonius automatic
diffractometer using graphite monochromated Mo
˚
Kα (0.71073 A) radiation. The crystal data, data col-
lection, and the refinement are given in Table 2. The
stability of crystals and experimental conditions was
checked every 2 h using three control reflections,
while the orientation was monitored every 200 re-
flections by centering two standards. No significant
decay was observed. An empirical absorption cor-
rection based on ψ-scans was applied. The structure
was solved by the direct method using the SIR [26]
program and refined by the full matrix least-squares
using SHELX-97 [27] program. All non-hydrogen
atoms were refined anisotropically. The hydrogen
atoms were calculated and refined as riding atoms.
All calculations were performed on PC using WinGX
[28] program. Cell parameters, data collection, and
data reduction were performed on an Alpha Station
200 computer using MolEN [29] program. All figures
were made using the program PLATON [30].
Crystallographic data for the structural analy-
sis have been deposited with the Cambridge Crystal-
lographic Data Centre CCDC nos. 647543, 647544,
and 647545. Copies of the data can be obtained
free of charge from The Director, CCDC, 12 Union
Road, Cambridge, CB2 1EZ, UK (fax: +44-(1223)-
336033; e-mail: deposit@ccdc.cam.ac.uk or www:
http://www.ccdc.cam.ac.uk).
[21] Kataeva, O. N.; Krivolapov, D. B.; Gubaidullin, A. T.;
Litvinov, I. A.; Kursheva, L. I.; Katsyuba, S. A. J Mol
Struct 2000, 554(2/3), 127–140.
[22] Kataeva, O. N.; Sinyashin, O. G. Izv Acad Nauk Ser
Khim 2001, 7, 1079–1087.
[23] Kursheva, L. I.; Kataeva, O. N.; Gubaidullin, A. T.;
Khasyanzyanova, F. S.; Vakhitov, E. V.; Krivolapov,
D. B.; Batyeva, E. S. Russ J Gen Chem 2003, 73(10),
1605–1610.
REFERENCES
[24] Kursheva, L. I.; Kataeva, O. N.; Krivolapov, D. B.;
Batyeva, E. S.; Sinyashin, O. G. Heteroatom Chem
2006, 17(3), 542–546.
[25] Nifant’ev, E. E . Chemistry of Phosphorus Organic
Compounds; Moscow State University: Moscow,
Soviet Union, 1971; 352 pp. (in Russian).
[26] Altomare, A.; Cascarano, G.; Giacovazzo, C.; Viterbo,
D. Acta Crystallogr, Sec A 1991, 47, 744–748.
[27] Sheldrick, G. M. SHELX-97: Programs for Crystal
Structure Analysis, University of Go¨ttingen, Insti-
tut fu¨r Anorganische Chemie der Universita¨t, Tam-
manstrasse 4, D-3400 Go¨ttingen, Germany, 1997.
[28] Farrugia, L. J. WinGX 1.64.05: J Appl Crystallogr
1999, 32, 837–838.
[1] (a) Churchill, M. R.; DeBoer, B. G.; Mendak, S. J Inorg
Chem 1975, 14(9), 2041–2047; (b) Churchill, M. R.;
Rotella, F. J Inorg Chem 1977, 16(12), 3267–3273;
(c) Goel, R. G.; Beauchamp, A. L. J Inorg Chem 1983,
22, 395–400; (d) Barron, P. F.; Dyason, J. C.; Engel-
hardt, L. M.; Healy, P. C.; White, A. H. J Inorg Chem
1984, 23, 3766–3769; (e) Dyason, J. C.; Healy, P. C.;
Engelhardt, L. M.; Pakawatchai, Ch.; Patrick, V. A.;
Raston, C. L.; White, A. H. J Chem Soc, Dalton Trans
1985, 831–838.
[2] Von Kaiser, J.; Hartung, H.; Lengies, E.; Richter, R. Z.
Anorg Allg Chem 1976, 422(11), 149–154.
[3] Bobrov, S. V.; Karasik, A. A.; Sinyashin, O. G. Phos-
phorus Sulfur Silicon 1999, 144–146, 289–292.
[4] Karasik, A. A.; Nikonov, G. N.; Dokuchaev, A. S.;
Litvinov, I. A. Russ J Coord Chem 1994, 20, 300–303.
[5] Cambridge Structural Database System, Ver. 5.27,
May 2006 release.
[29] Straver, L. H.; Schierbeek, A. J MOLEN Structure De-
termination System. Nonius B.V.: Delft, Netherlands,
1994, 1, 2.
[30] Spek, A. L. Acta Crystallogr, Sec A 1990, 46, C-34.
Heteroatom Chemistry DOI 10.1002/hc