Synthesis and structural characterization of copper(I) halide complexes containing bis(azol-1-yl)methane derived bisphosphines

Article abstract of DOI:10.1016/j.ica.2016.01.010

The copper(I) complexes containing bisphosphines such as bis(2-diphenylphosphinoimidazol-1-yl)methane (1), bis(5-diphenylphosphinopyrazol-1-yl)methane (2) and bis(5-diphenylphosphino-1,2,4-triazol-1-yl)methane (3) have been synthesized. The reaction of 1

Full text of DOI:10.1016/j.ica.2016.01.010

Accepted Manuscript
Synthesis and structural characterization of copper(I) halide complexes con-
taining bis(azol-1-yl)methane derived bisphosphines
Sajad A. Bhat, Joel T. Mague, Maravanji S. Balakrishna
PII:
S0020-1693(16)00021-9
http://dx.doi.org/10.1016/j.ica.2016.01.010
ICA 16838
DOI:
Reference:
To appear in:
Inorganica Chimica Acta
Received Date:
Revised Date:
Accepted Date:
1 September 2015
1 December 2015
6 January 2016
Please cite this article as: S.A. Bhat, J.T. Mague, M.S. Balakrishna, Synthesis and structural characterization of
copper(I) halide complexes containing bis(azol-1-yl)methane derived bisphosphines, Inorganica Chimica Acta
(
2016), doi: http://dx.doi.org/10.1016/j.ica.2016.01.010
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Synthesis and structural characterization of copper(I) halide complexes
containing bis(azol-1-yl)methane derived bisphosphines
a
b
a,*
Sajad A. Bhat , Joel T. Mague , Maravanji S. Balakrishna
a
Phosphorus Laboratory, Department of Chemistry, Indian Institute of Technology Bombay,
Powai, Mumbai, 400076, India
b
Department of Chemistry, Tulane University, New Orleans, Louisiana, 70118, United States
ABSTRACT: The copper(I) complexes containing bisphosphines such as bis(2-
diphenylphosphinoimidazol-1-yl)methane (1), bis(5-diphenylphosphinopyrazol-1-yl)methane
(
2) and bis(5-diphenylphosphino-1,2,4-triazol-1-yl)methane (3) have been synthesized. The
2
reaction of 1 with CuX (X = Cl, I) afforded homoleptic dinuclear complexes [Cu (µ-
2
X)
CuBr(CH
CuBr. The reaction of 2 with CuX (X = Cl, Br, I) also produced dinuclear complexes Cu
2
{CH
2
(1,3-C
3
H
2
N
2
PPh
2
)
2
}
2
-κ P,P] (X = Cl, 4; I, 6). However, a mononuclear complex
2
[
3
CN){CH
2
(1,3-C
3
H
2
N
2
PPh
2
)
2
}-κ P,P] (5) was isolated in the reaction of 1 with
(µ-
-κ P,P] (X = Cl, 7; Br, 8; I, 9). The reaction of 3 with CuCl
2
2
X)
yielded a novel 1D coordination polymer [Cu
whereas homoleptic dinuclear complexes [Cu
2
{CH
2
(1,2-C
3
H
2
N
2
PPh
2
)
2
}
2
2
2
(µ-Cl)
2
{CH
2
(1,2,4-C
2
2
HN
HN
3
3
PPh
2
)
)
2
2
}-κ P,N]
n
(10),
2
2
(µ-X)
2
{CH
2
(1,2,4-C
PPh
2
}
2
-κ P,P] (X =
Br, 11; I, 12) were obtained in the reactions of 3 with CuX (X = Br, I). Bisphosphines 1 and 2
2
showed bidentate (κ P,P) chelating mode of coordination, whereas 3 has adopted bidentate
2
(
κ P,N) chelating mode of coordination in 10. The crystal structures of 4‒7 and 10‒12 have
been established by single crystal X-ray crystallography.
Keywords: Bisphosphines; Copper(I); Dinuclear; Polymeric; bis(azol-1-yl)methane
*
Author to whom correspondence should be addressed. E-mail: krishna@chem.iitb.ac.in,
msb_krishna@iitb.ac.in (M. S. Balakrishna); Fax: +91-22-5172-3480/2576-7152.

1
. Introduction
Copper(I) complexes have attracted considerable attention over the years because of their
structural diversities, rich photophysical properties [1-16], and catalytic applications [17-22].
Several mono- to tetranuclear copper(I) complexes of nitrogen heterocycles and phosphines
have been reported in the literature; their formation often depends on the nature of the ligands
used, metal to ligand ratio and several other factors including the solvents employed and the
reaction conditions [23-30]. Many of the di- and tetranuclear copper(I) complexes have been
found to be emissive [31-36]. The most commonly employed bisphosphines in copper(I)
complexes are bis[2-(diphenylphosphino)phenyl]ether (POP), 1,2-bis(diphenylphosphino)-
benzene (dppb), 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)-
propane (dppp) and 1,l'-bis(dipheny1phosphino)ferrocene (dppf ) (Chart 1). Tertiary
phosphines containing imidazole, 1,2,3- and 1,2,4-triazoyl moieties represent an intriguing
class of hetero-donor ligands (Chart 1), as their reactions with CuX have produced several
interesting copper(I) complexes with remarkable photo-physical properties [16,37].
Given the numerous reports dealing with the diversity of copper(I) complexes of various
mono- and bisphosphines, copper(I) complexes of bisphosphines anchored on five membered
nitrogen heterocycles with methylene bridge have not been reported. In this context and as a
part of our continued interest on transition metal chemistry of phosphorus based ligands and
their applications [38], herein we report the synthesis and structural characterization of
various copper(I) complexes of bis(2-diphenylphosphinoimidazol-1-yl)methane (1), bis(5-
diphenylphosphinopyrazol-1-yl)methane (2) and bis(5-diphenylphosphino-1,2,4-triazol-1-
yl)methane (3).
2

2
. Results and discussion
2
.1. Synthesis of bisphosphines
The bisphosphine ligands, bis(2-diphenylphosphinoimidazol-1-yl)methane (1), bis(5-
diphenylphosphinopyrazol-1-yl)methane (2) and bis(5-diphenylphosphino-1,2,4-triazol-1-
yl)methane (3) were synthesized according to the reported literature procedures as shown in
Scheme 1 [39,40].
2
.2. Syntheses of copper(I) halide complexes
3

The reaction of 1 with CuX (X = I, Cl) in 1:1 molar ratio afforded dinuclear complexes,
2
[
Cu
2
(µ-X)
2
{CH
2
(1,3-C
3
H
2
N
2
PPh
2
)
2
}
2
-κ P,P] (X = Cl, 4; I, 6) containing Cu
2
X
2
rhombic unit
2
with each copper atom coordinated by the ligand in homoleptic chelating (κ P,P) mode as
shown in Scheme 2. The reaction of 1 with CuBr in 1:1 molar ratio afforded a mononuclear
2
complex [CuBr(NCCH
3
){CH
2
(1,3-C
3
H
2
N
2
PPh
2
)
2
}-κ P,P] (5). Similarly, the reactions of 2
and 3 with CuX (X = I, Br, Cl) in 1:1 molar ratio also yielded dinuclear complexes of the
2
type [Cu
2
(µ-X)
2
{CH
2
(1,2-C
3
H
2
N
2
PPh
2
)
2
}
2
-κ P,P] (X = Cl, 7; Br, 8; I, 9) and [Cu
2
(µ-
2
X) {CH (1,2,4-C
2
2
2
HN
3
PPh
2
)
2
}
2
-κ P,P] (X = Br, 11; I, 12) with rhombic Cu
2
X
2
units. In
contrast, similar reaction between 3 and CuCl in 1:1 ratio produced a novel 1D coordination
2
polymer [Cu
2
(µ-Cl)
2
{CH
2
(1,2,4-C
2
HN
3
PPh
2
)
2
}-κ P,N]
n
(10) with ligand exhibiting
2
heteroleptic chelating (κ P,N) mode of coordination (Scheme 2). The coordination modes
observed in the case of complexes 4, 6‒9, 11 and 12 are routinely adopted by many chelating
3
1
1
bisphosphines and N-heteroaromatic ligands [12,26,41]. Surprisingly, the P{ H} NMR
spectra of the complexes 4−12 in DMSO-d
6
showed single resonances around −32 ppm and
1
no considerable coordination shifts were observed. In the H NMR spectra of 4−12, the
signals corresponding to the CH protons are merged with the aromatic protons. The product
2
formation in case of 2 and 3 was found to be independent of stoichiometry of the reactants as
both 1:1 and 1:2 reactions led to the formation of the same product as confirmed from CHN-
analysis and mass spectrometry.
2
.3
UV-visible absorption spectroscopy
I
The absorption spectra of free ligands and their corresponding Cu complexes are given in
Figs.1 and 2, respectively. Ligands 1‒3 contain two types of aromatic groups: a bridging
bis(azol-1-yl)methane group and auxiliary phenyl groups on phosphorus atoms. They display
broad absorption bands in the UV region at 252, 256 and 247 nm, respectively, due to the
π‒π* transitions. The spectra of complexes 4−9, 11 and 12 are characterized by sharp
4

absorption bands in the region 225-235 nm and broad bands in the region 255-275 nm. These
can be assigned to spin allowed π‒π* ligand centred (LC) transitions within the phenyl rings
on the bisphosphine moieties as well as transitions localized on the five-membered nitrogen
heterocycles. The absorption spectrum of chloro bridged polymeric complex 10 could not be
recorded due to highly insoluble nature. Furthermore, these complexes show tails which are
not visible for the free ligands at longer wavelengths (>300 nm) that gradually decrease in
intensity. These low energy absorptions are assigned to metal-to-ligand charge-transfer
(
MLCT) transitions mixed with halogen-to ligand charge-transfer (XLCT) transitions and are
therefore assigned to (X+M)LCT states.
Fig. 1. UV-visible spectra of ligands 1‒3.
Fig. 2. UV-visible spectra of complexes 4−9, 11 and 12.
5

2
.4 Molecular structures of compounds 4−7 and 10−12
Perspective views of the molecular structures of compounds 4−7 and 10−12 with atom
numbering schemes are shown in Figs. 3−8. The crystal data and bond parameters are listed
in Tables 1‒4. The crystals of the complexes suitable for X-ray diffraction were obtained
either by slow diffusion of acetonitrile solution of copper halides into a dichloromethane
solution of the corresponding ligands at room temperature or by concentrating the reaction
o
mixture and cooling to 0 C.
The X-ray structure of 5 revealed the monomeric structure with copper centre coordinated
by 1, one bromide ion and an acetonitrile molecule as shown in Fig. 3. The eight membered
chelate ring shows boat conformation with slightly distorted tetrahedral geometry around
6

copper centre. The P1−Cu–P2 (108.863°) bite angle is smaller than the values reported for
2
the eight membered chelate rings of similar type in the literature [42]. One of the CH protons
I
is at nonbonding distances of 2.613 Å and 2.637 Å from Cu and Br atoms. The two Cu–P
bond distances [Cu1–P1 = 2.236(1) Å, Cu1−P2 = 2.252(1) Å], are shorter than those in
I
DPEphos-Cu complexes indicating stronger metal−ligand interactions [12], but longer than
those in copper complexes of five-membered nitrogen heterocycle based phosphine ligands
[
37a]. The Cu1–N5 [2.002(3) Å] and Cu1–Br1 [2.484(7) Å] bond distances compare well
with the reported values [43].
Fig. 3. Molecular structure of 5. Thermal ellipsoids are drawn at 50% probability level. All
hydrogen atoms are omitted for clarity.
As revealed by single-crystal X-ray diffraction analysis, complexes 4, 6, 7, 11 and 12 are
isostructural, differ only in the bridging atoms and bisphosphine ligands. These complexes
are characterized by a rhombic [Cu
each copper(I) ion. The copper(I) and the µ
which each copper(I) and halide ions occupy opposite corners. The planes formed by the
Cu {µ -X }] core and phosphorus atoms coordinated to the copper(I) centre are orthogonal
2
{µ
2
-X
2
}] structural unit with bisphosphines chelated to
2
-halide ions form a distorted square plane, in
[
2
2
2
to each other.
The Cu−Br bond distances [2.488(3) Å and 2.509(3) Å] in 11 (Fig. 6) are similar to those
in 5 and other related structures. The Cu1−P1 [2.262(5) Å] and Cu1−P2 [2.278(5) Å] bond
7

distances differ slightly, but are longer than those in 5. The Cu−I bond distances in case of 6
and 12 (Fig. 4) are almost similar [2.662(1) Å, 2.678(1) Å for 6 and 2.649(3) Å, 2.682(3) Å
for 12]. The two Cu−P bond distances in 12 are nearly the same [Cu1−P1 = 2.289(6) Å,
Cu1−P2 = 2.281(2) Å], but differ marginally in case of 6 [Cu1−P1 = 2.300(2) Å, Cu2−P2 =
2
.284(2) Å]. The Cu−P bond distances are longer than those found in copper(I) iodide
complexes of P∩N heterocyclic ligands [37a,b] based on substituted triazole and pyridine
(P∩N) Cu Cu
; (P∩N) ] [2.253(1)−2.251(1) Å; 2.240(9)−2.265(13) Å], but are
comparable with those in complex [(P∩P) Cu ] [2.283(1) Å, 2.275(1) Å] obtained during
[
3
2
I
2
3
2 2
X
2
2 2
I
the rearrangement of 1-benzyl-5-(diphenylphosphino)-1H-tetrazole on reaction with
copper(I) iodide [37a].
Fig. 4. Molecular structures of 6 and 12. Thermal ellipsoids are drawn at 50% probability
level. All hydrogen atoms are omitted for clarity.
8

Fig. 5. Molecular structures of 4 and 7. Thermal ellipsoids are drawn at 50% probability
level. All hydrogen atoms are omitted for clarity.
The two Cu−Cl bond lengths in case of 4 and 7 (Fig. 5) are 2.381(1) Å, 2.391(1) Å and
2
.342(8) Å, 2.396(9) Å. One of the Cu−Cl bond lengths in 7 is shorter but are within the
range of Cu−Cl bond distances of the related structures [41a,44]. The Cu1−P1 and Cu1‒P2
bond lengths in 4 and 7 [2.249(1) Å, 2.267(1) Å and 2.243(8) Å, 2.268(9) Å] are in good
I
agreement with the literature values reported for the same in tetracoordinated Cu
bisphosphine complexes [16].
The bite angle of the chelating bisphosphines in 4, 6, 7, 11 and 12 are in the range of
1
10.15(9)°−114.39(5)° and are closer to the values required for tetrahedral geometry.
However, as expected, these P1−Cu1−P2 bond angles are larger than the P1−Cu1−P2 angles
found in analogous six-membered chelate complexes of bisphosphines [41a,45] but are
comparable with those in eight-membered chelate complexes of the type [Cu
dppf) ] [46].
2 2
(µ-X) (µ-
2
9

Fig. 6. Molecular structure of 11. Thermal ellipsoids are drawn at 50% probability level. All
hydrogen atoms are omitted for clarity.
Fig. 7. Molecular structure of 10. Thermal ellipsoids are drawn at 50% probability level. All
hydrogen atoms are omitted for clarity.
Fig. 8. 1D polymeric view of 10. Thermal ellipsoids are drawn at 50% probability level. All
hydrogen atoms are omitted for clarity.
The molecular structure of 10 consists of a polymeric [{Cu
2
(µ-Cl) (µ-P∩N)}] core, with 3
2
2
exhibiting both chelating (κ -P,N) and bridging (µ-P,N) modes of coordination as shown in
1
0

Fig. 7. Though 1D copper(I) coordination polymers with various N-donor ligands have been
reported [26,47], complex 10 is a rare example of 1D copper(I) polymer containing
bisphosphine with two coordinating modes (Fig. 8). The Cu−P bond distances [Cu1−P1 =
2
.187(6) Å, Cu2−P2 = 2.193(6) Å] are shorter than those observed in chloro-bridged
complexes 4, 7 and also complexes of triazole and pyridyl based monophosphines [37a,b].
The Cu−Cl bond distances [Cu1−Cl1 = 2.315(6) Å, Cu1−Cl2 = 2.391(6) Å, Cu2−Cl1 =
2
.376(6) Å, Cu2−Cl2 = 2.348(6) Å] differ significantly but are in good agreement with the
reported values in [Cu (µ-Cl) (µ-dppp) ] and [Cu (µ-Cl) (µ-dppf)
2
2
2
2
2
2
] [41a,46]. The Cu−N
bond distances [Cu1−N5 = 2.068(2) Å, Cu1−N2 = 2.089(2) Å] are shorter than those found in
copper(I) complexes of phosphane-substituted pyridine heterocycles [37b], but are
comparable with those of triazole based monophosphines [37a]. The P1−Cu1−N5
[
112.78(6)°] and P2−Cu2−N7 [113.09(6)°] bond angles indicate the distorted tetrahedral
geometry around the copper and are closer to the values of 4, 6, 7, 11 and 12, where both the
phosphorus atoms are coordinated to the same metal atom. The two adjacent [Cu(µ-Cl) Cu]
2
planes are almost orthogonal to each other.
The Cu···Cu distances in 4, 6, 7, 11 and 12 are in the range of 3.00−3.343 Å, which are
slightly longer than those found in five- and six-membered chelate complexes Cu (µ-X) (µ-
dppb) (µ-X) (µ-dppp)
[2.837−2.898 Å] [12] and Cu [3.0314−3.1017 Å ] [41a], but are
shorter than the same observed in Cu (µ-X) (µ-dppf) [3.218−3.331 Å] [46]. This is probably
2
2
2
2
2
2
2
2
2
due to the less steric constraints in the complexes of the large-bite ligands as compared to the
short-bite ligands. The Cu···Cu distances have remarkable influence on the luminescence
properties of the copper halide clusters [48], however, these complexes have been found to be
non-emissive at room temperature both in solution as well as in the solid state.
2
The coordination polymer [Cu
2
(µ-Cl)
2
{CH
2
(1,2,4-C
2
HN
3
PPh
2
)
2
}-κ P,N]
n
(10) shows C–
H···Cl [C26–H···Cl1 (2.868 Å, 133°) and C3–H···Cl2 (2.637 Å, 161°)] type of hydrogen
1
1

2
bonding interactions. In case of [Cu
2
(µ-Cl)
2
{CH
2
(1,3-C
3
H
2
N
2
PPh
2
)
2
}
2
-κ P,P] (4), [Cu
2
(µ-
2
2
Br)
2
{CH
2
(1,3-C
3
H
2
N
2
PPh
2
)
2
}
2
-κ P,P] (6) and [Cu
2
(µ-I)
2
{CH
2
(1,2,4-C
2
HN
3
PPh
2
)
2
}
2
-κ P,P]
(
12), slipped π‒π stacking interactions are observed between C3···C4 and C23···C24 atoms
of phenyl rings of adjacent molecules with a closest C···C distance of 3.3789 Å, which fits
well in to the ideal phenyl-phenyl π‒π stacking interaction in the range of 3.3–3.8 Å [49]. In
2
[
Cu
2
(µ-Br)
2
{CH
2
(1,2,4-C
2
HN
3
PPh
2
)
2
}
2
-κ P,P] (11), CH···π [C16–H16···C5 (2.876 Å)]
interactions are observed along with C15–H15···N5 (2.435 Å, 164°) hydrogen bonding
interactions.
3
. Conclusions
Reaction of bis(azol-1-yl)methane based bisphosphine systems with copper(I) halides
showed preferential formation of dinuclear complexes with halide bridged rhombic [Cu
2
(µ-
X) ] core. However, the reaction of bis(5-diphenylphosphino-1,2,4-triazol-1-yl)methane with
2
CuCl afforded a novel 1D coordination polymer with the ligand showing P,N coordination,
whereas bis(2-diphenylphosphinoimidazol-1-yl)methane with CuBr produced a simple
mononuclear chelate complex with the fourth coordination site on copper being occupied by
an acetonitrile molecule.
4
. Experimental
4
.1. General procedures
All experimental manipulations were performed in oven-dried glassware using standard
Schlenk techniques under nitrogen atmosphere. Solvents were dried under standard
conditions. The compounds, bis(azol-1-yl)methanes [50], CuBr and CuCl [51] were prepared
according to the published procedures. CuI was purchased from Aldrich chemicals and used
as such without further purification. Other chemicals were obtained from commercial sources
1
31
1
13
and purified prior to use. The H, P{ H} and C NMR spectra were recorded at frequencies
4
00, 100 and 162 MHz, respectively, using Bruker AV 400 and 500 spectrometers. The
1
2

spectra were recorded in CDCl
3
6 3 6
(or DMSO–d ) solutions with CDCl (or DMSO–d ) as an
1
13
internal lock; chemical shifts of H and C NMR spectra are reported in ppm downfield from
3
1
1
TMS, used as an internal standard. The chemical shifts of P{ H} NMR spectra are referred
to 85% H PO as an external standard. The microanalyses were performed using Carlo Erba
Model 1112 elemental analyser. Mass spectra were recorded using Waters Q-Tof micro (YA-
3
4
1
05). The melting points were observed in capillary tubes and are uncorrected. The electronic
I
absorption spectra of free ligands 1‒3 and their Cu complexes 4−9, 11 and 12 were recorded
−5
in 10 M solution in dichloromethane at room temperature on a Perkin Elmer UV‒vis
spectrometer.
2
4
.2. Synthesis of [(CuCl)
2
{CH
2
(1,3-C
3
H
2
N
2
PPh
2
)
2
}
2
-κ P,P] (4)
A solution of cuprous chloride (5.8 mg, 0.058 mmol) in acetonitrile (10 mL) was added
dropwise to a well stirred solution of 1 (30 mg, 0.058 mmol) in dichloromethane (10 mL) at
room temperature with constant stirring. After stirring for 6 h, the solvent was removed under
reduced pressure and the residue obtained was further washed with petroleum ether to give 4
as white solid product. Yield: 71% (50 mg, 0.04 mmol). Mp: 215−219 °C. Anal. Calc. for
1
C
62
H
52
N
8
P
4
Cu
400 MHz, DMSO-d
DMSO-d ): δ −32.6 (s). HRMS (ESI): m/z = 579.09 (M−Cl).
.3. Synthesis of [CuBr(CH CN){CH (1,3-C PPh }-κ P,P] (5)
2
Cl
2
: C, 60.49; H, 4.26; N, 9.10. Found: C, 60.20; H, 4.17; N, 8.85%. H NMR
4
5
31
1
(
6 2
): δ 7.20−7.84 (m, 26H, Ar, CH , H , H ). P{ H} NMR (162 MHz,
6
2
4
3
2
3
H
2
N
2
2 2
)
This was prepared in an analogous manner similar to 4, using cuprous bromide (8.3 mg,
.058 mmol) and 1 (30 mg, 0.058 mmol). Yield: 73% (58 mg, 0.08 mmol). Mp: 237−240 °C.
0
Anal. Calc. for C33
H
29
N
5
P
2
CuBr: C, 56.54; H, 4.17; N, 9.99. Found: C, 56.49; H, 4.22; N,
): δ 2.01 (s, 3H, CH CN), 7.22−7.84 (m, 26H, Ar,
): δ −32.5 (s). HRMS (ESI): m/z = 579.09
1
9
.65%. H NMR (400 MHz, DMSO-d
6
3
4
5
31
1
CH
2
, H , H ). P{ H} NMR (162 MHz, DMSO-d
6
(
M−Br).
1
3

2
4
2 2 3 2 2 2 2 2
.4. Synthesis of [(CuI) {CH (1,3-C H N PPh ) } -κ P,P] (6)
This was prepared in an analogous manner similar to 4, using cuprous iodide (11 mg, 0.058
mmol) and 1 (30 mg, 0.058 mmol). Yield: 69% (55 mg, 0.04 mmol). Mp: 235−238 °C. Anal.
Calc. for C62
H
52
N
8
P
4
Cu
2
I
2
·2CH CN: C, 52.99; H, 3.91; N, 9.36. Found: C, 53.02; H, 3.59; N,
3
1
4
5
31
1
9
.02%. H NMR (400 MHz, DMSO-d
6
): δ 7.21−7.87 (m, 26H, Ar, CH , H , H ). P{ H}
2
NMR (162 MHz, DMSO-d
6
): δ −32.5 (s). HRMS (ESI): m/z = 579.09 (M−I).
2
4
.5. Synthesis of [(CuCl)
2
{CH
2
(1,2-C
3
H
2
N
2
PPh
2
)
2
}
2
-κ P,P] (7)
This was prepared in an analogous manner similar to 4, using cuprous chloride (5.8 mg,
.058 mmol) and 2 (30 mg, 0.058 mmol). Yield: 77% (54 mg, 0.044 mmol). Mp: >280 °C.
0
Anal. Calc. for C62
H
52
N
8
P
4
Cu
2
Cl
2
·1.5CH
2
Cl
2
: C, 56.14; H, 4.08; N, 8.24. Found: C, 56.25;
): δ 5.29 (s, 3H, CH Cl ), 5.64 (br s, 2H,
1
H, 4.17; N, 8.25%. H NMR (400 MHz, DMSO-d
6
2
2
4
3
31
1
H ), 7.02−7.72 (br m, 22H Ar, CH
2
6
, H ). P{ H} NMR (162 MHz, DMSO-d ): δ −32.5 (s).
HRMS (ESI): m/z = 579.09 (M−Cl).
2
4
.6. Synthesis of [(CuBr)
2
{CH
2
(1,2-C
3
H
2
N
2
PPh
2
)
2
}
2
-κ P,P] (8)
This was prepared in an analogous manner similar to 4, using cuprous bromide (8.3 mg,
.058 mmol) and 2 (30 mg, 0.058 mmol). Yield: 70% (53 mg, 0.04 mmol). Mp: >280 °C.
0
Anal. Calc. for C62
H
52
N
8
P
4
Cu
2
Br
2
·CH
2
Cl
2
: C, 53.86; H, 3.87; N, 7.98. Found: C, 54.18; H,
1
4
3
.77; N, 8.24%. H NMR (400 MHz, DMSO-d
6
): δ 5.6 (br s, 2H, H ), 6.9−7.60 (br m, 22H
3
31
1
Ar, CH
2
, H ). P{ H} NMR (162 MHz, DMSO-d
6
): δ −32.2 (s). HRMS (ESI): m/z = 579.09
(
M−Br).
2
4
.7. Synthesis of [(CuI)
2
{CH
2
(1,2-C
3
H
2
N
2
PPh
2
)
2
}
2
-κ P,P] (9)
This was prepared in an analogous manner similar to 4, using cuprous iodide (15 mg, 0.077
mmol) and 2 (40 mg, 0.077 mmol). Yield: 61% (60 mg, 0.042 mmol). Mp: >280 ⁰C. Anal.
1
4

1
Calc. for C62
52 8 4 2 2
H N P Cu I : C, 52.67; H, 3.71; N, 7.92. Found: C, 52.3; H, 3.89; N, 8.05%. H
4
3
NMR (400 MHz, DMSO-d
6
2
): δ 5.66 (d, 2H, H ), 7.02−7.52 (br m, 22H Ar, CH , H ).
3
1
1
P{ H} NMR (162 MHz, DMSO-d
6
): δ −32.8 (s). HRMS (ESI): m/z = 579.09 (M−I).
2
4
.8. Synthesis of [(CuCl)
2
{CH
2
(1,2,4-C
2
HN
3
PPh2)
2
}-κ P,N]
n
(10)
This was synthesized by the procedure similar to that for 4, using cuprous chloride (5.7
mg, 0.058 mmol) and 3 (30 mg, 0.058 mmol). Yield: 72% (50 mg, 0.07 mmol). Mp: >280 °C.
Anal. Calc. for C29
H24Cu
2
Cl
2
N
6
P
2
: C, 48.61; H, 3.37; N, 11.73. Found: C, 48.56; H, 3.26; N,
1
3
1
1.65%. H NMR (400 MHz, DMSO-d
6
): δ 8.2 (s, 2H, H ), 7.35−7.43 (br m, 22H, CH
2
, Ar).
3
1
1
P{ H} NMR (162 MHz, DMSO-d
6
): δ −32.5 (s). HRMS (ESI): m/z = 581.08 (M−Cl).
2
4
.9. Synthesis of [{Cu(µ-Br)}
2
{CH
2
(1,2,4-C
2
HN
3
PPh2)
2
}
2
-κ P,P] (11)
This was synthesized by the procedure similar to that for 4, using cuprous bromide (8.3
mg, 0.058 mmol) and 3 (30 mg, 0.058mmol). Yield: 68% (52 mg, 0.04 mmol). Mp: >280 °C.
Anal. Calc. for C58H48Cu
2
Br
2
N
12
P
4
: C, 52.61; H, 3.65; N, 12.69. Found: C, 52.85; H, 3.53; N,
1
3
1
2.32%. H NMR (400 MHz, DMSO-d
6
): δ 8.2 (s, 2H, H ), 7.35−7.43 (br m, 22H, CH
2
, Ar).
3
1
1
P{ H} NMR (162 MHz, DMSO-d
6
): δ −32.6 (s). MS (ESI): m/z = 581.08 (M−Br).
2
4
.10. Synthesis of [{Cu(µ-I)}
2
{CH
2
(1,2,4-C
2
HN
3
PPh
2
)
2
}
2
-κ P,P] (12)
This was synthesized by the procedure similar to that for 4, using cuprous iodide (15 mg,
.077 mmol) and 3 (40 mg, 0.077 mmol). Yield: 62% (62 mg, 0.044 mmol). Mp: >280 °C.
0
Anal. Calc. for C58
H
48
N
12
P
4
Cu
2
I
2
·2CH
3
CN: C, 49.64; H, 3.63; N, 13.07. Found: C, 49.83; H,
1
3
3
.27; N, 13.01%. H NMR (400 MHz, DMSO-d
6
): δ 8.2 (s, 2H, H ), 7.35−7.43 (br m, 22H,
3
1
1
CH
2
, Ar), 2.13 (s, 6H, CH
3 6
CN). P{ H} NMR (162 MHz, DMSO-d ): δ −31.8 (s). HRMS
(
ESI): m/z = 581.08 (M−I).
4
.11. X-ray Crystallography
1
5

Suitable single crystals of 4−7 and 10−12 for X-ray diffraction were obtained from
solvents mentioned in their respective synthetic procedures. Single crystal X-ray diffraction
data collections were performed at 100‒150 K temperature using Bruker Smart APEX CCD
diffractometer with graphite monochromated Mo-Kα radiation source. Full spheres of data
were collected using a combination of three sets of 400 frames (0.5° width in ω) at φ = 0, 90,
and 180° plus two sets of 800 frames (0.45° width in ω) at φ = −30, and 210° under the
2
control of the APEX2 program suite [52]. The raw data were reduced to F values using the
SAINT software [53], and global refinements of unit cell parameters using 4335−10179
reflections chosen from the full data sets were performed. Multiple measurements of
equivalent reflections provided the basis for empirical absorption corrections as well as
corrections for any crystal deterioration during the data collection (SADABS) [54]. The
structures were solved by direct methods, and refined by full-matrix least-squares procedures
using the SHELXTL program package [55,56]. Hydrogen atoms were placed in calculated
positions and included as riding contributions with isotropic displacement parameters tied to
those of the attached non-hydrogen atoms.
Acknowledgements
The work was supported by CSIR, New Delhi, India. S.A.B thanks I.I.T. Bombay for
Research Fellowship. We also thank the Department of Chemistry Instrumentation Facilities,
IIT Bombay, for spectral and analytical data. J.T.M thanks the Louisiana Board of Regents
for the purchase of the CCD diffractometer and the Chemistry Department of Tulane
University for support of the X-ray laboratory.
Appendix A. Supplementary material
Electronic Supplementary Information (ESI) available: CCDC 1408419 (4), 1408418 (5),
1
408422 (6), 1408423 (7), 1044938 (10), 1044939 (11) and 1044940 (12) contains the
1
6

supplementary Crystallographic data. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
Supplementary data associated with this article can be found, in the online version, at
http://dx.doi.org/10.1016/j.ica.2015.xx.xxx.
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2
1

Table 1
Selected Distances (Å) and Angles (°) for Complexes 4 - 7.
4
5
6
7
Cu1−P1
Cu1‒P2
Cu1‒X1
Cu1`‒X1`
Cu−NCCH
Cu···Cu
X···X
2.249(1)
2.236(1)
2.300(2)
2.243(8)
2.267(1)
2.381(1)
2.391(1)
2.252(1)
2.484(7)
2.284(2)
2.662(1)
2.678(1)
2.268(9)
2.342(8)
2.396(9)
3
2.002(3)
3.135
3.595
3.343
3.343
3.090
3.593
1
8
9
14.39(5)
2.18(4)
108.86(3)
111.50(3)
81.40(3)
98.60(3)
P1‒Cu1‒P2
Cu‒X‒Cu
X‒Cu‒X
110.15(9)
77.51(3)
102.49(4)
7.829(5)
Table 2
Selected Distances (Å) and Angles (°) for Complexes 10, 11 and 12.
1
0
11
2.262(5)
12
2.289(6)
Cu1‒P1
2.187(6)
2.193(6)
2.068(2)
2.089(2)
2.315(6)
2.348(6)
112.78(6)
113.09(6)
Cu1–P1
Cu2‒P2
Cu1–P2
2.278(5)
2.488(3)
2.509(3)
112.47(2)
103.29(1)
2.281(6)
2.649(3)
2.682(3)
111.45(2)
108.39(1)
Cu1–N5
X1–Cu1
Cu2–N2
X1´–Cu1´
P1–Cu1–P2
X–Cu1–X
Cu1–Cl1
Cu2–Cl2
P1–Cu1–N5
P2–Cu2–N2
Cu–X–Cu
Cu···Cu
X···X
76.71(1)
3.101
71. 61(1)
3.119
Cu···Cu
X···X
3.016
3.620
3.919
3.593
2
2

Table 3
Crystallographic Data for 4‒7.
4
5*
6
7
Empirical formula
C
62
H52Cl
2
Cu
2
N
8
P
4
C
33
29
H N
5
P
2
BrCu
C
62
H52Cu
2
I
2
N
8
P
4
C
62
H52Cl
2 2 8 4
Cu N P
2
3
(CH CN)
2
1.5 CH Cl
2
Fw
1230.98
Monoclinic
C2/c (No. 15)
24.864(6)
12.747(3)
23.576(5)
90
121.454(3)
90
6374(3)
4
710.00
Monoclinic
P2 (No. 4)
11.276(3)
12.724(3)
11.925(3)
90
114.838(3)
90
1522.7(7)
2
1495.98
Monoclinic
1358.36
Triclinic
P-1 (No. 2)
12.1338(11)
12.9400(12)
13.0276(12)
114.2810(13)
93.4290(14)
116.2980(14)
1596.6(3)
1
Cryst. System
Space group
a, Å
b, Å
c, Å
1
P2
1
/n (No. 14)
15.266(4)
15.128(4)
15.339(4)
90
118.795(3)
90
3116.6(14)
2
1.594
α, deg
β, deg
γ, deg
3
V, A
Z
-
3
Dcalc, g cm
1.283
0.895
2528
1.499
2.125
712
1.413
1.022
695
-
1
µ (Mo Ka), mm
F(000)
1.826
1496
crystal size, mm
T(K)
0.06, 0.15, 1.01
100
0.04 x 0.12 x 0.15
100
0.04 x 0.04 x 0.1
150
0.0x0.11x0.11
150
2
θ
range, deg
1.9 - 26.4
24810
1.9 - 28.5
13582
2.0 - 27.6
75345
1.9-29.1
29441
total no. Reflns
no. Of indep reflns
6505
6881
7170
8231
S
1.01
0.98
1.04
1.03
R
wR
l
0.0615
0.1494
0.0347
0.0740
0.0799
0.1845
0.0457
0.1276
2
*
x = 0.011(6) [flack parameter]
2
3

Table 4
Crystallographic Data for 10‒12.
1
0
11
Cu
12
Cu
CN
Empirical formula
C
29
H24Cl
2
Cu
2
N
6
P
2
C
58
H
48Br
2
2
N
12 4
P
C
58
H
48
I
2
2 12 4
N P
·
2CH
3
Fw
716.46
Triclinic
1323.86
Triclinic
1499.95
Triclinic
P-1 (No. 2)
12.0936(9)
12.2956(9)
13.2087(10)
66.250(1)
63.218(1)
87.3780(11)
1582.6(2)
1
Cryst. System
Space group
a, Å
b, Å
c, Å
α, deg
β, deg
γ, deg
V, A
Z
P-1 (No. 2)
8.7677(2)
9.2358(2)
20.6189(5)
80.5050(7)
83.9390(9)
82.7860(8)
1627.58(6)
2
P-1 (No. 2)
12.1743(8)
12.2027(1)
13.2886(9)
65.2460(9)
63.244(1)
88.1370(11)
1570.90(2)
1
3
-
3
Dcalc, g cm
1.462
4.281
724
1.399
2.096
668
1.574
1.800
748
-
1
µ (Mo Ka), mm
F(000)
crystal size, mm
T(K)
0.03 x 0.12 x 0.22
101
0.07 x 0.15 x 0.15
150
0.13 x 0.24 x 0.28
100
2
θ range, deg
4.4-72.6
20683
1.9-29.2
28955
1.8-29.2
29173
total no. Reflns
no. Of indep reflns
6067
8109
8201
S
1.07
1.04
1.05
R
wR
l
0.0352
0.0938
0.0303
0.0772
0.0296
0.0785
2
2
4

Highlights
•
Copper chemistry of bis(1,2,4-triazol-1-yl)methane, bis(imidazol-1-yl)methane and
bis(pyrazol-1-yl)methane derived bis(phosphines) has been described
Ligands show both bridging and chelating coordination modes
Ligands show both phosphorus and nitrogen coordination
1D-coordination polymer with P- and N-coordination has been structurally
characterized
•
•
•
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5

Synopsis for contents page
Synthesis and structural characterization of copper(I) halide complexes
containing bis(azol-1-yl)methane derived bisphosphines
Sajad A. Bhat, Joel T. Mague, Maravanji S. Balakrishna
Synopsis for contents page
Synthesis and structural characterization of copper(I) halide complexes
containing bis(azol-1-yl)methane derived bisphosphines
Sajad A. Bhat, Joel T. Mague, Maravanji S. Balakrishna
2
6

This paper describes the synthesis and structural characterization of copper(I) halide
complexes of bis(1,2,4-triazol-1-yl)methane, bis(imidazol-1-yl)methane and bis(pyrazol-1-
yl)methane derived bisphosphines.
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7