Copper(I) complexes of 2-methoxy-(5-trifluoromethyl-phenyl)-pyridine-2yl-methylene-amine: Impact of phosphine ancillary ligands on luminescence and catalytic properties of the copper(I) complexes

Article abstract of DOI:10.1016/j.poly.2015.11.050

Some copper(I) complexes of the type [Cu(L)(PPh₃)₂]X (X = Cl (1a), CN (1b), ClO₄ (1c), BF₄ (1d)) and [Cu(L)(dppe)]X (X = Cl (2a), CN (2b), ClO₄ (2c) and BF₄ (2d)) [where L = 2-methoxy-(5-trifluoromethyl-phenyl)-pyridine-2yl-methylene-amine; PPh₃ = triphenylphosphine; dppe = 1,2-bis(diphenylphosphino)ethane] have been prepared and characterized on the basis of elemental analyses, IR, UV-Vis, ¹H NMR and ³¹P NMR spectral studies. The representative complex of the series 1d and 2c are characterized by single crystal X-ray diffraction which reveal that, in each complex the central copper(I) ion assumes the irregular pseudo-tetrahedral geometry. All the complexes display a weak MLCT that varies considerably with phosphine ligands. Quasireversible redox behavior is accounted for all complexes corresponding to Cu(I)/Cu(II) couple and is sensitive to phosphine ligands. All the complexes exhibit blue-green emission originate from intra-ligand charge transfer (ILCT), ligand to ligand charge transfer (LLCT) transitions or mixture of them and vary markedly with the phosphine ligands. The copper(I) complexes with dppe ancillary ligand shows greater activity for the amination of iodobenzene as compared to PPh₃ ancillary ligand in the complexes.

Full text of DOI:10.1016/j.poly.2015.11.050

Accepted Manuscript
Copper(I) Complexes of 2-methoxy-(5-trifluoromethyl-phenyl)-pyridine-2yl-
methlyeneamine: Impact of Phosphine Ancillary Ligands on Luminescence and
Catalytic Properties of the Copper(I) Complexes
S.S. Chavan, S.K. Sawant, S.B. Pawal, M.S. More
PII:
S0277-5387(15)00745-7
DOI:
http://dx.doi.org/10.1016/j.poly.2015.11.050
POLY 11696
Reference:
To appear in:
Polyhedron
Received Date:
Accepted Date:
31 October 2015
29 November 2015
Please cite this article as: S.S. Chavan, S.K. Sawant, S.B. Pawal, M.S. More, Copper(I) Complexes of 2-methoxy-
5-trifluoromethyl-phenyl)-pyridine-2yl-methlyeneamine: Impact of Phosphine Ancillary Ligands on
Luminescence and Catalytic Properties of the Copper(I) Complexes, Polyhedron (2015), doi: http://dx.doi.org/
0.1016/j.poly.2015.11.050
(
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Copper(I) Complexes of 2-methoxy-(5-trifluoromethyl-phenyl)-pyridine-2yl-
methlyeneamine: Impact of Phosphine Ancillary Ligands on Luminescence and
Catalytic Properties of the Copper(I) Complexes
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S. S. Chavan*, S. K. Sawant, S. B. Pawal, M. S. More
Department of Chemistry, Shivaji University, Kolhapur (MS) India-416004
Abstract
Some copper(I) complexes of the type [Cu(L)(PPh
and [Cu(L)(dppe)]X (X= Cl (2a), CN (2b), ClO
trifluoromethyl-phenyl)-pyridine-2yl-methylene-amine; PPh
(diphenylphosphino)ethane] have been prepared and characterized on the basis of elemental
3 2
)
]X (X= Cl (1a), CN (1b), ClO
(2c) and BF (2d)) [where L = 2-methoxy-(5-
=triphenylphosphine; dppe=1,2-bis
4 4
(1c), BF (1d))
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analyses, IR, UV-visible, H NMR and P NMR spectral studies. The representative complex of
the series 1d and 2c are characterized by s
ingle crystal X-ray diffraction which reveal that, in each complex the central copper(I) ion assumes
the irregular pseudo-tetrahedral geometry. All the complexes display a weak MLCT that varies
considerably with phosphine ligands. Quasireversible redox behaviour is accounted for all
complexes corresponding to Cu(I)/Cu(II) couple and is sensitive to phosphine ligands. All the
complexes exhibit blue-green emission originate from intra-ligand charge transfer (ILCT), ligand to
ligand charge transfer (LLCT) transitions or mixture of them and vary markedly with the phosphine
ligands. The copper(I) complexes with dppe ancillary ligand shows greater activity for the
3
amination of iodobenzene as compared to PPh ancillary ligand in the complexes
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Keywords: Copper(I) complexes; X-ray diffraction; Photoluminescence, Amination of iodobenzene
Corresponding author Tel.: +91 231 2609381; fax: +91 231 2691533.
E-mail: sanjaycha2@rediffmail.com

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1. Introduction
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The monovalent copper(d ) chemistry have drawn special attention because of its instability,
unusual structural features, utility in solar energy and supramolecular devices, luminescent
material, catalysis and biological relevance [1-5]. They are being environmentally friendly, less
expensive, intriguing coordination modes and exhibit rich photochemical and photophysical
properties. Due to the favourable soft acid-soft base interaction, the coordination chemistry of
1
0
this closed-shell d metal ion is largely based upon the coordination of the ligands such as N,
P, S and halide donor ligands. The steric, electronic and conformational effects imparted by
these ligands play an essential role in stabilizing the copper(I) state and modifying the physical
and chemical properties of the prepared complexes. Copper(I) complexes particularly with
N,N-donor ligands are of growing interest as most of these complexes possesses remarkable
features like ease of preparation, electrochemical behaviour, light absorption in the visible
region, characteristic structural flexibility, supramolecular architecture, long-lived electronically
excited states and intense luminescence [6-9]. The formation of these complexes can be related
with experimental conditions of their synthesis, structure of ligands and also metal-ligand
interaction. The copper(I) complexes with phosphorous containing ligands are used to carry
wide range organic transformations such as allylic amination, hydrogenation, copolymerization,
cross coupling reactions etc. [10-14]. The steric crowding and π–acidic character imparted by these
ligands are most important prerequisites for stabilizing the copper(I) complexes and their
redox, photophysical and catalytic behaviour. Compared to monophosphines, bis(phosphine) are
the most versatile phosphine ligands capable of binding to the metal ion in variety of ways:
monodentate, chelating or bridging. They possess high covalency as well as ligand field effects to
enforce the drastic change in electronic and other behaviour of the resulting compounds[15].
In order to understand these facts we report here the ligational behaviour of 2-methoxy-(5-trifluoro
methyl-phenyl)-pyridine-2yl-methylene-amine with copper(I) in presence of triphenylphosphine
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3
(PPh ) or 1,2-bis(diphenylphosphino)ethane (dppe) as coligand and to study the impact of secondary
ligand (PPh
3
or dppe) on the catalytic and luminescence behaviour of the prepared complexes.

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Some mixed ligand complexes of the type [Cu(L)(PPh
3
) ]X (1a-d) and [Cu(L)(dppe)]X (2a-d)
2
have been prepared and characterized by physico-chemical and spectroscopic techniques (IR,
1
31
UV-visible, H NMR and P NMR spectral studies) and compound 1d and 2c by X-ray
crystallography. The luminescence behaviour and thermal stability of the complexes have been
studied. The catalytic performance of all the copper(I) complexes in the amination of
iodobenzene has also been discussed.
2. Experimental
2.1 Materials and methods
2-methoxy-(5-trifluoromethyl-phenyl)-pyridine-2yl-methylene-amine (L) was prepared by
previously reported procedure [16]. The reagents used in synthesis were of reagent grade and used
without further purification. The copper(I) compounds CuCl [17], Cu(MeCN)
4 4
]ClO [18] and
[Cu(MeCN) ]BF [18] were prepared according to the literature procedure.
4
4
Elemental analyses (C, H and N) of the copper(I) complexes were conducted on Thermo Finnegan
FLASH EA-1112 CHNS analyzer. IR spectra were recorded on a Perkin-Elmer-100 FTIR
1
Spectrometer, H NMR spectra of the samples dissolved in CDCl
3
were measured on a AMX 400
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MHz instrument using TMS[(CH
3
) Si] as an internal standard of chemical shifts (ppm). P NMR
4
spectra were recorded using a Varian Mercury-300 FT-NMR spectrometer. The UV-Vis
-4
absorption spectra were recorded in dichloromethane (10 M) on Shimadzu 3600 UV-Vis-NIR
spectrophotometer. Mass spectra were measured on GCMS Shimadzu-2010. Emission spectra
were measured using a Perkin-Elmer LS 55 spectrofluorometer equipped with quartz cuvette of
3
1 cm path length at room temperature. Luminescence lifetime measurements were carried out by
using time-correlated single photon counting from HORIBA Jobin Yvon. Thermal analysis of the
complexes was carried out on a Perkin-Elmer thermal analyzer in nitrogen atmosphere at a heating
rate of 10 °C/min
2.2 Synthesis
3 2
2.2.1. Preparation of [Cu(L)(PPh ) ]Cl(1a)
To a solution of CuCl (1 mmol, 0.098 g) in 10 ml acetonitrile was added a solution of two
equivalent of triphenylphosphine (2 mmol, 0.522 g). The reaction mixture was stirred for 30 min.

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at room temperature under nitrogen atmosphere and allowed to evaporate slowly. The
crystalline product [Cu(MeCN) (PPh ]Cl obtained was subsequently added to a stirring
2
)
3 2
solution of 2-methoxy-(5-trifluoromethyl-phenyl)-pyridine-2yl-methyleneamine (L) (1 mmol,
0.280 g) in 10 ml dichloromethane. The mixture was stirred at room temperature for 2h and
then the solution was evaporated to small volume under vacuum. The light yellow coloured
complex was developed by diffusion of diethyl ether into the filtrate.
Yield 84%, M.P. 167 ºC; Elemental analyses (C, H and N, wt %) Anal. Calc. For C50
H
41ClCuF
3
N
2
OP
2
:
-1
C, 66.44; H, 4.57; N, 3.10; Found: C, 66.74; H, 4.59; N, 3.11; IR (KBr) (cm ): 1585, υ(HC=N);
3
-1
-1
1480, 1434, 694, 516, υ(PPh
3
); UV-vis (CH
) (400 MHz): δ 9.10 (s, HC=N), δ 3.80 (s, OCH
).
]CN (1b)
2
Cl
2
) λmax (nm) (ε x10 , M cm ): 284 (12.4), 296
1
(9.3), 442 (1.8); H NMR (CDCl
3
3
), δ 6.77-
31
93
94
95
96
97
98
99
9.00 (m, Ar-H); P NMR: δ 1.76 (s, PPh
3
2.2.2. Preparation of [Cu(L)(PPh
3 2
)
Complex 1b was prepared similar to the procedure performed in the preparation of 1a except
that CuCl was replaced by CuCN (1 mmol, 0.089 g)
Yield 87%, M.P. 163 ºC; Elemental analyses (C, H and N, wt %) Anal. Calc. For C51
H
41CuF
3
N
3
2
OP :
-1
C, 68.49; H, 4.62; N, 4.70; Found: C, 68.58; H, 4.60; N, 4.72; IR (KBr) (cm ): 1584, υ(HC=N);
3
-1
-1
1480, 1435, 694, 516, υ(PPh
3
); 2108, υ(C≡N); UV-vis (CH
2
Cl
) (400 MHz): δ 9.12 (s, HC=N), δ 3.79 (s, OCH
δ 6.77-8.33 (m, Ar-H); P NMR: δ 1.76 (s, PPh ).
2.2.3. Preparation of [Cu(L)(PPh ]ClO (1c)
Complex 1c was prepared similar to the procedure performed in the preparation of 1a except
that CuCl was replaced by [Cu(MeCN) ]ClO (1 mmol, 0.327 g).
3 2 5 2
Yield 85%, M.P. 154ºC; Elemental analyses (C, H and N, wt %) Anal. Calc. For C50 41ClCuF N O P :
2
) λmax (nm)(ε x 10 , M cm ): 288
1
1
00
(13.2), 306 (9.2), 448 (1.7); H NMR (CDCl
3
3
),
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3
3
)
2
4
4
4
H
-1
C, 62.05; H, 4.27; N, 2.89; Found: C, 61.46; H, 4.84; N, 2.92; IR (KBr) (cm ): 1587, υ(HC=N)
3
-1
-1
1480, 1435, 694, 516, υ(PPh3); 1094, 623 υ(ClO
4
); UV-vis (CH
) (400 MHz): δ 9.12 (s, HC=N), δ 3.79 (s, OCH
δ 6.77-8.23 (m, Ar-H); P NMR: δ 1.76 (s, PPh ).
2
Cl
2
) λmax (nm) (ε x10 , M cm ): 296
1
(13.2), 305 (9.4), 446 (1.4); H NMR (CDCl
3
3
),
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3

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2.2.4. Preparation of[Cu(L)(PPh
Complex 1d was prepared similar to the procedure performed in the preparation of 1a except
that CuCl was replaced by [Cu(MeCN) ]BF (1 mmol, 0.314 g);
Yield 88%, M.P. 120 ºC; Elemental analyses (C, H and N, wt %) Anal. Calc. For C50 :
3 2 4
) ]BF (1d)
4
4
H
41B CuF
7
N
2
OP
2
-1
C, 62.87; H, 4.33; N, 2.93; Found: C, 63.10; H, 4.35; N, 2.94; IR (KBr) (cm ) 1587, υ(HC=N);
3
-1
-1
1480, 1435, 694, 516, υ(PPh
3
); 1092, υ(BF
4
); UV-vis (CH
2
Cl ) λmax (nm)(ε x10 , M cm ):
2
1
288 (13.7), 303 (9.4), 443 (1.3); H NMR (CDCl
3
) (400 MHz): δ 9.10 (s, HC=N), δ 3.79
3
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(s, OCH
3 3
), δ 6.77-9.00 (m, Ar-H); P NMR: δ 1.76 (s, PPh )
2.2.5. Preparation of [Cu(L)(dppe)]Cl (2a)
To a solution of 2-methoxy-(5-trifluoromethyl-phenyl)-pyridine-2yl-methylene-amine (L)
(1 mmol, 0.280 g) was added a solution of 1,2-bis(diphenylphosphino)ethane (1 mmol, 0.397 g)
and CuCl (1 mmol, 0.098 g) in 10 ml dichloromethane. The reaction mixture was stirred under
nitrogen atmosphere at room temperature for 2h and then the solution was evaporated to small
volume under vacuum. The pale brown coloured complex was developed by diffusion of diethyl
ether into the filtrate.
Yield 85%, M.P. 172ºC; Elemental analyses (C, H and N, wt %) Anal. Calc. for C40
H
35ClCuF
3
N
2
OP
2
:
-1
C, 61.78; H, 4.54; N, 3.60; Found: C, 61.98; H, 4.53; N, 3.63; IR (KBr) (cm ): 1590, υ(HC=N);
3
-1
-1
1483, 1435, 1167, 693, υ(dppe); UV-vis (CH
2 2
Cl
) λmax (nm) (ε x10 ,M cm ): 284 (12.4), 296 (9.3),
1
460 (1.8); H NMR (CDCl
3
) (400 MHz): δ 9.45 (s, HC=N), δ 7.16-8.80 (m, Ar-H), δ 3.80 (s, OCH
3
),
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δ 2.66 (s, PCH
2 2
CH P); P NMR: δ -4.8 (s, dppe).
2.2.6. Preparation of [Cu(L)(dppe)]CN (2b)
Complex 2b was prepared similar to the procedure performed in the preparation of 2a except
that CuCl was replaced by CuCN (1 mmol, 0.089 g)
Yield 88%, M.P. 164 ºC; Elemental analyses (C, H and N, wt %) Anal. Calc. for C41
H
35CuF
3
N
3
OP
2
:
-1
C, 64.10; H, 4.59; N, 5.47; Found: C, 64.54; H, 4.62; N, 5.49; IR (KBr) (cm ): 1585, υ(HC=N);
3
-1
-1
1483, 1435, 1166, 693, υ(dppe); 2110, υ(C≡N); UV-vis (CH
2 2
Cl
) λmax (nm) (ε x10 , M cm ): 280
1
(12.7), 304 (9.1) 464 (1.1); H NMR (CDCl
3
) (400 MHz): δ 9.47 (s, HC=N), δ 7.18-8.82 (m, Ar-H),
3
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1
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δ 3.79 (s, OCH
3
), δ 2.67 (s, PCH
2
CH P); P NMR: δ -4.8 (s, dppe).
2

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2.2.7. Preparation of [Cu(L)(dppe)]ClO
Complex 2c was prepared similar to the procedure performed in the preparation of 2a except
that CuCl was replaced by [Cu(MeCN) ]ClO (1 mmol, 0.327 g).
Yield 84%, M.P. 148ºC; Elemental analyses (C, H and N, wt %) Anal. Calc. for C40 P :
4
(2c)
4
4
H
35 ClCuF
3
N
2
O
5
2
-1
C, 57.08; H, 4.19; N, 3.33; Found: C, 57.43; H, 4.20; N, 3.36; IR (KBr)(cm ): 1590, υ(HC=N);
3
-1
1483, 1435, 1165, 693, υ(dppe); 1096, 621 υ(ClO
4
); UV-vis (CH
cm ): 294 (12.8), 304 (8.4), 458 (1.8); H NMR (CDCl
δ 7.16-8.78 (m, Ar-H), δ 3.79 (s, OCH ), δ 2.67 (s, PCH CH
2.2.8. Preparation of [Cu(L)(dppe)]BF (2d)
Complex 2d was prepared similar to the procedure performed in the preparation of 2a except
that CuCl was replaced by [Cu(MeCN) ]BF (1 mmol, 0.314 g).
Yield 82%, M.P. 115ºC; Elemental analyses (C, H and N, wt %) Anal. Calc. for C40
2
Cl
2
) λmax (nm) (ε x10 , M
-1
1
3
) (400 MHz): δ 9.46 (s, HC=N),
3
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1
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1
1
45
46
47
48
49
50
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3
2
2
P); P NMR: δ -4.8 (s, dppe).
4
4
4
H
35B CuF
7
-1
N
2
OP
2
: C, 57.95; H, 4.26; N, 3.38; Found: C, 58.11; H, 4.28; N, 3.41; IR (KBr) (cm ): 1592,
3
-1
υ(HC=N); 1483, 1435, 1165, 693, υ(dppe); 1056, υ(BF
4
); UV-vis (CH
2 2
Cl ) λmax (nm) (ε x10 , M
-1
1
cm ): 288 (12.5), 307 (8.3), 462 (1.1); H NMR (CDCl
3
) (400 MHz): δ 9.45 (s, HC=N), δ 7.16-8.80
3
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1
1
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1
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(m, Ar-H), δ 3.80 (s, OCH
3
), δ 2.66 (s, PCH
2
CH P); P NMR: δ -4.8 (s, dppe).
2
2.3. Catalytic activity for the amination of aryl halide
The amination of iodobenzene catalyzed by copper(I) complexes was carried out according to the
procedure (scheme 1): 0.05 mmol of copper(I) catalyst was added to 4 mmol of respective aryl
amine, 8 mmol of iodobenzene, 12 mmol of KOt-Bu in toluene and the reaction mixture was
0
stirred for 12h at 90 under nitrogen. The reaction mixture was then cooled to room temperature
and the solution was filtered to remove the precipitated base. The filtrate was concentrated and
crude product was purified by column chromatography using ether: chloroform (9:1). The purified
1
product was then characterized by elemental analyses, IR, H NMR and mass spectral studies.
2.4. X-ray crystallography
A single crystal of the complexes [Cu(L)(PPh
3 2 4 4
) ]ClO (1d) and [Cu(L)(dppe)]BF (2c) suitable
for X-ray analyses was obtained by slow diffusion of diethylether into solution of complex in

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dichloromethane. The intensity data were collected on a Nonius MACH-3 four-circle
diffractometer with graphite-monochromatized MoKα radiation. The details of crystal data,
data collection and the refinement are given in Table 1. The structure was solved by direct
methods using the SHELXS 93 program and refined by using SHELXL 97 software [19]. The
non-hydrogen atoms were refined with anisotropic thermal parameters. All of the hydrogen
atoms were geometrically fixed and refined using a riding model.
3. Results and discussion
The copper(I) complexes [Cu(L)(PPh
[Cu(L)(dppe)]X (X= Cl (2a), ClO (2b), BF
equivalent of triphenylphosphine (PPh ) or one equivalent of 1,2-bis(diphenylphosphino)ethane
(dppe) with appropriate copper(I) salt (CuCl, CuCN, [Cu(CH CN) ]ClO and [Cu(CH CN) ]BF
)
3 2
4 4 6
]X (X= Cl (1a), ClO (1b), BF (1c), PF (1d)) and
4
4
(2c), PF (1d) were synthesized by the reaction of two
6
3
3
4
4
3
4
4
)
followed by the addition of one equivalent of 2-methoxy-(5-trifluoromethyl-phenyl)-pyridine-2yl-
methyleneamine (L). All the copper(I) complexes are microcrystalline solids and soluble in
common organic solvents such as dichloromethane, chloroform, acetonitrile, THF, methanol,
ethanol etc. The results of elemental analyses (C, H and N) which are given in section 2 confirm
the assigned composition of the complexes. At room temperature all the complexes are
10
diamagnetic, which is characteristic of the presence of Cu(I) (d ).
3.1 Spectroscopic properties:
The IR frequencies of selected groups in the spectra of all copper(I) complexes are given in
-1
experimental section. The IR spectra of ligand L exhibit a strong band at 1607 cm is
-
1
attributed to (HC=N) imine group [20]. On coordination this band observed at 1584-1587 cm
-
1
in 1a-d and 1585-1592 cm in 2a-d indicate the coordination of imine nitrogen to the metal
-1
ion [21]. Another characteristic band observed at 997cm in L is associated with pyridine ring
-1
-1
breathing mode of vibration shifted to higher energy at around 1022 cm in 1a-d and 1028 cm in
2a-d indicating copper nitrogen bond formation. The spectra of 1a-d exhibit the expected
-1
bands at around 1480, 1435, 694, and 516 cm is due to PPh
3
ligand whereas; 2a-d shows band
-
1
at 1483,1435,1166 and 693 cm is due to dppe ligand in the complexes. The characteristic

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-
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strong absorption at around 2110 cm in 1b and 2b indicate existence of noncoordinated CN
-1
anion [22].The perchlorate complexes 1c and 2c shows broad band at 1095 cm (ν
3
) and strong
-1
-
band at 621 cm (ν
4
), respectively is devoid of any splitting suggesting that the ClO
4
anion is
-1
-1
not coordinated to the copper atom [23]. However, a broad band at 1092 cm in 1d and 1056 cm
-
in 2d corresponds to presence of BF
4
anion in the complexes [24].
-
4
2 2
The electronic absorption spectra of complexes were recorded in CH Cl solution (10 M) in
the wavelength range 200-800 nm. The complexes exhibit a transition at 284-294 and 296-306
∗
nm in 1a-d and 280-294 and 296-307 nm in 2a-d corresponding to intraligand π→π transition
of heterocyclic and its conjugate system. The shifting of these transitions in 1a-d and 2a-d
compared to those of L which is in support of coordination to the metal ion. The copper(I)
complexes are diamagnetic and hence provide no optical absorption band; no d-d transition is
1
0
encountered for copper(I) ion with a d configuration. However, a broad band with true
maxima was observed at 442-448 nm in 1a-d and 458-464 nm in 2a-d. This band remains
absent in free ligand L and is assigned to the admixture of the MLCT and LLCT transitions,
Cu(dπ)/L→L(π*) [25]. Compare to 1a-d, metal-ligand charge transfer band (MLCT) in 2a-d
shifted to longer wavelength due to increasing electron donating character of dppe ligand [26].
This variation of MLCT band supports that ancillary phosphine ligands evidently affect the
MLCT state of copper(I) complexes.
1
2
2
2
2
10
11
12
13
The H NMR spectra of ligand L in CDCl
3
exhibit a singlet at δ 8.98 ppm assigned to imine
(HC=N) proton. The downfield shift of this signal relative to corresponding signals in the free
ligand L can be attributed to deshielding effect resulting from the coordination of imine
1
nitrogen [27]. The methoxy proton appeared as a singlet at around δ 3.79 ppm in the H NMR
2
2
2
2
2
14
15
16
17
18
spectra of all the complexes [28].The broad multiplet observed in the range δ 6.77-9.00 ppm in
1a-d and δ 7.16–8.82 ppm in 2a-d, respectively assigned to phenyl group of PPh
3
or dppe
together with ring protons of L in respective complexes. The H NMR spectra of 2a-d exhibit a
broad singlet at approximately δ 2.67 ppm is due to CH protons of the dppe ligand in the
complexes [29].
1
2

3
1
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
3 4
The P NMR spectra of 1a-d shows one singlet at ∼1.76 ppm relative to H PO indicated that
two phosphorous nuclei of triphenylphosphine are equivalent in nature [30]. In the chelating
phosphine complexes 2a-d, the two phosphorous nuclei must be cis to each other and therefore
singlet observed at -4.8 ppm [31].
3.2. Crystal structure
The single crystal X-ray data and structure refinement parameters of [Cu(L)(PPh
)
3 2
]BF
4
(1d) and
[Cu(L)(dppe)]ClO (2c) are summarized in Table 1. The selected bond lengths and bond angles
4
are given in Table 2. The monomeric complexes 1d and 2c exhibit distorted tetrahedral
geometry around copper(I) achieved by two nitrogen atoms of ligand L and two phosphorus
atoms of triphenylphosphine in 1d and two nitrogen atoms of L and two phosphorus atoms of
dppe in 2c (Fig. 1 and 2). Complexes crystallizes in the triclinic space group P-1 in 1d and
+
-
–
4 4
monoclinic space group P-21/C in 2c consists of [Cu(NN)(PP)] cation and BF and ClO as a
counter anion, respectively. The intra-ligand N(1)-Cu(1)-N(2) angle in 1d and N(1)-Cu(1)-N(2)
and P(1)-Cu(1)-P(2) angles in 2c are much less than 109.4º, being 78.87(13)º, 81.21(9)º and
0
92.18(3)º, respectively. It was observed that the N(1)-Cu(1)-N(2) bond angles in 2c (81.21(9) ) is
0
much greater than that observed in 1d (78.87(13) ) is due to reduced steric congestion. The
angles N(1)-Cu(1)-P(2), N(2)-Cu(1)-P(2), N(1)-Cu(1)-P(1), N(2)-Cu(1)-P(1) and P(2)-Cu(1)-
P(1) in 1d are 115.13(9)º, 105.05(9)º, 110.39(9)º, 117.86(10)º and 121.80(4)º, respectively are
closer to tetrahedral complexes whereas; N(2)-Cu(1)-P(2), N(1)-Cu(1)-P(2), N(2)-Cu(1)-P(1)
and N(1)-Cu(1)-P(1) angles in 2c are126.70(7)º, 124.16(6)º, 119.46(7)º and 116.21(6)º are
larger than those observed in tetrahedral complexes. These geometrical parameters suggest that
copper(I) center in 1d and 2c localizes in a highly distorted tetrahedral geometry in the
complexes. The distortion from ideal tetrahedral geometry in 1d and 2c is mainly due to
restricted bite angle of chelating iminopyridine ligand. The average Cu–N bond distance in 1d
(2.100 Å) and 2c (2.051Å) is comparable to those reported for copper(I) pseudo-tetrahedral
complexes. All Cu–P bond lengths are as one would expect i.e. close to the average value (2.257 Å)
as found in similar copper(I) complexes [32]. The imine C(6)-N(2) distance in 1d (1.270(5) Å)

2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
and C(12)-N(1) in 2c (1.282(3) Å) is in the range of accepted carbon nitrogen double bond.
These results are comparable well with those complexes reported earlier [33].
3.3.Thermogravimetric Analysis:
In order to examine the thermal stability of the complexes, the thermal decomposition studies
of all copper(I) complexes (1a-d and 2a-d) were carried out between 25-800°C under nitrogen
atmosphere. The perchlorate complexes (1c and 2c) are potentially explosive and hence were
not studied for safety reason. The thermal decomposition process of complexes 1a, 1b, 1d, 2a,
2b and 2d involves two decomposition processes. The TGA curve of complexes 1a, 1b and 1d
shows that, the first decomposition stage is assigned to the decomposition of coordinated
triphenylphosphine and takes place in the region 232-328 (1a), 213-334 (1b) and 222-318°C
(1d) corresponding to mass loss of 58.11, 58.32 and 54.76%, respectively (theoretical mass
loss 58.03 (1a), 58.62 (1b), and 54.91% (1d)). The second stage keeps losing weight from 328-
468, 334-465 and 318-457°C accompanied by a mass loss of 30.11 (1a), 32.12 (1b) 29.60 % (1d)
4
attributed to the decomposition of ligand L leaving CuCl, CuCN and CuBF as a residue
(theoretical mass loss 31.00, 31.33 and 29.33%). The complexes 2a, 2b and 2d show very
similar behaviour to the above complexes, once again the complexes undergo a rapid and
significant weight loss of 36.10 (2a), 36.33 (2b) and 33.79 (2d) in the temperature range 201-
342 (2a), 180-323 (2b) and 193-318°C (2d) corresponding to decomposition of dppe ligands
(theoretical mass loss 36.03, 36.47 and 33.80%, respectively). While second stage occurs in the
temperature range 342-575 (2a), 323-513 (2b) and 318-561°C (2d) indicative of gradual
breakdown of coordinated ligand L (observed weight loss of 51.17, 51.72 and 47.90%
theoretical mass loss 51.23 (2a), 51.86 (2b) and 48.05% (2d)) leaving CuCl, CuCN and CuBF
4
at the end.
3.4. Cyclic voltammetry:
The electrochemical properties of all the copper(I) complexes have been examined cyclic
-3
voltammetrically in 10 M CH
2 2 4 4
Cl solution containing 0.05 M n-Bu NClO as supporting
electrolyte and redox potentials are expressed with reference to Ag/AgCl. All the measurements

-
1
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
were carried out in the potential range +1.5 to -1.5 V with scan rate 100 mVs . The electrochemical
data for the complexes are given in Table 3. All the copper(I) complexes displayed oxidative
response at 0.71-0.74 V (Epa) in 1a-d and 0.55-0.58 V (Epa) in 2a-d which is attributed to
Cu(I)/Cu(II) oxidation. While the potential appeared in the range 0.63-0.65V (Epc) in 1a-d and
0.41-0.46V (Epc) in 2a-d are associated with reduction of Cu(II) to Cu(I). The quasireversible
p p
character is accounted for all complexes from the values of ∆E (∆E = Epa-Epc) ranging from
70-150 mV under the conditions of measurements. The redox processes for 1a-d appear at more
positive potential (0.675-0.695 V) as compared to 2a-d (0.480-515V). This trend may be due to
3
existence of bulkier PPh ligands in 1a-d which are more appropriate to Cu(II) oxidation state which
play a key role in shifting the oxidation potential to higher values for 1a-d relative to 2a-d [34].
3.5. Emission behaviour:
2 2
The emission properties of the compounds were studied at room temperature in CH Cl
solution at room temperature. The emission spectra of 1a-d and 2a-d exhibit broad emission
band at λmax 456-474 nm for 1a-d and 498-532 nm for 2a-d upon excitation at 300-310 and 310-
330 nm, respectively (Figure 3 and 4). The complexes do not show significant emission when
they are excited at MLCT band maxima. Thus the emission originate in all these complexes
may belong to intra-ligand charge transfer (ILCT), ligand to ligand charge transfer (LLCT)
transitions or mixture of them. The high emission intensities for 1a-d and 2a-d may be
explained by the conjugated structure of ligands whereas more rigidity is imposed after complex
formation. It was also observed that the emission maxima in 2a-d is shifted to longer wavelength
3
(by about 42-58 nm) than 1a-d and such red shift can be related to the replacement of PPh via
stronger electron donating dppe ligand which raise the HOMO level and leads to decrease the
HOMO-LUMO energy gap [35]. The observed X-ray crystal structure differences in 1d and 2c
reflected in the emission behaviour of the complexes 1a-d and 2a-d.
The emission quantum yield (ϕ) of all the complexes was determined with reference to quinine
sulfate (ϕ = 0.52 at 298 K) and it is found to be 0.051-0.057 for 1a-d and 0.045-0.049 for 2a-d
(Table 4). Further the complexes comprising PPh ancillary ligand (1a-d) have higher quantum
3

3
3
3
3
3
3
3
3
3
00
01
02
03
04
05
06
07
08
efficiencies relative to the complexes with the dppe ancillary ligand (2a-d). Significant effect
was also observed on quantum efficiencies of 1a-d and 2a-d due to increase in size of the counter
4 4
anion in the complexes and follows the sequence ClO >BF >CN>Cl. This trend may be due to
the enlarge energy gap that decreases the nonradioactive rate constant of copper(I) complexes.
These results are in good agreement with those values reported in the literature [36, 37]. Life time
data are obtained upon excitation at 320 nm and are summarized in Table 4. The decay profile of
the excited state of 1a-d and 2a-d fit well with single exponential nature of the complexes. The
average lifetime value of 1a-d is observed to be shorter than those observed for 2a-d. These results
could be attributed due to red shifted emission and reduced emission intensity observed in 1a-d as
compare to 2a-d.
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
09
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
3.6. Catalytic properties
In order to study the scope of copper(I) complex (1a-d and 2a-d) as a catalyst for the amination of
iodobenzene with various anilines was carried out by using KOt-Bu as a base in solvent toluene at
0
90 C. Under this experimental condition the isolated product obtained was characterized by
1
31
elemental analyses, IR, H NMR, P NMR and mass spectral studies (Table 5). With these
optimized conditions it was observed that copper(I) complexes 1a-d and 2a-d significantly
enhance the conversion of iodobenzene into desired triarylamine in good yield. The catalytic
efficiency was compared with the previously reported similar copper(I) complexes [38] and it was
found that all the reactions were smoothly carried out at relatively low temperature and reached the
amination yield up to 56 to78% for 1a-d and 65 to 79% for 2a-d (Table 6). By using 1a-d, the
amination yield of 4-bromo-N,N-diphenylaniline with p-bromoaniline was observed up to 56 to
68%. The amination yield of N, N-diphenyl-aniline with aniline was 59 to 71%. However, the
amination yield of 4-methoxy-N,N'-diphenylaniline with p-anisidine considerably increases up to
71 to 78%. For 2a-d, the amination yield of 4-bromo-N,N-diphenylaniline with p-bromoaniline
reached up to 65 to 71%. However the amination yield of N, N-diphenyl-aniline with aniline and
4-methoxy-N,N'-diphenylaniline with p-anisidine observed up to 67 to 74 and 71 to 79%,
respectively. These results confirm that the variety of functional group such as bromo and methoxy
group on aniline tolerated on aryl amine component under the reaction condition and significant

3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
increase in yield was observed with electron donating methoxy group on para position of the
aniline [39]. Compared to 1a-d , complexes 2a-d shows greater activity for catalytic amination
of iodobenzene. These results might be due to steric strain caused by the dppe ligand is less
3
than the PPh ligand which is more susceptible to the structural relaxation during the catalytic
reaction. It was also observed that the efficiency of copper(I) catalyst with different counter
-
4
anions exhibit different activities. It is evident that the copper(I) complex catalyst with ClO
-
-
-
anion shows greater activities than the complexes with Cl , CN , BF
4
and reached the
amination yield up to 78% for 1c and 79% for 2c. The catalytic activity of these complexes
-
-
-
-
decreases in order of ClO
attributed to difference in coordination ability of Cl , CN , BF
as difference in solubility of complexes in solvent during the reaction.
4 4
> BF >CN >Cl as their counter anions. These results could be
-
-
-
-
4
and ClO with metal ion as well
4
The probable mechanistic route for the amination of iodobenzene using 1a-d and 2a-d is
illustrated in Scheme 2 and 3, respectively. At first copper(I) complexes 1a-d remove one of
3
the PPh whereas; complexes 2a-d remove one of the arm of dppe molecule to give
corresponding active species I. These species I is then coordinated by activated aniline Ph-NH-
formed by base results into formation of species II which is then by oxidative addition of aryl halide
leads to formation of compounds III. Compounds III again activated in presence of base to give
species IV which followed by oxidative addition of aryl halide results into triarylamine (Ph
and generate the corresponding copper(I) catalyst.
4. Conclusions
3
N)
Some copper(I) complexes of the type [Cu(L)(PPh
L = 2-methoxy-(5-trifluoromethyl-phenyl)-pyridine-2yl-methleneamine, PPh
dppe = 1,2-bis(diphenylphosphino)ethane, X = Cl, CN, ClO and BF have been prepared and
characterized on the basis of elemental analyses and spectroscopic studies and compound
[Cu(L)(PPh ]ClO (1c) and [Cu(L)(dppe)]BF (2d) also by X-ray analysis. Quasireversible redox
3 2
) ]X (1a-d) and [Cu(L)(dppe)]X (2a-d) [where
3
= triphenylphosphine,
4
4
)
3 2
4
4
behaviour is accounted for all complexes corresponding to Cu(I)/Cu(II) couple and is sensitive to
phosphine ligands. Thermogarvimetric analysis (TGA) reveals that copper(I) complexes based on
PPh ligand are thermally more stable than the dppe complexes. The complexes with dppe ligand
3

3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
shows enhanced emission properties as compared to PPh
3
ligand. All the complexes worked as an
complexes, dppe
effective catalyst for amination of iodobenzene in good yield. Compared to PPh
3
complexes shows greater activity for the amination of iodobenzene due to less steric strain caused
by the dppe ligand which is more susceptible for its structural relaxation during the reaction.
5. Supplementary material
CCDC 1434343 and CCDC 1434342 contain the supplementary crystallographic data for complexes
1d and 2c. These data can be obtained free of charge via http://www.ccdc.ac.uk/conts/retrieving.html,
or from The Cambridge Cystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK;
fax: (+44) 1223-336-033; or email: deposit@ccdc.cam.ac.uk

3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
84
85
86
87
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64
65
Figure captions:
Scheme 1: Amination reaction catalyzed by copper(I) complexes
4
4
4
4
4
4
4
66
67
68
69
70
71
72
Scheme 2: Probable mechanistic route for the amination of iodobenzene using 1a-d
Scheme 3: Probable mechanistic route for the amination of iodobenzene using 2a-d
Fig. 1: Molecular structure of [Cu(L)(PPh
3
)
2
4
]BF (1d)
Fig. 2: Molecular structure of [Cu(L)(dppe)]ClO
4
(2c)
Fig. 3. Emission spectra of complexes 1a-d
Fig. 4. Emission spectra of complexes 2a-d

Figures:
Fig. 1:
Fig. 2:

Fig. 3.
Fig. 4.

copper(I) catalyst
N2 atm, KOtBu
N
R
NH2
+
2 I
R= Br, H, OMe
p-substitted N,N diphenylaniline
Scheme 1:
+
Ph3P
Ph3P
Cu
L
-
X
Ar
Ar
+
Ph-NH + KOt-Bu
N
Ph
Ph3P
2
Cu
L
-
X
I
ButOH +KX
Ar-X
+
+
Ph3P
Ph
Ar
Ph
Ph3P
L
Cu
N
Cu
II
N
L
H
IV
Ar-X
ButOH +KX
+
Ph3P
L
Ph
Ar
+
-
Cu
N
H
KOt-Bu
X
III
Scheme 2

+
P
P
Cu
L
-
X
Ar
Ar
P
P
L
+
Ph-NH + KOt-Bu
N
Ph
2
Cu
-
X
I
ButOH +KX
Ar-X
P
P
+
+
P
Ph
Ar
Ph
P
Cu
N
Cu
N
L
L
H
II
IV
Ar-X
ButOH +KX
P
P
+
Ph
Ar
Cu
+
N
H
KOt-Bu
L
-
X
III
Scheme 3

Table 1: Crystallographic data and refinement parameters for complexes 1d and 2c
1
d
2c
Empirical formula
Formula weight
Crystal system
Space group
a (Å)
C H BCuF N O P
C H ClCuF N O P
5 2
50
41
7
2
3
2
40 35
3
2
955.14
Triclinic
P-1
841.63
Monoclinic
P-21/c
12.754(2)
14.959(3)
15.036(3)
63.821(3)
75.921(3)
87.909(3)
2488.8(7)
2
14.387(5)
10.231(4)
b (Å)
c (Å)
25.622(5)
90
α (°)
β (°)
97.709(5)
90
γ (°)
3
V (A )
3737(2)
4
Z
3
Density (mg/m )
1.275
1.496
-1
μ (M K )(mm )
0.566
0.804
0
α
F (000)
980
1728
Temperature (K)
θ minimum-maximum (deg)
Data set [h, k, l]
Observed data
150(2)
100(2)
2.00 to 26.00
1.96 to 25.00
-15/14,-17/13,-17/16
>2σ(I)
-17/13,-11/13,-31/31
>2σ(I)
R , R
0.0695, 0.0840
0.2010, 0.2170
1.083
0.0573, 0.0450
0.1428, 0.1822
1.22
1
1
wR wR
2
2
,
Goodness-of-fit

Table 2: Selected bond lengths (Ǻ) and bond angles (°) for 1d and 2c
1
d
2c
Cu(1)-N(1)
2.103(3)
Cu(1)-N(1)
2.079(2)
2.024(2)
2.2492(8)
2.2459(12)
1.282(3)
81.21(9)
116.21(6)
Cu(1)-N(2)
2.097(3)
Cu(1)-N(2)
Cu(1)-P(1)
2.2560(11)
2.2594(12)
1.270(5)
Cu(1)-P(1)
Cu(1)-P(2)
Cu(1)-P(2)
N(2)-C(6)
N(1)-C(12)
N(1)-Cu(1)-N(2)
N(1)-Cu(1)-P(2)
78.87(13)
115.13(9)
N(1)-Cu(1)-N(2)
N(1)-Cu(1)-P(1)
N(2)-Cu(1)-P(2)
N(1)-Cu(1)-P(1)
N(2)-Cu(1)-P(1)
P(2)-Cu(1)-P(1)
105.05(9)
110.39(9)
117.86(10)
121.80(4)
N(1)-Cu(1)-P(2)
N(2)-Cu(1)-P(1)
N(2)-Cu(1)-P(2)
P(1)-Cu(1)-P(2)
124.16(6)
119.46(7)
126.70(7)
92.18(3)

Table 3 : Electrochemical data for copper(I) complexes (1a-d and 2a-d)
Complex
Epa (V)
0.71
0.73
0.74
0.73
0.55
0.56
0.58
0.57
Epc (V)
0.64
0.65
0.65
0.63
0.41
0.44
0.43
0.46
∆E (mV)
E (V)
p
1/2
1
a
70
80
0.675
0.690
0.695
0.680
0.480
0.500
0.505
0.515
1
b
1
c
90
1
d
100
140
120
150
110
2
a
2
b
2
c
2
d
Supporting electrolyte: n-Bu NClO (0.05 M); complex: 0.001 M; solvent: CH Cl ; E =
4
4
2
2
1/2
-1
½
( E + E ); scan rate: 100 mVs
pa pc

Table 4: Emission data of copper(I) complexes in CH Cl (1a-d and 2a-d)
2
2
complex
λex
nm)
λem
(nm)

τ
(ns)
−1
7
−1
9
K (s /10 ) K (s /10 )
r
nr
(
1
a
310
300
310
310
310
320
320
330
456
459
468
474
498
517
524
532
0.051
0.053
0.057
0.055
0.045
0.047
0.049
0.048
2.19
2.328
0.433
0.380
0.386
0.407
0.402
0.379
0.386
0.383
1
b
2.49
2.44
2.32
2.37
2.51
2.46
2.48
2.128
2.336
2.370
1.898
1.872
1.991
1.935
1
c
1
d
2
a
2
b
2
c
2
d

Table 5. Microanalytical and spectral data of amination product
-
1
1
C, H, N found (calculated)
Compound
IR (cm )
Mass
H NMR ( ppm)
C
H
N
+
N, N-diphenyl-aniline
87.76
6.10
5.89 1587, 1491,1461 m/z 245 [(Ph) N] , 168
δ 6.07-6.36, (m, Ar -H)
3
+
+
(
(
(
88.13) (6.16) (5.71)
82.47 6.13
82.88) (6.22) (5.09)
67.13 4.31
66.68) (4.35) (4.32)
[(Ph) N] ,77 [Ph]
2
+
4
4
- methoxy N, N-diphenyl-aniline
-bromo-N, N-diphenyl-aniline
5.87 1586, 1490, 1461 m/z 275 [(Ph) N-OMe] , 245
3
δ 3.84, (s, 3H, OMe),
+
+
+
[(Ph) N] , 168 [(Ph) N] , 77 [Ph] δ 6.78 -7.85, (m, Ar-H)
3
2
+
4.67 1586, 1493, 1461 m/z 323 [(Ph) NBr] , 245
δ 6.89-7.31, (m, Ar -H)
3
+
+
+
[(Ph) N] , 168 [(Ph) N] , 77 [Ph]
3
2

Table 6: Amination reaction of iodobenzene catalyzed by copper(I) complexes.
Entry
Aryl amine
Product
Complex
1a
% yield
59
63
71
68
71
74
78
76
56
61
68
64
67
68
74
69
71
73
79
77
65
67
71
68
1
2
3
4
5
6
7
8
9
1b
1c
N
NH2
1d
1a
MeO
1b
1c
N
MeO
NH2
1d
1a
Br
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
1b
1c
N
Br
NH2
1d
2a
2b
2c
N
NH2
2d
2a
MeO
2b
2c
N
MeO
NH2
2d
2a
Br
2b
2c
N
Br
NH2
2d
Reaction conditions: Ph-I, 8 mmol; aryl amine, 4 mmol; Cu(I) catalyst, 0.05 mmol;
0
KOt-Bu, 12 mmol; Toluene, 20 ml; temperature 90 C; reaction time 12 h.

1
2
3
Graphical abstract Pictogram:
4
5
6
7
8
Copper(I) Complexes of
2-methoxy-(5-trifluoromethyl-phenyl)-pyridine-2yl-
methlyeneamine: Impact of Phosphine Ancillary Ligands on Luminescence and
Catalytic Properties of the Copper(I) Complexes
2