A new access to tri(1-naphthyl)phosphine and its catalytically active palladacycles and luminescent Cu(I) complex

Article abstract of DOI:10.1016/j.inoche.2017.09.008

New approach to synthesis of tri(1-naphthyl)phosphine (Np₃P) and its application for design of new Pd(II) and Cu(I) complexes are reported. This phosphine has been prepared in 32% yield through exhaustive P–H arylation of РН₃ with 1-chloronaphthalene in the superbasic t-BuOK/DMSO system at 70 °C. The Np₃P was found to readily reacts with chloro-bridged dimers, [(κ²-C,N)Pd(μ-Cl)]₂ (κ²-C,N = PhCH₂NMe₂ (2a) or FcCH₂NMe₂ (2b), to give new mononuclear palladacycles [(κ²-C,N)Pd(Np₃P)Cl] (3, 4), in which metal has a square-planar geometry. These complexes show good catalytic activity in the Sonogashira reaction under low catalyst loadings (2 mol% Pd) and relatively mild conditions. We also synthesized and characterized first Cu(I) complex with Np₃P, namely, [Cu(phen)(Np₃P)I], that exhibits red emission (λ_max = 650 nm) at room temperature.

Full text of DOI:10.1016/j.inoche.2017.09.008

Accepted Manuscript
A new access to tri(1-naphthyl)phosphine and its catalytically
active palladacycles and luminescent Cu(I) complex
Alexander V. Artem'ev, Vladimir A. Kuimov, Elena A. Matveeva,
Irina Yu. Bagryanskaya, Anastasia I. Govdi, Sergey F. Vasilevsky,
Mariana I. Rakhmanova, Dmitry O. Samultsev, Nina K.
Gusarova, Boris A. Trofimov
PII:
DOI:
Reference:
S1387-7003(17)30448-3
doi: 10.1016/j.inoche.2017.09.008
INOCHE 6764
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Inorganic Chemistry Communications
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Accepted date:
26 May 2017
7 September 2017
13 September 2017
Please cite this article as: Alexander V. Artem'ev, Vladimir A. Kuimov, Elena A.
Matveeva, Irina Yu. Bagryanskaya, Anastasia I. Govdi, Sergey F. Vasilevsky, Mariana I.
Rakhmanova, Dmitry O. Samultsev, Nina K. Gusarova, Boris A. Trofimov , A new access
to tri(1-naphthyl)phosphine and its catalytically active palladacycles and luminescent
Cu(I) complex, Inorganic Chemistry Communications (2017), doi: 10.1016/
j.inoche.2017.09.008
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Inorganic Chemistry Communications
journal homepage: www.elsevier.com/locate/jorganchem
A new access to tri(1-naphthyl)phosphine and its catalytically active palladacycles
and luminescent Cu(I) complex
Alexander V. Artem’ev,a,b Vladimir A. Kuimov,a Elena A. Matveevaa, Irina Yu. Bagryanskaya,c,d
Anastasia I. Govdi,e Sergey F. Vasilevsky,e Mariana I. Rakhmanova,b Dmitry O. Samultsev,a Nina K.
Gusarova,a Boris A. Trofimov a*
a A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky Str., 664033 Irkutsk, Russian Federation
b Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, 3, Akad. Lavrentiev Ave., Novosibirsk 630090, Russia
c N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, 9 Lavrentiev Ave., 630090, Novosibirsk,
Russian Federation
d Novosibirsk State University, 2 Pirogova Str., Novosibirsk, 630090, Russian Federation
e V.V. Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences, 3 Institutskaya str., Novosibirsk, 630090,
Russian Federation
*Corresponding author. Tel. +7 395242 14 11; fax: +7 395241 93 46.
E-mail address: boris_trofimov@irioch.irk.ru
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
New approach to synthesis of tri(1-naphthyl)phosphine (Np3P) and its application for design of
new Pd(II) and Cu(I) complexes are reported. This phosphine has been prepared in 32% yield
through exhaustive P–H arylation of РН3 with 1-chloronaphthalene in the superbasic t-
BuOK/DMSO system at 70 °C. The Np3P was found to readily reacts with chloro-bridged
dimers, [(κ2-C,N)Pd(μ-Cl)]2 (κ2-C,N = PhCH2NMe2 (2a) or FcCH2NMe2 (2b), to give new
mononuclear palladacycles [(κ2-C,N)Pd(Np3P)Cl] (3, 4), in which metal has a square-planar
geometry. These complexes show good catalytic activity in the Sonogashira reaction under low
catalyst loadings (2 mol% Pd) and relatively mild conditions. We also synthesized and
characterized first Cu(I) complex with Np3P, namely, [Cu(phen)(Np3P)I], that exhibits red
emission (λmax = 650 nm) at room temperature.
Available online
Keywords:
Tri(1-naphthyl)phosphine
Palladacycles
Phosphine
Sonogashira coupling
Copper(I)
2016 Elsevier Ltd. All rights reserved.
Luminescence
Tertiary phosphines are widely used as versatile ligands in
coordination and organometallic chemistry [1]. They have also
multiple applications in organic synthesis, catalysis and material
science [2]. A special attention is currently devoted to the
phosphines bearing bulky and sterically hindered substituents at
the phosphorus atom [3]. Typically, these phosphines show
remarkable results in metal-catalyzed reactions, in which
common phosphine ligands (such as Ph3P and related ones) are
either of low efficiency or do not work at all. One of typical
representatives of such ligands is tri(1-naphthyl)phosphine [4],
that was firstly synthesized in 1939 [5]. Later, this phosphine has
been found to be highly efficient ligand for performance of
diverse metal-catalyzed reactions [4]. For example, utilizing
tri(1-naphthyl)phosphine, Pd-catalyzed addition of arylboronic
acids to aldehydes has been implemented, providing a variety of
diarylmethanols in good to high yields [6]. The Pd(OAc)2/Np3P
combination has been used as excellent catalyst for the cross-
coupling of arylboronic acids or their esters with methyl iodide
[7] and α-bromoacetic acid derivatives [8]. The similar catalytic
system has been exploited for Pd-catalyzed dehydroarylation of
naphthyl)phosphine has been used for preparation of Au(I) [17],
Rh(I) [18], Pd(II) [19] complexes, Ru and Os clusters [20].
Meanwhile, despite the fact that tri(1-naphthyl)phosphine is
commercial product, it remains of a limited access due to the
high price. The traditional syntheses of this compound via
reaction of lithiated 1-bromonaphthalene with PCl3 are laborious
and low-yielding. In 2011 [21], novel synthesis of this phosphine
has been developed basing on the direct reaction of 1-
bromonaphthalene with red phosphorus in the KOH/DMSO
system at 47-70 oC or under microwave irradiation. However, the
yields of tri(1-naphthyl)phosphine did not exceed 25% [21].
Thus, the elaboration of a higher yield synthesis of tri(1-
naphthyl)phosphine is a steady challenge for progressing
coordination and organometallic chemistry.
In this work, we report new approach to synthesis of tri(1-
naphthyl)phosphine via P-H arylation of PH3 with 1-
chloronaphthalene in superbasic medium. Phosphine (PH3) is an
industrial tail gas from phosphorus chemical industry [22] and
can serve as cheap source of P, therefore search for its utilization
is an urgent problem. Also, to uncover some new facets of
application of this phosphine, e.g. design of new catalytically
active palladacycles and first Cu(I) complex with Np3P, seems to
be a timely task.
triarylmethanols [9],
a cross-coupling of aldehydes and
organoboronic acids [10] as well as for monofluoromethylation
of arylboronic esters [11]. Np3P ligand has been also successfully
employed in Rh-catalyzed asymmetric hydrogenation [12],
hydroformylation of 1-hexene [13] and vinyl acetate [14],
stereoselective 1,4-hydrosilylation of α,β-unsaturated ketones
[15] and several other reactions [16]. Furthermore, tri(1-
Tri(1-naphthyl)phosphine (1) has been synthesized by arylation
of РН3 with available and cheap 1-chloronaphthalene in the t-
BuOK/DMSO superbasic system (Scheme 1). As a phosphine
source, its mixture with Н2 generated from red phosphorus and

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60%-aqueous alkali [23] has been used. Currently, РН3 is widely
used in organic synthesis [24]. However, commercial РН3 is on
sale in cylinders, where phosphine is under pressure that limits its
application in organic chemistry. The approach to the synthesis
of РН3 from elemental phosphorus developed in this work is
facile and safe since РН3 is generated without isolation and
purification and the reactions are carried out under atmospheric
pressure [25]. The exhaustive arylation of РН3 has been realized
under the following conditions. 1-Chloronaphthalene has been
heated at 70 °С for 2.5–3 h in the t-BuOK/DMSO system, while
the steady flow of phosphine through the reaction mixture has
been sustained. To convert the intermediate primary and
secondary phosphines (31P NMR data) into the target tri(1-
naphthyl)phosphine, the PH3 has been blown out from reaction
mixture and additional amount of 1-chloronaphthalene and t-
BuOK have been added. The mixture has been further stirred at
the same temperature for 2 h. Since the used commercial 1-
chloronaphthalene (85%, Alfa Aesar) contains about 15% of 2-
chloro isomer, the crude product consists of, along with major
phosphine 1, the admixtures of tri(2-naphthyl)-, di(1-naphthyl)(2-
naphthyl)- and di(2-naphthyl)(1-naphthyl)phosphines. These
impurities, however, are higher soluble (as compared to 1) and
can be removed by successive washing of the crude product with
acetonitrile and methanol (for details, see ESI). The isolated yield
of phosphine 1, thus prepared, being 32% (Scheme 1).
8.6°. On the whole, all observed bond lengths and bond angles
are comparable with those in the literature analogs of 3 [26] and
4 [27, 28]. The two pentagonal rings of the ferrocenyl moiety are
planar and deviation from parallel is 6.5°, compared to those
within “Ph3P analog” [27].
Fig. 1. Molecular structure of 3 determined by single crystal X-ray
diffraction (the H atoms are omitted for clarity). Selected bond lengths (Å)
and bond angles (deg): Pd(1)–C(7) 2.038(2), Pd(1)–Cl(1) 2.3931(6), Pd(1)–
P(1) 2.2850(6), Pd(1)–N(1) 2.153(2), P(1)–C 1.833(2)–1.843(2), P(1)–Pd(1)–
N(1) 172.42(6), Cl(1)–Pd(1)–C(7) 172.18(7), Cl(1)–Pd(1)–P(1) 92.43(2),
Cl(1)–Pd(1)–N(1) 90.06(5), P(1)– Pd(1)–C(7) 94.97(7), N(1)–Pd(1)–C(7)
82.29(8).
Scheme 1. Synthesis of tri(1-naphthyl)phosphine (1).
We found that the phosphine 1 easily reacts with chloro-
bridged dimers 2a,b in 2:1 molar ratio (acetone, 20-40 °С, 30
min) to give mononuclear palladacycles 3 and 4 in 97 and 67%
isolated yield, respectively (Scheme 2).
Scheme 2. Synthesis of palladacycles 3 and 4.
Fig. 2. Molecular structure of 4 determined by single crystal X-ray diffraction
(the H atoms are omitted for clarity). Selected bond lengths (Å) and bond
angles (deg): Pd(1)–C(10) 1.994(5), Pd(1)–Cl(1) 2.4094(14), Pd(1)–N(1)
2.194(4), Pd(1)–P(1) 2.2710(13), Cg(Cp)∙∙∙Fe 1.660, Cg(C5H3)∙∙∙Fe 1.654,
C(10)–Pd(1)–N(1) 83.07(18), C(10)–Pd(1)–P(1) 93.89(15), N(1)–Pd(1)–P(1)
175.33(12), C(10)–Pd(1)–Cl(1) 170.71(15), N(1)–Pd(1)–Cl(1) 88.19(11),
P(1)–Pd(1)–Cl(1) 94.63(5), Cg(Cp)∙∙∙Fe∙∙∙Cg(C5H3) 175.75.
The structures of 3 and 4 have been established by X-ray
diffractometry (Figures 1 and 2). The crystallographic data are
summarized in Table (ESI). Both structures consist of discrete
molecules of the palladacycles, separated by short C–H…π and
C–H…Cl contacts. The Pd atom has a slightly distorted square-
planar geometry (τ′4 = 0.106 for 3 and 0.082 for 4), formed by the
Cl, P, N and C atoms, as in Ph3P analogs of 3 (0.082) [26] and 4
(0.126) [30]. The Np3P ligand in the 3 and 4 is located at trans-
position to the N(1) atom. The five-membered [(κ2-C,N)Pd]
cycles in the complexes have an envelope conformation; the
deviation of N(1) atom from the mean plane PdC3 being 0.518
(for 3) and 0.349 Å (for 4). The phosphorus atoms of 3 and 4
1
In H spectrum, the δ value of free Cp’ ring is shifted from
downfield (4.28 ppm) in 2b to upfield (3.01 ppm) in 4, but Me
protons are shifted from upfield (2.85 and 3.02 ppm) in 2b to
downfield (3.05 and 3.16 ppm) in 4 and is a doublet due to
splitting by phosphorus. But one Np’ ring in 4 is strongly shifted
downfield from non-coordinated ligand due to sterically hindered
rotation. The large shift of the signal for proton 8, and also for
the protons 4 and 5 toward low field is characteristic [17, 29].
The catalytic activity of palladacycles 3 and 4 has been
evaluated on example of cross-coupling of 1-ethynyl-4-
nitrobenzene with 1-iodo-4-nitrobenzene and 1-iodo-4-
methoxybenzene in presence of 2 mol% of the Pd(II) source and
CuI co-catalyst (Et3N, benzene, 75 °С, Scheme 3).
adopt
a tetrahedral geometry (τ′4 = 0.902 and 0.883,
correspondingly) with the C–P bond lengths being normal.
Within 3 and 4, the Pd–P, Pd–C and Pd–Cl distances are
slightly elongated by ca. 0.03-0.04, 0.01-0.03 and 0.01 Å,
correspondingly, compared to those within “Ph3P analog” [26,
27]. Such elongation of the Pd–X bonds may be explained by a
greater steric effect of the Np3P ligand. The ferrocene unit in 4
has a nearly eclipsed conformation with average twist angle of

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Scheme 3. Cross-coupling of 1-iodoarenes with 1-ethynyl-4-nitrobenzene
room temperature. The excitation and emission spectra of 6 are
displayed in Fig. 4. The excitation maximum is about 480 nm.
The powder of 6 exhibit red photoluminescence with a broad
emission with maximum at about 650 nm.
For comparison, the reaction has been performed with the
commonly used complex, Pd(PPh3)2Cl2 (5), under the same
conditions. The results obtained are summarized in Table 1. As
the data show, palladacycles 3 and 4 show equally high reactivity
in the reaction of 1-ethynyl-4-nitrobenzene with EWG-
substituted iodoarene (1-iodo-4-nitrobenzene), while the reaction
with classical catalyst completes twice faster (5 vs 2.5 h). The
yields of the corresponding diarylacetylene, however, are close
for all three cases (92-95%). In the coupling of 1-ethynyl-4-
nitrobenzene with EDG-iodoarene (1-iodo-4-methoxybenzene),
the reaction time is doubled for all three catalysts (Table 1).
Moreover, when the complexes 3 and 4 are used, unreacted
iodoarene (up to 31%) and 1,4-diyne (up to 15%) are detected in
the reaction mixture. The yields of the cross-coupling product in
these cases are 51-60%.
Table 1. Cross-coupling of 1-iodoarenes with 1-ethynyl-4-nitrobenzene.a
Productb
[Pd]
source
time, h
Entry
R
major
95
92
95
51
minor
4
5
1.6
15
7
1
2
3
4
5
6
NO2
NO2
3
4
5
3
4
5
5
5
2.5
11
11
5
Fig. 3. Molecular structure of 6·CH2Cl2 determined by single crystal X-ray
diffraction (the hydrogen atoms and solvate molecule are omitted for clarity).
Selected bond lengths (Å) and bond angles (deg): Cu(1)–I(1) 2.6326(6),
Cu(1)–N(2) 2.100(3), Cu(1)–N(1) 2.118(3), Cu(1)–P(1) 2.2368(12), N(2)–
Cu(1)–N(1) 79.31(13), N(2)–Cu(1)–P(1) 119.83(10), N(1)–Cu(1)–P(1)
118.58(10), N(2)–Cu(1)–I(1) 108.60(10), N1–Cu(1)–I(1) 100.92(9), P1–
Cu(1)–I(1) 121.00(3).
NO2
OMe
OMe
OMe
60
93
1
a Conditions: 1-ethynyl-4-nitrobenzene (0.65 mmol), 1-iodoarene (0.5 mmol),
[Pd] (0.005 mmol), CuI (0.01 mmol), Et3N (7 mmol), benzene (2 mL), 75 °С.
b The composition of the reaction mixture according to GC-MS data (%).
The first Cu(I) complex with tri(1-naphthyl)phosphine,
namely, [Cu(phen)(Np3P)I] (6), has been prepared by us using
reaction of CuI with phosphine 1 and 1,10-phenanthroline (1:1,
CH2Cl2) at room temperature (Scheme 4). The product 6·CH2Cl2
was isolated in 30% yield (non-optimized) as air-sensitive
crystals, soluble in organic solvents.
Scheme 4. Synthesis of complex 6·CH2Cl2.
Fig. 4. Absorption spectrum of 6 in acetonitrile solution. Excitation and
emission spectra are displayed for a powder of 6.
The crystal structure of 6·CH2Cl2 has been determined by
XRD analysis and is shown in Fig. 3 (see Table in ESI). The
Cu(I) atom is four-coordinated with the τ′4 = 0.839 {cf. with the
τ′4 value for [Cu(phen)(Ph3P)I] being 0.778 [30]}. Thus,
geometry of the metal can be described as a distorted tetrahedral.
The phosphorus atom has also distorted tetrahedral environment
(τ′4 = 0.846). The N(1)-Cu(1)-N(1) bite angle [79.31(13)°] is
almost the same as that in [Cu(phen)(Ph3P)I] (79.94°). All
remaining bond lengths and bond angles around Cu and P atoms
are comparable with those in related complexes [30, 31].
To summarize, the arylation of РН3 with 1-chloronaphthalene
has been implemented as a new approach to the synthesis of
tri(1-naphthyl)phosphine. The reaction effectively proceeds in the
superbase system t-BuOK/DMSO at 70 °С for 5 h to provide the
target phosphine in 32% isolated yield. The disclosed method is
based on cheap reagents and simple procedure that makes this
promising phosphine to be more available for further
investigation in catalysis and coordination chemistry. As
example, we have prepared and characterized two square-planar
cyclopalladated complexes bearing tri(1-naphthyl)phosphine,
[(κ2-C,N)Pd(N3P)Cl], which exhibit good catalytic activity in the
alkynylation of iodoarenes under relatively low catalyst loadings
(2 mol% Pd) and mild conditions. Also, the first Cu(I) tri(1-
naphthyl)phosphine complex has been synthesized and
The absorption spectrum of 6 in acetonitrile (Fig. 4) displays
an intense band at 254 nm, assigned to π→π* intraligand
transitions. Two broad bands with λmax at about 305 and 400 nm
are much weaker and may be attributed to MLCT transitions,
which are typical for Cu(I) complexes. In general, UV-Vis
spectrum is consistent with that of related complexes [32, 33].
The photoluminescent properties of solid 6 have been studied at

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structurally characterized. The latter, in solid state, manifests red
photoluminescence with emission maximum at 650 nm.
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Acknowledgments
This work was supported by the President of the Russian
Federation (program for the support of leading scientific schools,
grant NSh-7145.2016.3). The authors are grateful to the Baikal
Analytical Center for the spectral measurements.
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ACCEPTED MANUSCRIPT
Graphical Abstract
A new access to tri(1-naphthyl)phosphine and its catalytically active palladacycles and luminescent
Cu(I) complex
Alexander V. Artem’ev, Vladimir A. Kuimov, Elena A. Matveeva, Irina Yu. Bagryanskaya, Anastasia I. Govdi, Sergey
F. Vasilevsky, Mariana I. Rakhmanova, Dmitry O. Samultsev, Nina K. Gusarova, Boris A. Trofimov*

ACCEPTED MANUSCRIPT
Highlights
 Catalyst- and PCl3-free synthesis of tri(1-naphthyl)phosphine has been elaborated
 Exhaustive P–H arylation of РН3 with 1-chloronaphthalene in the superbasic system is used for the
synthesis
 The new mononuclear palladacycles [(κ2-C,N)Pd(Np3P)Cl] are prepared
 These palladacycles show good catalytic activity in the Sonogashira reaction under low catalyst
loadings
 First Cu(I) complex [Cu(phen)(Np3P)I] is prepared that exhibits red emission (λmax = 650 nm) at
room temperature