Coordination studies of the ferrocenyl phosphine selenide ligand FcCON(CH2CH2PPh2Se)2 Dedicated to Prof. Maria José Calhorda on the occasion of her 65th birthday.

Article abstract of DOI:10.1016/j.jorganchem.2013.12.017

The oxidation of the ferrocenyl phosphine ligand FcCON(CH ₂CH₂PPh₂)₂ with elemental selenium leads to the synthesis of the ferrocenyl phosphine selenide FcCON(CH ₂CH₂PPh₂Se)

Full text of DOI:10.1016/j.jorganchem.2013.12.017

Journal of Organometallic Chemistry 760 (2014) 84e88
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Coordination studies of the ferrocenyl phosphine selenide ligand
FcCON(CH2CH2PPh2Se)2
*
Silvia Canales, M. Dolores Villacampa, Antonio Laguna, M. Concepción Gimeno
Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), CSIC e Universidad de Zaragoza, E-50009 Zaragoza,
Spain
a r t i c l e i n f o
a b s t r a c t
Article history:
The oxidation of the ferrocenyl phosphine ligand FcCON(CH2CH2PPh2)2 with elemental selenium leads to
the synthesis of the ferrocenyl phosphine selenide FcCON(CH2CH2PPh2Se)2 (L1). The coordination
chemistry of this ligand with group 11 metals and palladium has been studied, and several complexes
with coordination of the metal to the selenium atoms have been prepared. The ligand L1 reacts with
Received 9 October 2013
Received in revised form
4 December 2013
Accepted 5 December 2013
pentafluorophenyl gold(I) or gold(III) species leading to the complexes [{Au(C6F5)}2(
m-L1)] or
[{Au(C6F5)3}2( -L1)], respectively. The reaction of two equivalents of L1 with silver(I) or copper(I) salts
m
Dedicated to Prof. Maria José Calhorda on
the occasion of her 65th birthday.
gives the tetra-coordinate complexes [M(L1)2]X (M ¼ Cu, X ¼ PF6; Ag, X ¼ OTf), or with trans-
[PdCl2(NCPh)2] affords the square planar palladium derivative [PdCL2(L1)]. The ligand L1 and the gold(I)
complex [{Au(C6F5)}2(
m
-L1)] have been characterized by X-ray diffraction.
Ó 2013 Elsevier B.V. All rights reserved.
Keywords:
Gold compounds
Group 11 compounds
Ferrocene derivatives
Amidephosphine ligands
Palladium compounds
Phosphine selenide ligands
1. Introduction
chalcogenides are not well studied in coordination chemistry
although some metal complexes can serve as excellent precursors
of semiconductor materials [15]. In particular phosphineeselenide
complexes have been little studied in general and also in group 11
metal chemistry, in spite of these metals, especially gold, form
strong bonds with the selenium atom. Only a few reports have dealt
with the coordination of gold and silver to SePR3 [16], dppmSe
(dppm ¼ bis(diphenylphosphino)methane) [17], SedppmSe [18],
SedppfSe [19] or SePPh2NPPh2Seꢀ or SePPh2NHPPh2Se [20]. With
the aim of studying group 11 complexes with ferrocenyl selenide
phosphines, which may have interest as precursors of metal sele-
nides as well as biologically relevant gold complexes, here we
report on the synthesis of the ligand and the study of its coordi-
nation chemistry towards group 11 and palladium metals.
Ferrocene is a very attractive and versatile molecule with
important properties such as high electron density, aromaticity and
redox reversibility. These characteristics, together with the well
established routes to mono and 1,10-disubstituted ferrocene de-
rivatives with a great variety of organic fragments containing donor
atoms such as O, N, S, P, make ferrocene a very suitable building
block in many fields of research [1e3]. These functionalized ferro-
cene derivatives and its metal complexes represent an important
topic of research in many areas that seek special properties of such
species, e.g. non-linear optical properties, charge transport, liquid
crystals, electrochemical recognition, catalysis, nanoparticles,
immunoassay reagents or biological applications [1e12].
Ferrocene phosphines have been thoroughly studied as repre-
sented for the well-known 1,10-bis(diphenylphosphine)ferrocene
(dppf) [1]. We have described the formation of several amide-
phosphines containing ferrocene units, studied their coordination
chemistry [13] and also showed that some gold and silver com-
plexes are active as antitumoral agents [14]. However phosphine
2. Results and discussion
The ferrocenyl phosphino-amide ligand FcCON(CH2CH2PPh2)2
has been previously described by us by reaction of chlorocarbonyl-
ferrocene with the amino-phosphine N(CH2CH2PPh2)2 in
dichloromethane, and in the presence of triethylamine [14]. The
reaction of this phosphine-amide with elemental selenium gives
the ferrocenyl phosphine selenide ligand FcCON(CH2CH2PPh2Se)2
(L1) as an orange air and moisture stable solid (see Equation (1)).
* Corresponding author.
E-mail address: gimeno@unizar.es (M.C. Gimeno).
0022-328X/$ e see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jorganchem.2013.12.017

S. Canales et al. / Journal of Organometallic Chemistry 760 (2014) 84e88
85
The AueSe bond distances are Au(1)eSe(1) 2.4227(7) and Au(2)e
ꢀ
Se(2) 2.4145(8) A, which are also of the same order than those
found in complexes with AueSe]P bonds such as [Au(SedppfSe)]
ꢀ
[AuCl2] (AueSe 2.4000(9)e2.4217(8) A) [19a]. The PeSe distances
ꢀ
are P(1)eSe(1) 2.1686(18) and P(2)eSe(2) 2.1633(18) A, which are
longer than those in the starting ligand L1, as expected after the
coordination of the gold atoms.
The treatment of L1 with the gold(III) compound
[Au(C6F5)3(tht)] in a molar ratio 1:2 gives the gold(III) species
Equation 1. Synthesis of the ligand L1.
[{Au(C6F5)3}2(m-L1)] (2), where the gold centres are coordinated to
The IR spectrum shows in addition to the absorptions arising at
the selenium atoms. The IR spectrum presents, apart from other
absorptions, the vibrations due to the pentafluorophenyl groups
bonded to gold(III) at 1505(s), 996(s), 805(s) and 795(s) cmꢀ1. The
31P{1H} NMR spectrum presents one broad singlet at room tem-
perature indicating that both phosphorus are equivalent, however
at ꢀ55 ꢁC there are two singlets because the phosphorus becomes
inequivalent. The 1H NMR spectrum shows the expected reso-
nances for the ferrocenyl phosphine ligand, with a different
chemical shift. In the 19F NMR spectrum of 2 several resonances
appears; usually the three C6F5 groups attached to the gold atom
give two different 19F sets of resonances in a 1:2 ratio for the non-
equivalent C6F5 groups (one of them trans to selenium and the
other two trans each other, respectively). In complex 2 both
“Au(C6F5)3” are inequivalent and then up to twelve resonances
should appear, but in this case some of the resonances are over-
lapped. In the mass spectrum (LSIMSþ) the molecular peak does not
appears but it does the fragment arising at the lost of a Au(C6F5)3
fragment at m/z ¼ 1512 (40%).
the ferrocenyl and phosphine units, the
n
(C]O) vibration at
1627 cmꢀ1 and the new
n
(P]Se) vibration at 535 cmꢀ1. In the 31P
{1H} NMR spectrum two resonances appear at 32.4 and 27.8 ppm,
indicating the inequivalence of the phosphorus atoms, these two
resonances have selenium satellites with J(PSe) of 743 and 737 Hz,
respectively, corroborating the coordination of the phosphorus
atoms to selenium. The 1H NMR spectrum shows two multiplets for
the
a and b protons of the substituted cyclopentadienyl ring and a
singlet for the unsubstituted cyclopentadienyl moiety. The reso-
nances for the methylene protons appear as two broad multiplets,
indicating that these protons have a close chemical shift. In the
mass spectrum (LSIMSþ) the molecular peak at m/z ¼ 811 (60%)
appears.
The ligand L1 has been characterized by X-ray diffraction studies
and the molecule is shown in Fig. 1. The nitrogen atom of the amide
is found in a trigonal planar coordination with angles of C(11)e
N(1)eC(12) 127.6(7)ꢁ, C(11)eN(1)eC(14) 115.9(7)ꢁ and C(12)e
N(1)eC(14) 116.1(7)ꢁ. The NeC distance to the amide carbon is
The reaction of the ligand L1 with [Cu(NCMe)4]PF6 or AgOTf in a
2:1 molar ratio affords the tetra-coordinated complexes [M(L1)2]X
(M ¼ Cu, X ¼ PF6 (3); Ag, X ¼ OTf (4)). Complexes 3 and 4 are orange
solids and behave as 1:1 electrolytes in acetone solutions. The IR
spectra show the absorptions for the anion PF6 in 3 at 844 (s) cmꢀ1
and those for the trifluoromethanesulphonate at 1265 (vs, br)
ꢀ
C(11)eN(1) 1.372(10) A. The P]Se bonds are Se(1)eP(1) 2.107(2)
ꢀ
and Se(2)eP(2) 2.097(3) A, which agrees with a double bond P]Se.
The C]O unit points out to one of the phosphine arms, which can
be the reason that both phosphorus becomes inequivalent in
solution.
The reaction of L1 with [Au(C6F5)(tht)] in a 1:2 molar ratio gives
the complex of stoichiometry [{Au(C6F5)}2(m-L1)] (1) (see Scheme
[
[
nas(SO3)], 1223 (s) [ns(CF3)], 1150 (vs, br) [nas(CF3)] and 1023 (s)
ns(SO3)] cmꢀ1 in 4. The 31P{1H} NMR spectrum of 3 shows a broad
1) as an orange solid. The IR spectrum for this compound shows
singlet at room temperature with a J(PSe) of 655 Hz; however
at ꢀ55 ꢁC the resonance splits into three singlets in an approximate
ratio 1:2:1, which indicates the inequivalence of all the phosphorus
atoms, but two of the resonances are overlapped because the close
chemical shift. In the 1H NMR spectrum also broad resonances
the absorptions arising at the vibrations of the pentafluorophenyl
rings at 1500 (vs), 954 (s) and 800 (m) cmꢀ1. The
n(C]O) and n(C]
N) vibrations around 1640 and 1587 cmꢀ1 are also present. The 1H
NMR spectra show several resonances for the different protons in
the molecule: a singlet for the protons of the unsubstituted cyclo-
pentadienyl ring at 4.22 ppm, two multiplets for the
a and b pro-
tons of the substituted cyclopentadienyl ring at 4.36 and 4.75 ppm,
two multiplets for the methylene protons at 3.03 and 3.89 ppm of
the phosphine ligands, and several multiplets for the phenylic
protons. The 31P{1H} NMR spectrum presents two resonances for
the inequivalent phosphorus atoms at 30.6 and 26.8 ppm with
selenium satellites and coupling constants of J(PSe) of 552 and
551 Hz, respectively. The 19F NMR spectrum of 1 presents two
multiplets for the equivalent ortho and meta fluorine at ꢀ160.0
and ꢀ116.5, respectively, and other multiplet at ꢀ162.5 for the para
fluorine. In this case the pentafluorophenyl rings appear as equiv-
alent, although the phosphorus atoms are not, and this is probably
because there is a higher degree of rotation around the bond Aue
C6F5. The LSIMSþ mass spectrum shows the molecular peak at m/
z ¼ 1541 (25%) and the fragment arising at the lost of one penta-
fluorophenyl ring at m/z ¼ 1370 (15%).
The crystal structure of complex 1 has been established by X-ray
diffraction studies and the molecule is shown in Fig. 2. The gold
atoms are in a linear geometry, slightly distorted, with angles of
Fig. 1. Molecular structure of the compound L1, with the atom labelling scheme.
ꢁ
ꢀ
Selected bond lengths (A) and angles ( ): Se(1)eP(1) 2.107(2), Se(2)eP(2) 2.097(3),
N(1)eC(11) 1.372(10), N(1)eC(12) 1.462(9), N(1)eC(14) 1.474(9), O(1)eC(11) 1.228(9);
C(11)eN(1)eC(12) 127.6(7), C(11)eN(1)eC(14) 115.9(7), C(12)eN(1)eC(14) 116.1(7),
C(31)eP(1)eSe(1) 113.4(3), C(13)eP(1)eSe(1) 112.3(3), C(21)eP(1)eSe(1) 113.5(3),
C(15)eP(2)eSe(2) 113.7(3), C(61)eP(2)eSe(2) 113.2(2), C(51)eP(2)eSe(2) 113.1(2),
C(41)eP(2)eSe(2) 114.1(3).
C(41)eAu(1)eSe(1)
178.78(19)ꢁ
and
C(71)eAu(2)eSe(2)
175.32(18)ꢁ. The AueC distances are Au(1)eC(41) 2.007(7) and
ꢀ
Au(2)eC(71) 2.023(7) A, which are of the same order and similar to
other complexes with pentafluorophenyl rings bonded to gold(I).

86
S. Canales et al. / Journal of Organometallic Chemistry 760 (2014) 84e88
6
Scheme 1. Synthesis of the metal complexes: i) 2[Au(C6F5)(tht)], ii) 2[Au(C6F5)3(tht)], iii) ½[Cu(NCMe)4]PF6 or ½Ag(OTf), iv) trans-[PdCl2(NCPh)2].
appear as one broad signal for all the ferrocene protons, two mul-
tiplets for the methylene protons and a multiplet for the phenylic
protons. At ꢀ55 ꢁC the ferrocene protons appear as the typical
singlet for the unsubstituted ferrocene and two multiplets for the
substituted ferrocene protons, but the methylene protons now only
one broad multiplet appears. The 31P{1H} NMR spectrum of 4 also
shows a broad singlet at room temperature with a J(PSe) of 653 Hz
and at ꢀ55 ꢁC the resonance widens but does not resolve. The 1H
NMR spectrum is similar at both temperatures and the typical
resonances for the ligand appear. The mass spectra (LSIMSþ) show
the cation molecular peaks at m/z ¼ 876 (100%) for 3 and 920 (55%)
for 4.
The reaction of L1 with trans-[PdCl2(NCPh)2] in a 1:1 molar ratio
leads, after the displacement of the benzonitrile ligands, to the
formation of complex [PdCl2L1] (5). Complex 5 is a red solid, stable
to air and moisture, that behaves as non-conductor in acetone so-
lutions. The 31P{1H} NMR spectrum of 5 shows two singlets at 34.5
and 30.0 ppm. The 1H NMR spectrum presents two multiplets for
the methylene protons, a singlet for the protons of the unsub-
stituted Cp ring, two multiplets for the protons of the substituted
Cp ring and the multiplets due to the phenylic protons. The mass
spectrum does not show the molecular ion peak but the fragment
Fig. 2. Molecular structure of complex 1 in the crystal showing the atom labelling
[PdL1]þ appears at m/z ¼ 918 (5%).
ꢁ
ꢀ
scheme. H atoms are omitted for clarity. Selected bond lengths (A) and angles ( ):
Au(1)eC(41) 2.007(7), Au(1)eSe(1) 2.4227(7), Au(2)eC(71) 2.023(7), Au(2)eSe(2)
2.4145(8), P(1)eSe(1) 2.1686(18), P(2)eSe(2) 2.1633(18), C(11)eO(1) 1.243(7), C(11)e
3. Conclusions
ꢀ
N(1) 1.359(7), N(1)eC(12) 1.460(7), N(1)eC(14) 1.462(7) A; C(41)eAu(1)eSe(1)
178.78(19), C(71)eAu(2)eSe(2) 175.32(18), P(1)eSe(1)eAu(1) 93.58(5), P(2)eSe(2)e
Au(2) 93.34(5), C(11)eN(1)eC(12) 116.5(5), C(11)eN(1)eC(14) 125.0(5), C(12)eN(1)e
C(14) 115.5(5)ꢁ.
The ferrocenyl phosphine selenide ligand FcCON(CH2CH2PPh2Se)2
(L1) has been prepared by oxidation of the ferrocenyl phosphine

S. Canales et al. / Journal of Organometallic Chemistry 760 (2014) 84e88
87
Table 1
FcCON(CH2CH2PPh2)2 with elemental selenium. The crystal structure
X-ray data for compounds L1 and 1.
revealed that both arms of the phosphine selenide ligand are not
equivalent because the C]O bond points out to one of them. Several
gold(I), gold(III), silver(I), copper(I) and palladium complexes have
been synthesized with this ligand of different stoichiometries,
showing than the phosphine selenide coordinates as bridging or
chelating ligand. The crystal structure of the gold(I) species
[{Au(C6F5)}2(m-L1)] (1) showed that the gold centres coordinate to the
selenium atoms and an elongation of the P]Se bond lengths takes
place.
Compound
L1
1
Formula
Mr
Habit
C39.5H37ClFeNOP2Se2
852.86
Orange prism
0.16 ꢂ 0.10 ꢂ 0.10
Monoclinic
C54H43Au2Cl3F10FeNOP2Se2
1687.89
Orange prism
0.22 ꢂ 0.20 ꢂ 0.16
Triclinic
Crystal size (mm)
Crystal system
Space group
Cell constants
C2/c
P-1
ꢀ
a (A)
12.5906(13)
23.321(3)
25.603(3)
90
101.167(3)
90
7375.4(14)
8
1.536
13.7406(8)
15.1267(9)
15.2415(9)
66.9560(10)
71.9100(10)
79.9360(10)
2765.9(3)
2
ꢀ
b (A)
ꢀ
c (A)
4. Experimental
a
b
g
(ꢁ)
(ꢁ)
(ꢁ)
4.1. Instrumentation
3
ꢀ
V (A )
Infrared spectra were recorded in the range 4000e200 cmꢀ1 on
a PerkineElmer 883 spectrophotometer using Nujol mulls between
polyethylene sheets. Conductivities were measured in ca.
5 ꢂ 10ꢀ4 mol dmꢀ3 solutions with a Philips 9509 conductimeter. C,
H, N and S analyses were carried out with a PerkineElmer 2400
microanalyzer. Mass spectra were recorded on a VG Autospec, with
the liquid secondary-ion mass spectra (LSIMS) technique, using
nitrobenzyl alcohol as matrix. NMR spectra were recorded on
Bruker ARX 300 and Bruker ARX 400 spectrometers in CDCl3,
otherwise stated. Chemical shifts are cited relative to SiMe4 (1H,
Z
Dx (Mg mꢀ3
)
2.027
7.143
1610
m
(mmꢀ1
)
2.575
3440
F(000)
T (ꢁC)
ꢀ173
ꢀ173
2
qmax
50
51
No. of refl.
Measured
Independent
Transmissions
Rint
19,815
6480
0.6834e0.7828
0.112
464
490
15,725
10,139
0.3025e0.3945
0.028
685
Parameters
Restraints
0
external), CFCl3 (19F, external) and 85% H3PO4 31P, external).
(
wR (F2, alle refl.)
0.165
0.075
0.036
0.855
1.03
R (I, >2
S
Max. Dr (e A
s
(I))
0.053
0.761
1.05
4.2. Starting materials
ꢀꢀ3
)
The starting materials FcCON(CH2CH2PPh2)2 [14], [Au(C6F5)
(tht)] [21], [Cu(NCMe)4]PF6 [22] were prepared according to pub-
lished procedures. All other reagents were commercially available.
5 mL and addition of hexane (10 mL) gave complex 2 as an orange
solid. Yield 76%, 167.4 mg. L 3.8 Uꢀ1 cm2 molꢀ1. C75H37Au2F30
M
-
FeNOP2Se2 (2207.70): calcd. C 40.80, H 1.69, N 0.63; found C 40.56,
4.3. Synthesis of FcCON(CH2CH2PPh2Se)2 (L1)
H 1.67, N 0.74. 1H NMR,
d
: 3.20 (m, 8H, CH2), 4.13 (m, 2H, C5H4), 4.17
(m, 2H, C5H4), 4.20 (m, 5H, C5H5), 7.43e7.76 (m, 20H, Ph). 31P{1H},
d:
To a solution of FcCON(CH2CH2PPh2) (0.653 g, 1 mmol) in tet-
rahydrofurane (20 mL) was added selenium powder (0.158 g,
2 mmol) and the mixture was stirred for 8 h. Evaporation of the
solvent to ca. 5 mL and addition of hexane (10 mL) gave ligand L1 as
27.5 (s, 2P); ꢀ55 ꢁC,
d
: 28.1 (s, 1P), 25.9 (s, 1P). 19F,
d
: ꢀ120.0 (m, 4F,
o-F), ꢀ121.8 (m, 2F, o-F), ꢀ122.6 (m, 6F, o-F), ꢀ156.9 (m, 2F, p-F),
156.9 (m, 2F, p-F), ꢀ157.3 (t, 1P, p-F, J(FF) 19 Hz), ꢀ159.1 (t, 1P, p-F,
J(FF) 19 Hz), ꢀ160.0 (t, 1P, p-F, J(FF) 21 Hz), ꢀ160.9 (m, 4F, m-
F), ꢀ161.5 (m, 2F, m-F), ꢀ162.8 (m, 2F, m-F), ꢀ163.1 (m, 4F, m-F).
an orange solid. L1: Yield 85%, 689 mg. L 1.3 Uꢀ1 cm2 molꢀ1
.
M
C
39H37FeNOP2Se2 (811.43): calcd. C 57.73, H 4.60, N 1.73; found C
57.32, H 4.56, N 1.77. 1H NMR,
d: 3.03 (m, 4H, CH2), 3.89 (m, 4H,
4.6. Synthesis of [M(L1)2]X (M ¼ Cu, X ¼ PF6 (3); Ag, X ¼ OTf (4))
CH2), 4.22 (s, 5H, C5H5), 4.36 (m, 2H, C5H4), 4.75 (m, 2H, C5H4), 7.15e
7.85 (m, 20H, Ph). 31P{1H},
d: 32.4 (s, 1P, J(PSe) 743 Hz), 27.8 (s, 1P,
To a solution of L1 (0.081 g, 0.1 mmol) in dichloromethane
(20 mL) was added [Cu(NCMe)4]PF6 (0.018 g, 0.05 mmol) or AgOTf
(0.013 g, 0.05 mmol) and the mixture was stirred for 1 h. Evapo-
ration of the solvent to ca. 5 mL and addition of diethyl ether
(10 mL) gave complexes 3, or 4 as orange solids. Complex 3: Yield
J(PSe) 737 Hz).
4.4. Synthesis of [{Au(C6F5)}2(m-L1)] (1)
To a solution of L1 (0.081 g, 0.1 mmol) in dichloromethane
(20 mL) was added [Au(C6F5)(tht)] (0.090 g, 0.2 mmol) and the
mixture was stirred for 30 min. Evaporation of the solvent to ca.
5 mL and addition of hexane (10 mL) gave complex 1 as an orange
80%, 147 mg. L 107.7 Uꢀ1 cm2 molꢀ1. C78H74CuF6Fe2N2O2P5Se4
M
(1831.37): calcd. C 51.15, H 4.07, N 1.53; found C 51.03, H 4.19, N 1.65,
S. 1H NMR,
d: 2.88 (m, 8H, CH2), 3.44 (m, 8H, CH2), 5.08 (m, 18H,
C5H4 þ C5H5), 7.1e7.9 (m, 40H, Ph). 1H, ꢀ55 ꢁC,
d: 3.08 (m,16H, CH2),
solid. Yield 65%, 100.1 mg. L 14 Uꢀ1 cm2 molꢀ1. C51H37Au2F10Fe-
M
3.89 (m, 18H, C5H4 þ C5H5), 7.1e7.9 (m, 40H, Ph). 31P{1H},
d: 29.0 (s,
NOP2Se2 (1540.92): calcd. C 39.78, H 2.42, N 0.91; found C 39.54, H
4P, J(PSe) 655 Hz); ꢀ55 ꢁC,
d: 32.7 (s, 1P), 28.8 (s, 2P), 32.7 (s, 1P).
2.47, N 0.93. 1H NMR,
d: 3.30 (m, 4H, CH2), 3.75 (m, 4H, CH2), 4.14
Complex 4: Yield 77%, 142 mg.
L
M
99.8 Uꢀ1 cm2 molꢀ1
.
(s þ m, 5 þ 2H, C5H5 þ C5H4), 4.59 (m, 2H, C5H4), 7.52e7.83 (m, 20H,
Ph). 31P{1H}, ꢀ55 ꢁC,
d
: 30.6 (s, 1P, J(PSe) 552 Hz), 26.8 (s, 1P, J(PSe)
C
79H74AgF3Fe2N2O2P4SSe4 (1831.80): calcd. C 51.80, H 4.07, N 1.53, S
1.75; found C 51.43, H 4.11, N 1.61; S 1.71. 1H NMR, r.t. and ꢀ55 ꢁC,
d:
551 Hz). 19F,
4F, m-F).
d
: ꢀ116.5 (m, 4F, o-F), ꢀ160.0 (m, 2F, p-F), ꢀ162.5 (m,
3.0e4.8 (m, 34H, C5H4 þ C5H5 þ CH2), 7.2e7.8 (m, 40H, Ph). 31P{1H},
d
: 55 ꢁC, r.t. and ꢀ55 ꢁC,
d: 31.7 (s, 4P, J(PSe) 653 Hz).
4.5. Synthesis of [{Au(C6F5)3}2(m-L1)] (2)
4.7. Synthesis of [PdCl2(L1)2] (5)
To a solution of L1 (0.081 g, 0.1 mmol) in dichloromethane
(20 mL) was added [Au(C6F5)3(tht)] (0.154 g, 0.2 mmol) and the
mixture was stirred for 30 min. Evaporation of the solvent to ca.
To a solution of L1 (0.081 g, 0.1 mmol) in dichloromethane
(20 mL) was added trans-[PdCl2(NCPh)2] (0.038 g, 0.1 mmol) and

88
S. Canales et al. / Journal of Organometallic Chemistry 760 (2014) 84e88
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20H, Ph). 31P{1H},
d
: 27.5 (s, 2P); ꢀ55 ꢁC,
d: 28.1 (s, 1P), 25.9 (s, 1P).
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We thank the Ministerio de Economía y Competitividad-FEDER
(CTQ2010-20500-C02-01), the Departamento de Ciencia, Tecnolo-
gía y Universidad del Gobierno de Aragon (E77) and the Fondo
Social Europeo for financial support.
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CCDC 925249 (L1) and 925250 (1) contain the supplementary
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