Inorganica Chimica Acta 495 (2019) 118945

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Inorganica Chimica Acta

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Palladium(II) complexes of hemilabile NNS and NNSe iminophosphorane T

ligands: Synthesis, characterization, and reactivity
Carla Gabriela Martínez-De-Leóna, Aurora Rodríguez-Álvareza, Angelina Flores-Parrab,
Jean-Michel Grévya,
⁎

a
Centro de Investigaciones Químicas, Instituto de Investigación en Ciencias Básicas y Aplicadas, Universidad Autónoma del Estado de Morelos, Avenida Universidad #
1001, Chamilpa, CP 62209 Cuernavaca, Morelos, Mexico
b
Department of Chemistry, Cinvestav, A. P. 14-740, Mexico City 07000, Mexico

ARTICLE INFO ABSTRACT

Keywords: Four terdentate ligands combining (2-indolyl)iminophosphorane with a thioether or selenoether moiety, with
Iminophosphorane general formula 2-C8H6N(Ph2P = NC6H4XR) [X = S, R = CH3 (2), C6H5 (3); X = Se, R = CH3 (4), C6H5 (5)],
Hemilability were synthesized and fully characterized, including the structure of ligand (2) by single-crystal X-ray crystal-
Non-symmetrical pincer lography. Treatment of ligands 2–5 with PdCl2(CH3CN)2 produces non-symmetrical N,N,X-Pd(II) pincer com-
Palladium
plexes [PdCl{2-C8H5N(Ph2P = NC6H4XR-κ3-N,N,X)}] [X = S, R = CH3 (6), C6H5 (7); X = Se, R = CH3 (8), C6H5
Selenoether ligand
(9)]. All complexes were fully characterized spectroscopically and by single-crystal X-ray crystallography. In
Thioether ligand
presence of NaPF6 or NaBF4, treatment of 6 with neutral ligands NEt3, Pyridine and PPh3 gives mononuclear
cationic complexes 10, 11, 12 where Cl− is replaced by the corresponding ligand. The solid state structure of
cationic complexes 10–12 show that κ3-N,N,X pincer coordination is preserved. Reaction of 6 with diphosphane
Ph2P(CH2)2PPh2 (dppe) in 1:1 ratio promotes liberation of the sulfur donor atom from Pd(II) and gives the
mononuclear cationic complex 13 bearing the ligand in bidentate N,N chelation and the diphosphane in P,P
chelation. Solid-state structure of 13 determined by X-ray crystallography confirms the labile character of the
thioether group and reveals a strong interaction between the iminic nitrogen and sulfur atom, holding the
thioether group very close to the metal center. Reversibility of the process is proven by reformation of the pincer
structure upon treatment of 13 with O2 and release of Ph2P(O)(CH2)2P(O)Ph2 (dppeO2). When complexes 7–9
are treated with the same sequence of reactions, 31P NMR monitoring indicates that pincer complexes with
selenoether donors undergo the same reversible hemilability.

1. Introduction
Polydentate ligands containing at least two notably different donor
groups such as hard and soft donor atoms have been the center of
growing interest for chemists mainly because of their hemilabile be-
havior. The term hemilabile, which was first introduced by Jeffrey and
Rauchfuss in 1979 [1], describe hybrid ligands with a weakly chelating
group that can be displaced from the metal to provide an open co-
ordination site during reactivity, while a strongly bond portion keep the
ligand anchored to the metal center. The decoordination of the weakly
chelating group of the ligand must be reversible once the complex
completed the chemical transformation it was intended for. Also, when
the uncoordinated hemilabile group stays within a convenient distance
from the metal center it can be used to assist the chemical reaction. The
interest in transition metal complexes with hemilabile ligands comes
not only from their remarkable stability and performance in catalysis
[2], small molecule activation [3], chemical sensing [4], and stabili-
zation of reactive transition metal species, but also from their potential
in the field of bioinorganic chemistry. For example the concept of
hemilability is the foundation in the development of supramolecular
allosteric enzyme mimics assembled via the weak link approach [5].
Experimental evidences of hemilability usually rely on the observation
of fluxional behavior in the metal complex or on the spectroscopic
detection of the species with different chelating bites. The reversible
association/dissociation process of hemilabile ligand can also be de-
tected by kinetic method [6]; however, the effects of hemilability are
more commonly based on assumptions than established experimentally.
In few cases the release of the weakly chelating group has been de-
monstrated through the reactivity of a complex, and usually with strong
nucleophiles, but the reversibility of the phenomenon is rarely

⁎
Corresponding author.
E-mail address: jeanmichelg@gmail.com (J.-M. Grévy).

https://doi.org/10.1016/j.ica.2019.05.044
Received 5 April 2019; Received in revised form 23 May 2019; Accepted 29 May 2019
Available online 30 May 2019
0020-1693/ © 2019 Elsevier B.V. All rights reserved.
C.G. Martínez-De-León, et al.
Scheme 1. Synthesis of terdentate iminophosphorane ligands 2–5.
established [7,8].
The introduction of an iminophosphorane moiety in the design of
polydentate ligands is expected to be advantageous for catalytic ap-
plications due to the strong sigma donor capacity of the group, still
examples of such ligands remain rather limited. The pioneering work on
the subject was reported by Urriolabeitia who described the ortho-
palladation of an iminophosphorane functionalized with a pyridine-2-
carbonyl group attached to the iminic N, obtaining a new C,N,N non-
symmetrical pincer complex of formula [Pd(C6H4-2-PPh2 = N−C(O)-2-
NC5H4-k3-C,N,N)Cl] [9] which exhibited moderate catalytic activity in
the Mizoroki-Heck process using methyl acrylate and p-substituted
benzene halides. The same group later reported on the orthopalladation
of other iminophosphorane ligands functionalized with different donor
atoms, obtaining the corresponding C,N,X (X = O, N, S) non-symme-
trical pincer complexes [10]. Within the structure, the orthometallated
five membered cycle was found to be remarkably stable while the other
N,X chelate cycle appeared less stable, so that the coordination of the
ancillary functional group could be considered as hemilabile. Although
the authors did not report any potential catalytic activity for these
complexes at the time, it came to our attention that bringing together in
a Pd(II) complex strong sigma donors, such as an iminophosphorane
and a thioether, and the hemilability of an ancillary group could be of
interest for catalytic and biological applications. In addition to the work
of Urriolabeitia cited before, few other examples of complexes derived
from iminophosphoranes functionalized with a sulfur donor atom and
showing N,S quelation have been reported in the literature [11–14].
Therefore, we recently envisaged the synthesis of new non-symmetrical
C,N,S pincer complexes of palladium by direct orthopalladation of a
series of iminophosphoranes functionalized with a strong donor thioe-
ther ancillary group. These complexes showed good catalytic activity in
the Suzuki-Miyaura and Mizoroki-Heck reactions under conventional
heating and in very mild conditions upon microwave activation
[15–16]. We also prepared the corresponding Pt(II) derivatives to
evaluate their cytotoxicity against different human cancer cell lines,
finding some of them more cytotoxic than cisplatin [17].
It has also been shown that selenium-ligated pincer complexes can
display improved catalytic properties compared to those containing
lighter elements, such as P and S, due to the stronger σ donor ability of
Se. For example Yao et al. synthesized a Pd(II) Se,C,Se pincer complex
that turned out to be an extremely active catalyst, outplaying the cor-
responding phosphorus and sulfur analogues in the Heck coupling of
various aryl bromides, including deactivated and heterocyclic ones
[18]. Szabó and co-workers later reported the same Se,C,Se pincer to
catalyze the boronation of various vinyl substrates under mild and
neutral conditions [19] and the highly regio- and stereoselective cou-
pling of allyl alcohols with aldehydes [20]. In 2010, Cadierno and
coworkers published the first and unique example to date of imino-
phosphoranes functionalized with a selenium donor group. They char-
acterized several Ru(II) C,N,Se and C,S,Se complexes derived from
(iminophosphoranyl)(selenophenyl)methane ligands and studied their
reactivity to form carbene complexes [21]. On the other hand, orga-
noselenium compounds are also being extensively studied for their
bioactivity with promising therapeutic perspectives [22] and various
2
Inorganica Chimica Acta 495 (2019) 118945
organoselenium compounds have been investigated for the treatment of
cancer [23].
Following our research on the development of new non-symmetrical
systems with potential use in both cross-coupling catalysis and cyto-
toxic activity we envisaged the construction of new N,N,S and N,N,Se
pincer-type palladium complex. In this work, we present the synthesis
and full characterization of iminophosphorane ligands derived from a
new 2-indolyldiphenyl phosphine and functionalized with a thioether
or, as far as we know, for the first time with selenoether ancillary group.
We also describe the synthesis of the corresponding N,N,X (X = S, Se)
non-symmetrical Pd(II) pincer complexes and, to probe the hemilability
of the ligands, the reactivity of the chloride in the fourth position was
investigated toward a number of nucleophiles. The experimental evi-
dence of hemilabile coordination for both thioether and selenoether
functions is reported by 31P monitoring and with solid-state structure
determination for the thioether function. The reversibility of this pro-
cess is also established experimentally for all complexes.
2. Results and discussion
2.1. Synthesis of the ligands
The new ligands 2–5 were prepared following the procedure de-
scribed in Scheme 1. First, 2-indolyldiphenyl phosphine 1 was synthe-
sized following the method reported by Katritzky and co-workers [24]
for the selective substitution at the C2 position of unsubstituted indoles.
Using chlorodiphenylphosphine as the electrophile led to the obtention
of 1 in very good yield after removal of all volatiles (> 90%). Although
a variety of indolylphosphines have been reported in the past [25], it is
worth mentioning here that 1 is the first 2-indolylphosphine with no
substituent on position 3.
Compound 1 was fully characterized by multinuclear NMR spec-
troscopy in solution, showing a single 31P−{1H} NMR signal at δ
−27 ppm. Complete NMR assignments are reported in experimental
section and the substitution at C2 position is evidenced in the 13C NMR
spectrum by the coupling of C2 (δ 133 ppm) with 31P, showing a value
of 17 Hz typical for 1JPC in phosphine compounds.
Iminophosphorane ligands 2–5 were prepared in almost quantita-
tive yields under anhydrous conditions using the Staudinger reaction,
between 2-indolyl-diphenylphosphine 1 and the corresponding azides
prepared in the laboratory using a previously reported procedure [26].
All the compounds were isolated as cream-colored powders that can be
kept for days under nitrogen without decomposition. The ν(P]N) vi-
bration observed for 4 at 1303 cm−1 is typical for a free iminopho-
sphorane, however the same stretch is shifted at lower frequencies for
the other ligands [1258 (2), 1275 (3), and 1274 cm−1 (5)] compared to
those usually observed for free iminophosphoranes (≈ 1315 cm−1).
This shift is probably due to a strong interaction between the iminic
nitrogen and the indolic proton that weakens the P]N bond. In
31
P−{1H} NMR the ligand formation results in the observation of a
single signal in the expected region for iminophosphoranes, strongly
deshielded (Δδ ≈ +20 ppm) compared to phosphine 1 [δ −7.7 (2),
−6.8 (3) −7.6 (4), −7.0 ppm (5)]. Neither the nature of the chalcogen
C.G. Martínez-De-León, et al. Inorganica Chimica Acta 495 (2019) 118945

Table 1 2.2. Synthesis of the complexes

Selected bond lengths (Å) and angles (deg) data for 6–9.
6 7 8 9 Treatment of iminophosphorane ligands (2–5) with PdCl2(MeCN)2
and excess Na3PO4 in dichloroethane at 80 °C readily led to the for-
P]N 1.626(3) 1.630(3) 1.630(3) 1.633(4) mation of the corresponding N,N,S (6, 7) and N,N,Se (8, 9) un-
N(1)-Pd(1) 2.032(3) 2.024(4) 2.046(3) 2.035(4)
symmetrical pincer palladium complexes in good yields (Scheme 2).
N(2)-Pd(1) 2.032(3) 2.032(4) 2.035(3) 2.040(4)
X(1)-Pd(1) 2.2489(9) 2.252(1) 2.3474(4) 2.3545(7)
The compounds were isolated as air and moisture-stable orange solids,
Cl(1)-Pd(1) 2.308(1) 2.297(1) 2.3146(9) 2.289(2) which are moderately soluble in polar and non-polar solvents. The
Pd(1)-N(1)-P(1) 116.8(1) 116.6(2) 116.6(6) 113.9(2) realization of κ3-N,N,X-coordination (X = S, Se) in complexes 6–9 was
Pd(1)-N(1)-C(9) 117.4(2) 118.5(3) 119.0(2) 119.8(3) unambiguously confirmed based on the multinuclear NMR (1H, 13C,
P(1)-N(1)-C(9) 125.1(2) 124.6(3) 123.9(2) 122.7(3) 31
P) and IR spectroscopic data. The IR spectrum of the complexes shows
N(1)-Pd(1)-N(2) 86.3(1) 86.6(1) 86.0(1) 87.1(2)
N(1)-Pd(1)-X(1) 86.83(8) 86.6(1) 88.03(7) 86.9(1) the ν(P]N) stretching band almost unchanged compared to the cor-
N(2)-Pd(1)-Cl(1) 100.07(8) 99.2(1) 100.40(8) 98.2(1) responding one in the free ligands [1259 (6), 1279 (7), 1261 (8) and
X(1)-Pd(1)-Cl(1) 86.89(4) 87.80(4) 85.72(2) 88.00(5) 1263 cm−1 (9)]. In the 1H NMR spectrum, the disappearance of the
P(1)-N(1)-Pd(1)-N(2) 7.30(2) 2.4(2) 8.0(2) 14.9(2)
downfield broad signal attributed to the indolic NH proton in the li-
X(1)-Pd(1)-N(1)-C(9) 1.5(2) −0.5(3) 3.8(2) −9.4(3)
gands confirms the coordination of indole through the N. Another no-
ticeable consequence of the new-formed N−Pd bond in the complexes
atom of the pending arm, sulfur or selenium, nor its substituent, Me or is the downfield shift (Δδ ≈ 1.3 ppm) of the signal belonging to the
Ph, have a significant influence on the phosphorus chemical shift. The closest aromatic proton (H7) when compared to the one in the corre-
1
H NMR spectra of the four compounds also show a downfield shift of sponding free ligand. The N,X (X = S, Se) chelate coordination is also
the broad NH signal [δ 9.69 (2), 9.29 (3), 9.53 (4), 9.47 ppm (5)] confirmed by both 1H and 13C NMR spectra that also show downfield
compared to 1 [Δδ = 1.85 (2), 1.45 (3), 1.69 (4), 1.63 (5) ppm] upon shifts for the nucleus belonging to the aniline ring and the substituent
formation of the P]N bond. There is a tendency for the NH signal to be on the chalcogen atom. The 31P−{1H} NMR spectra show a single
more deshielded when the substituent is Me versus Ph, unregarding the signal for the phosphorus shifted around 40 ppm downfield [δ ppm: 32
nature of the chalcogen atom. Given the large internuclear distance that (6), 33 (7), 34 (8), 34 (9)] when compared to that of the corresponding
separates the NH proton from the Me substituent and the absence of a free ligand, this is a typical shift when the coordination of the iminic
conjugated system between the two groups, this effect is not expected to nitrogen to the metal center is accompanied by the formation of a 5
be a direct inductive influence. We rather believe that the more electron membered chelate ring with an endocyclic P]N group.
donating Me group on the chalcogen atom increases the electronic Suitable crystals of complexes 6–9 were grown by slow concentra-
density on the iminic N, reinforcing a N H−N hydrogen interaction tion of saturated dichloromethane (6–8) or dichloroethane (9) solu-
that led to the deshielding of the NH signal. tions. Complexes 6–8 crystalized with a dichloromethane solvent mo-
Crystals of 2 suitable for X-ray diffraction studies were grown by lecule per asymmetric unit. The ORTEP views for 6 and 7 are shown in
slow vapor diffusion of propanol into a saturated dichloromethane so- Fig. 2, and for 8 and 9 in Fig. 3. The four crystals consist of discrete
lution of the compound. The ligand crystallizes in the triclinic space molecules with the ligands in meridional κ3-N,N,X (X = S, Se) co-
group P-1. Selected bond lengths and bond angles are given in Table 1 ordination to the metal center, confirming the non-symmetrical pincer
and Fig. 1 shows the ORTEP view of 2. The molecular structure of 2 structures proposed on the basis of spectroscopic evidence. Selected
consists of dimers linked by two equivalent strong N H−N hydrogen interatomic distances and angles are listed in Table 1.
bonds between the indolic NH proton and the iminic nitrogen of two All structures show a slightly distorted square-planar geometry for
molecules [d(NN) = 2.853 Å, N−H−N 164.67°]. The P atom is in a the palladium center bonded to four different donor atoms, the indole N
slightly distorted geometry, surrounded by three C atoms at a normal (2) nitrogen, the iminic nitrogen N(1), the chalcogen X(1) (X = S, Se),
distance [1.790(3) to 1.811(3) Å] and the iminic N atom. This N atom is and also to the chlorine atom Cl(1). The pincer coordination typically
sp2 hybridized [P−N−C 127.7(2)°] and the P−N distance of 1.569(2) results in two adjacent and coplanar five-membered palladacycles, al-
Å falls into the typical range for iminophosphorane compounds [27], though in this case these cycles belong to a larger planar system ex-
showing that the N H−N hydrogen bonding as no incidence on the tending from the indole to the aniline ring. For instance the maximum
P−N distance. Finally, as a result of a typical hypervalent interaction in deviations found in the best least-square planes defined by [N(2)C(1)P
organosulfur compounds the intramolecular 1,4 S−N distance in the (1)N(1)Pd(1)] and [N(1)C(9)C(14)X(1)Pd(1), X = S, Se] are respec-
thioaniline residue (2.953 Å) is shorter than the sum of van der Waals tively only 0.054 Å and 0.013 Å for 6, 0.074 Å and 0.008 Å for 7,
radii (3.35 Å) [28]. 0.138 Å and 0.029 Å for 8, 0.074 Å and 0.071 Å for 9. The dihedral
angle between these two planes is only 6.28 (6), 1.18° (7), 7.52 (8) and

Fig. 1. ORTEP representation for 2. Thermal ellipsoid plots shown at the 40% probability level. Hydrogen atoms are omitted for clarity.

3
C.G. Martínez-De-León, et al. Inorganica Chimica Acta 495 (2019) 118945

Scheme 2. Synthesis of pincer complexes

6–9.

Fig. 3. Thermal ellipsoid plots for 8 (a) shown at the 50% probability level and
9 (d) shown at 30% probability level. Hydrogen atoms and a dichloromethane
solvent molecule in (a) have been omitted for clarity.

Fig. 2. Thermal ellipsoid plots for 6 (a) shown at the 30% probability level and
for 7 (b) shown at the 50% probability level. Hydrogen atoms and a di- minor increase in the N(2)−Pd distances in 8 and 9 (X = Se) compared
chloromethane solvent molecule have been omitted for clarity. to those in 6 and 8 (X = S) indicates that the trans influence of Se is
barely stronger than that of S. The P]N distance is fairly the same for
2.34 (9) and the angle between the planes of the indole and the aniline all complexes [1.626(3) Å 6, 1.630(3) Å 7 and 8, 1.633(4) Å 9] and due
aromatic rings is small: 11.88° (6), 6.69° (7), 15.40° (8), 10.54° (9). The to coordination of the N atom to Pd it is slightly longer than the P]N
distance observed in ligand 2 (1.569 Å). Also, these distances are very
angles between adjacent atoms in the palladium coordination sphere
similar to those previously reported by us for Pd(II) non-symmetrical
show limited deviations from the ideal 90°, with the most noticeable
iminophosphorane C,N,S pincer complexes [15], and only slightly
distortion in the N(2)−Pd(1)−Cl(1) angle of 100°, probably a con-
longer then those reported for related N,N Pd(II) quelate complexes
sequence of the steric restriction imposed by the geometry of indole.
based on mixed pyridine-iminophosphorane ligands. For instance, the
The sum of the angles around the iminic nitrogen N(1) [P(1)−N(1)−Pd
longest P]N distance for a Pd(II) complex with a pyridine-iminopho-
(1), C(13)−N(1)−Pd(1) and C(13)−N(1)−P(1)] are very close to 360°
sphorane ligand was reported for the compound
and reveal the trigonal planar geometry of an sp2 hybridized nitrogen
[PdCl2{(Ph3P = N−CH2−2−NC5H4)-κ2-N,N}] [1.610(3) Å] [29].
atom. In general, the Pd(1)−N(1), Pd(1)−N(2) , Pd(1)−X(1) (X = S,
The intermolecular packing of 8 and 9 is further stabilized by sig-
Se) and Pd(1)−Cl(1) distances are within the expected standards for
nificant intermolecular interactions of Se−π and CH−π types (see
these types of complexes. Apart form the S−Pd and Se−Pd distances,
Fig. 4). In both complexes two identical Se−π interactions occurred
which only differ as a consequence of different atomic radius for S and
between the Se of one molecule and the aniline π system of a second
Se, the presence of different chalcogene donor centers has almost no
molecule, forming a dimer. The short Se−π distances (3.734 Å in 8 and
influence on the lengths of coordinative bonds around palladium. The
3.815 Å in 9) and the small angles between the normal to the C6 plane

4
C.G. Martínez-De-León, et al.
Fig. 4. Intermolecular Se−π (red) and CH−π (blue) interactions forming di-
mers in the molecular structures of 8 (a) and 9 (d). Hydrogen atoms are omitted
for clarity. (For interpretation of the references to color in this figure legend,
the reader is referred to the web version of this article.)
through the aryl ring and the vector passing through the centroid to the
Se atom (24.95° in 8 and 24.06° in 9) satisfy the two geometric re-
strictions imposed by Tiekink et al. to consider an existing Se−π in-
teraction, i.e. the distance should be equal to or less than 4 Å, and the
angle should be equal to or less than 30° [30]. According to the lit-
erature these Se−π interactions are important in selenoproteins struc-
tures [31,32] and have a significant influence upon supramolecular
aggregation in the crystal structure of organoselenide compounds. In
addition and again in both complexes, the dimeric arrangement is
further stabilized by two identical CH−π interactions between a CH
from the aniline residue and the π system of a phenyl ring on P (see
Fig. 4) showing CH−π distances of 3.442 Å in 8 and 3.691 Å in 9.
Considering all the data we can see that these interactions in 7 are
stronger than the ones in 9, probably because of both the strongest
electron donating capacity and smallest steric hindrance of Me when
compared to Ph.
2.3. Reactivity of complex 6
Soft thioether and selenoether ligands can bind weakly to transition
metals, and their potential hemilability has frequently been suggested
to be accountable for the catalytic performance of their complexes. In
order to probe the potential hemilability of the five-membered ring
chalcogenoether donors in our complexes, we performed reactivity
studies with a variety of mono- and bidentate neutral donor ligands
(Scheme 3). Complex 6 was chosen as archetype and reactions were
conveniently monitored by 31P–{1H} NMR spectroscopy. Treating so-
lutions of 6 only with nucleophiles gave complex mixtures that pro-
gressively led to decomposition with precipitation of black palladium.
However, performing the exchange of chlorine by less coordinating
anions such as PF6– and BF4– gave clean reactions and very stable
products. Generally, the deep orange solution of 6 turned to a light
yellow color few minutes after the addition of the nucleophile and salt
5
Inorganica Chimica Acta 495 (2019) 118945
at room temperature.
2.3.1. Reaction with triethylamine
Treatment of 6 with triethylamine and NaPF6 in dichloromethane
gave cationic mononuclear compound 10 as an orange air-stable solid,
which was fully characterized. The IR spectrum shows no shift of the
ν(P]N) vibration at 1260 cm−1 compared to that in (6). Two signals in
the 31P–{1H} NMR spectrum are assigned to two distinct 31P nuclei, a
singlet at 32.0 ppm for the coordinated P]N group and a septet at
−146.0 for the PF6− counterion. The 1H and 13C spectra of the N,N,S
coordinated ligand are virtually identical for 10 and the starting com-
plex 6. However both spectra unmistakably show the new signals for
one coordinated triethylamine molecule, notably deshielded compared
to those of free triethylamine. Cleavage of the Pd−S bond was not
observed even with a large excess of triethylamine and use of prolonged
reaction times.
2.3.2. Reaction with pyridine
Reaction of 6 with pyridine and NaPF6 in dichloromethane at room
temperature gave cationic compound 11 in high yield with PF6− as
counterion. The compound was isolated as an orange, air-stable solid
and fully characterized. The IR spectrum shows the ν(P]N) stretch
almost unchanged at 1259 cm−1. The 31P–{1H} NMR spectra of 11 is
similar to that obtain for 10, showing a downfield singlet resonance at
34 ppm corresponding to the coordinated P]N group, and an upfield
septet at −146.00 ppm consistent with the PF6− anion. The 1H and 13C
NMR spectra also confirm the coordination of one pyridine molecule
with largely deshielded resonances compared to free pyridine. The most
striking change in 1H NMR spectra of cationic compound 11 compared
to neutral complex 6, is the 3.49 ppm upfield shift of indolic H7 re-
sonance (8.71 ppm in 6; 5.22 ppm in 11). Such an upfield shift indicates
that H7 in 11 points directly to the aromatic ring of pyridine and suffers
the effect of magnetic anisotropy. The effect is perceptible on the re-
sonance of SMe protons that is also shifted upfield, albeit to a much
lesser extent (Δδ = 0.16 ppm). As already described with triethylamine,
the treatment of 6 with a large excess of pyridine, higher temperature
and longer reaction time never indicated the breaking of the Pd−S
bond.
Good quality crystals of compound 11 were obtained by slow eva-
poration from a concentrated solution of deuterated chloroform. An
ORTEP view of 11 is shown in Fig. 5. Selected interatomic distances and
angles are listed in Table 2. The cationic complex crystallizes in the
monoclinic space group P21/n with one molecule of deuterated
chloroform. The structure is similar to that of starting compound 6, only
with the chlorine atom substituted by a pyridine ring. The κ3-N,N,S
coordination is preserved with the palladium center in a slightly dis-
torted square planar geometry and the indole, the two chelate rings and
the aniline still form an extended planar system. The pyridine plane is
perpendicular to the main plane of the pincer complex, allowing a
strong CH−π interaction between the H7 of the indole ring and the
aromatic system of pyridine (3.575 Å). This interaction further reduces
the angle N(2)-Pd(1)-N(3) [94.78(1)°] compared to the angle N(2)-Pd
(1)-Cl(1) [100.07(8)°] in the neutral complex. This structural feature is
consistent with the strong shielding of H7 observed in 1H NMR spectra
in solution. The P]N bond distance of 1.63(2) Å in (11) do not vary
significantly from that in 6 and in general all the remaining distances
and angles are within the expected range for this type of complexes and
are very close to those in compound 6.
2.3.3. Reaction with triphenylphosphane
Treatment of 6 with triphenylphosphine and NaPF6 in di-
chloromethane at room temperature led to the clean formation of ca-
tion 12 as an orange, air stable solid that could be fully characterized
(Scheme 3). The IR spectrum shows the ν(P]N) stretch slightly shifted
from 1259 cm−1 to 1274 cm−1. The 31P–{1H} NMR spectrum is con-
sistent with the coordination of a triphenylphosphine molecule in place
C.G. Martínez-De-León, et al. Inorganica Chimica Acta 495 (2019) 118945

Scheme 3. Reactivity of complex 6 with

neutral ligands.

Fig. 5. Thermal ellipsoid plots for 11 shown at the 50% probability level.
Fig. 6. Thermal ellipsoid plots for 12 shown at the 50% probability level.
Hydrogen atoms, CDCl3 solvent molecule and PF6− counterion are omitted for
Hydrogen atoms, CH2Cl2 solvent molecules and PF6− counterions are omitted
clarity.
for clarity.

Table 2
in Fig. 6. Selected interatomic distances and angles are listed in Table 2.
Selected bond lengths (Å) and angles (deg) data for 11–13.
The compound crystalizes in the triclinic space group P-1 with 3 in-
6 11 12 13 dependent and identical molecules per asymmetric unit and 2 solvent
molecules. The molecular structure consists of discrete cationic com-
P]N 1.626(3) 1.63(2) 1.618(2) 1.618(3)
N(1)-Pd(1) 2.032(3) 2.030(2) 2.081(2) 2.141(3) plexes and is very similar to that of 11, although with a triphenyl-
N(2)-Pd(1) 2.032(3) 2.018(2) 2.084(2) 2.084(3) phosphane ligand bonded to the palladium atom instead of a pyridine
S(1)-Pd(1) 2.2489(9) 2.2663(7) 2.2816(8) 2.2687(11) * ligand. The κ3-N,N,S coordination is preserved and all bond lengths and
L(1)-Pd(1) 2.308(1) 2.029(2) 2.2799(7) 2.2602(11)
angles are within the expected standards. The palladium center adopts a
S(1)-C(15) 1.812(5) 1.816(4) 1.7806 (10)
Pd(1)-N(1)-P(1) 116.8(1) 114.72(1) 116.4(1) 106.97(11)
slightly distorted square planar geometry, the sum of the angles around
Pd(1)-N(1)-C(9) 117.4(2) 117.56(2) 119.8(2) 128.4(3) Pd is 360° and they differ only a little compared with those in complex 6
P(1)-N(1)-C(9) 125.1(2) 124.37(2) 123.3(2) 124.6(3) or cation 11, probably due to the steric bulk of PPh3. There is some
N(1)-Pd(1)-N(2) 86.3(1) 88.72(1) 86.43(9) 82.84(13) lengthening of the Pd(1)–N(1) and Pd(1)–N(2) bonds, 2.081(2) and
N(1)-Pd(1)-S(1) 86.83(8) 88.41(7) 83.54(6) 94.41(10)*
2.084(2) Å respectively, as compared to complex 6, 2.032(3) and
N(2)-Pd(1)-L(1) 100.07(8) 94.78(1) 99.49(6) 98.48(9)
S(1)-Pd(1)-L(1) 86.89(4) 92.67(7) 90.54(3) 84.67(4)*
2.032(3) Å, and cation 11, 2.030(2) and 2.018(2) Å. This is due to a
P(1)-N(1)-Pd(1)-N(2) 7.30(2) −17.5(1) 1.8(1) −38.40 combination of the stronger trans influence and steric hindrance of the
S(1)-Pd(1)-N(1)-C(9) 1.5(2) 6.8(2) −3.8(8) −19.60 phosphane ligand compared to chloride or pyridine. On the other hand
the P]N bond distance [1.618(2) Å] remains typical for coordinated
*Accurate labeling for 13: bond length P(3)-Pd(1); angles N(1)-Pd(1)-P(3) and iminophosphorane in a pincer mode and appears unaffected by ligand
P(2)-Pd(1)-P(3).
exchange.

of the Cl atom in revealing two singlet signals assigned to two distinct

31
P nuclei coordinated to the palladium center: at δ 29.0 for the co-
ordinated P]N group and δ 24.0 for the coordinated PPh3. Also, the
PF6– anion gave the expected upfield septet at −146.00 ppm. 1H and
13
C NMR spectra also confirm the cationic structure showing the pre-
sence of one coordinated molecule of triphenylphosphine and the sig-
nals attributed to the ligand practically unchanged. Only H7 again
suffers a large upfield shift of 2.39 ppm upon substitution of Cl− by
PPh3, due to the magnetic anisotropy influence of the aromatic rings of
the phosphine. The SMe protons experience the effect to some extent as
their signal is shifted 0.9 ppm upfield, and also appear as a doublet due
to indirect coupling with the 31P of the triphenylphosphine [4J
(HP) = 1 Hz]. The addition of more equivalents of triphenylphosphine
and NaPF6 still do not led to the release of the thioether function.
Good quality crystals of compound 12 were obtained by slow con-
centration of dichloromethane solution. An ORTEP view of 12 is shown
2.3.4. Reaction with dppe: Hemilability
Reaction of 6 with 1,2-bis(diphenylphosphino)ethane (dppe) in
1:1 M ratio and NaBF4 in CH2Cl2 gave novel cationic complex 13 as the
only product in good yields. The compound could be separated as a
yellowish air-stable solid and fully characterized. The IR spectrum
shows no significant shift of the ν(P]N) stretch at 1267 cm−1. The
31
P–{1H} NMR spectra for complex 13 shows a doublet of doublets and
a singlet signals, as expected for three chemically unequivalent 31P
nuclei: an AB system centered at δ = 61.56 ppm (Δν = 63 Hz), readily
assigned to the two 31P of the coordinated diphosphane with a 2J(PP)
coupling value of 13 Hz, and a singlet signal at δ = 35 ppm assigned to
the coordinated iminic phosphorus. The two 31P nuclei of the co-
ordinated dppe give very similar frequencies and cannot clearly be
differentiated, showing that the trans influence of the iminic N and
indolic N are of the same order. The δ 31P of 35 ppm for the iminic P is a

6
C.G. Martínez-De-León, et al.
Fig. 7. a) Thermal ellipsoid plots for 13 (a) shown at the 30% probability level.
Hydrogen atoms are omitted for clarity. b) Detail of the N S interaction and
the short distance between S(1) and Pd(1).
strong indication that the 5 membered N,N chelate ring is preserved.
The 1H and 13C analysis are in agreement with the chelate coordination
of dppe and the release of the thioether function from the metal center.
The main modification in 1H NMR analysis is a clear shifting for all
signals of the thioaniline ring at lower frequencies compared to those in
6, and the effect is most significant for H13 (Δδ = 1.2 ppm). Again,
indolic proton H7 is shifted upfield (Δδ = 1.93 ppm) certainly due to
the effect of magnetic anisotropy from the close Ph rings of dppe. The
effect is also visible on the SMe signal, which is shifted 0.83 ppm at
higher frequencies compared to that same one in 6.
Single crystals of 13 suitable for X ray diffraction analysis were
grown by slow vapor-diffusion of diethyl ether into a dichloromethane
solution. An ORTEP plot of 13 is shown in Fig. 7, and selected intera-
tomic distances and angles are listed in Table 2.
Compound 13 crystalizes in the triclinic P-1 space group with one
ethanol molecule and one BF4– ion that are seriously disordered. So, the
contribution of the highly disordered solvent and counterion to the
scattering was removed with SQUEEZE option of PLATON [33]. The
molecular structure consists of discrete molecules and confirms the
prediction based on NMR data. The palladium atom is in a slightly
distorted square-planar conformation, coordinated to two different bi-
dentate ligands forming two coplanar five membered chelating rings: a
N,N chelate ring containing the iminophosphorane and a P,P bis
7
Inorganica Chimica Acta 495 (2019) 118945
(diphenylphosphino)ethane ring. The sulfur donor atom has been re-
leased from the palladium center, proving the labile coordination of the
thioether function. A remarkable new feature in this structure is the
strong interaction between the sulfur atom S(1) and the iminic nitrogen
N(1) resulting in a N(1)–S(1) distance of 2.812 Å, considerably shorter
(16%) than the sum of the corresponding van der Walls radii {Σr(vdW)
[S, N] = 3.35 Å}. Despite that strong N S interaction, the sum of the
angles with covalently bonded atoms around N(1) [P(1)N(1)Pd(1), Pd
(1)N(1)C(9) and P(1)N(1)C(9)] is still 360°, showing that N(1) keeps an
sp2 hybridization, and the P]N bond length remains unchanged
[1.618(3) Å]. The bond distances around Pd are within the expected
values with almost equivalent Pd–P bond lengths [2.2687(11) Å] and
2.2602(11) Å]. However, there is a significant lengthening of the Pd
(1)–N(1) bond in 13 [2.141(3) Å] compared to that same one in 6
[2.032(3) Å] or even in 12 [2.081(2) Å]. This is imputable not only to
the stronger trans influence of P compared to that of Cl, but also to the
strong N S interaction implicating the iminic N(1). It is worth men-
tioning here that recently, José M. Vila et al. reported a C,N,O dinuclear
pincer species obtained from the orthopalladation of an iminopho-
sphorane ligand derived from 2-aminophenol
[Ph3P = N−(2−OHC6H4)] [34]. Treatment of this pincer complex
with dppe also promoted liberation of the phenol ligand, but in that
case no interaction was observed between the phenolic oxygen and the
rest of the molecule. The strong N S interaction in our case is inter-
esting in that the uncoordinated thioether ligand is held very close to
the metal center in the expectation of back coordination, the distance
between the sulfur atom and the palladium metal center is even slightly
shorter than the sum of vdW radii {d(S−Pd) 3.33 Å < Σr(vdW)[S,
Pd] = 3.43 Å} (see Fig. 7b). Based on the structural analysis this in-
teraction can be described as a non-bonded contact between a nucleo-
phile and a divalent sulfur compound. For instance, both the large
C15S1N1 angle (159.62°) and the small deviation of N1 from the
C14S1C15 plane (0.083 Å) meet the requirements for a classical n
(N1)−σ*(S−C15) interaction [35].
Aiming at proving the reversibility of thioether dissociation, we
anticipated that oxidation of dppe would produce dppeO2, a larger and
harder ligand less prone to chelate Pd(II). After stirring for few days a
dichloromethane solution of 13 saturated with O2, the orange reaction
mixture turned light yellow. The 31P–{1H} NMR spectrum of the crude
medium revealed a singlet at δ 18.5 ppm characteristic for un-
coordinated 1,2-bis(diphenylphosphino)ethane dioxide (dppeO2) and a
singlet at δ 30 ppm attributed to the coordinated iminophosphorane
group, showing that 1,2-bis(diphenylphosphino)ethane was effectively
released from the metal center and transformed into the dioxide
(dppeO2). After addition of triphenylphosphine the dppeO2 could ea-
sily be removed by extraction with diethyl ether, and the cationic
complex 14 was isolated and fully characterized (See Scheme 4). The
31
P−{1H} NMR spectrum shows two singlets, one at 30.9 ppm assigned
to the coordinated iminophosphorane group, and one at 27.3 ppm
corresponding to the coordinated triphenylphosphine. The 1H and 13C
NMR spectra show typical deshielded resonances for the nuclei be-
longing to the thioaniline ring due to the coordination of the thioether
group to the Pd(II) and reformation of the κ3-N,N,S pincer structure. In
general all the signals are identical to those obtained in the analysis of
12, as the sole difference between 12 and 14 is the nature of the
counterion [PF6– (12), BF4– (14)]. Upon liberation of dppe ligand from
the palladium center, the thioether group coordinated back to palla-
dium, reforming the pincer complex. This reaction sequence proved the
reversibility of the labile coordination of the thioether function in 6.
Intending to demonstrate experimentally the hemilability of both
thioether and selenoether ligands in our complexes, solutions of com-
pounds 7–9 were treated with the same sequence. In all reactions,
31
P−{1H} NMR monitoring after treatment with dppe and NaBF4 gave
a spectrum with the expected AB system assigned to two chemically
unequivalent 31P nucleus, belonging to a coordinated dppe around
60 ppm, and one singlet for an iminophosphorane group coordinated in
C.G. Martínez-De-León, et al.
Scheme 4. Reformation of pincer complex upon oxidation of dppe in 13.
Table 3
31
P−{1H} NMR data of the crude reaction between complexes 6–9 and dppe.
31
Complex δ P coordinated dppe [2J(PP) Hz]
6 61.71/61.40 [13.0]
7 59.49/58.46 [19.3]
8 61.48/61.42 [17.8]
9 60.25 (broad signal)
endo mode close to 34 ppm (see Table 3 and ESI). Upon formation of a
dppe chelate ring in reactions of 8 and 9, the selenoether donor dis-
sociates from the Pd(II) center in the same way the thioether does. After
stirring solutions of the corresponding dppe chelates with O2 for few
days, the 31P−{1H} NMR spectra show for all of them two singlets, one
at δ 18.5 ppm indicative of complete dissociation and oxidation of dppe
into free dppeO2, and one at ≈ 30 ppm, assigned to the iminopho-
sphorane group of the unsymmetrical pincer cationic complex. These
results demonstrate the true hemilability of both thioether and sele-
noether donor groups in complexes 6–9, unregarding the nature of the
chalcogene substituent.
3. Experimental
3.1. Crystal structure determinations of 2, 6–9 and 11–13
Single crystals of X-ray quality were grown by vapor diffusion of
propanol (2) or diethyl ether (13) into a dichloromethane solution, also
by slow concentration of dichloromethane (6–8 and 12), deuterated
chloroform (11) and dichloroethane (9) solutions of the compounds at
room temperature. The X-ray intensity data were measured at 298 K for
the complex (7) on a Bruker SMART APEX (7 and 9) and Agilent
Technologies SuperNova instruments, CCD-based three-circle X-ray
diffractometer system using Mo-Kα (λ = 0.71073 Å) or Cu-Kα radiation
(1.54184 Å). The frames were integrated with the Bruker SAINT
Software package [36] using a narrow-frame integration algorithm. The
structures were solved with OLEX2 program [37].
3.2. Materials and methods
All manipulations of air and moisture-sensitive compounds were
performed under an atmosphere of dry nitrogen gas using standard high
vacuum Schlenk and cannula techniques. Solvents were dried and dis-
tilled under nitrogen using standard procedures [38] before use. tert-
butyllitium, n-butyllitium, indole, Pyridine, chlorodiphenylphosphine,
ethylenebis(diphenyposphine), PPh3, NaPF6, NaBF4 2-(phenylthio)
aniline and 2-(methylthio) aniline were obtained commercially from
Aldrich Chem. Co and were used without further purification. Cl2Pd
(NCMe)2 [39] and the azides compounds [21] were synthesized fol-
lowing a literature procedure. NEt3 was dried with CaH2 and distilled
under nitrogen atmosphere. Mass measurements (FAB+) were per-
formed at a resolution of 3000 using magnetic field scans and the
matrix ions as the reference material or, alternatively, by electric field
scans with the sample peak bracketed by two (poly- ethylene glycol or
Inorganica Chimica Acta 495 (2019) 118945
δ 31
P P]N
34.84
32.12
33.89
34.28
Fig. 8. Labeling scheme.
cesium iodide) reference ions. NMR spectra were acquired at ambient
temperature with Varian Mercury Plus 400 MHz, Varian Unity Inova
400 MHz and Bruker AVANCE III HD 500 MHz instruments in CDCl3,
which was used as internal reference. Labelling of atoms is shown in
Fig. 8. 31P−{1H} NMR spectra were recorded with complete proton
decoupling and are reported in ppm. Melting points are uncorrected
and they were measured using sealed capillaries. Infrared spectra were
recorded using the ATR technique in a Thermo Scientific Nicolet in-
strument. Elemental analyses were determined on a Flash 2000 Organic
Elemental Analyzer.
3.3. Experimental section
3.3.1. Compound [2-C8H6N(PPh2)] 1
Butyllithium (5.1 mL, 2.5 M hexane solution, 12.80 mmol) was
added dropwise to a solution of indole (1.5 g, 12.80 mmol) in dry THF
(25 mL) at −78C. The resulting suspension was kept at −78 °C for 1 h,
CO2(g) was then bubbled through the mixture for 30 min, and the clear
solution was allowed to stand for 45 min. The solvent was evaporated,
the white residue was dissolved in 25 mL of dry THF and cooled to
−78 °C, and tert-butyllithium (7.5 mL, 1.7 M pentane solution,
12.80 mmol) was added dropwise. After having held the resulting
cream solution at −78 °C for 1 h, Ph2PCl (2.3 mL, 12.80 mmol) was
added. The reaction mixture was kept at −70 °C for 30 min. A saturated
aqueous solution of NH4Cl (30 mL) was then poured under stirring,
ether (15 mL) was added, and the organic phase was separated, dried
over MgS04, and evaporated affording a white solid in 92% yield
(3.5 g). M.p. 98–100 °C. Anal. Calc. For C20H16N1P1 (301.1): C, 79.72;
H, 5.35; N, 4.65. Found: C, 79.71; H, 5.36; N, 4.64. MS (FAB+) 301 m/z
(M+) 100%. 31P NMR (162 MHz, CDCl3, 20 °C): δ −26.8; 1H NMR
(400 MHz, CDCl3, 20 °C): δ 7.84 (m, NH), 6.65 (m, H2), 7.51 (m, H4,
3
JH4H5 = 8 Hz), 7.01 (ddd, H5, 3JH5H4 = 8 Hz, 3JH5H6 = 7.2 Hz,
4
JH5H7 = 1.2 Hz), 7.10 (ddd, H6, 3JH6H7 = 8 Hz, 3JH6H5 = 7.2 Hz,
4
JH6H4 = 1.2 Hz), 7.20 (d, H7, 3JH7H6 = 8 Hz), 7.25–7.31 (m, 10H, Ho-
Hp); 13C NMR (100 MHz, CDCl3, 20 °C): δ 132.75 (C1, 1JCP = 17 Hz),
113.38 (C2, 2JPC = 22 Hz), 128.53 (C3), 121.0 (C4), 120.2 (C5), 123.11
(C6), 111.1 (C7), 138.86 (C8), 136.32 (2C, Phipso1JCP = 7.3 Hz), 129.1
(4C, Pho 2JPC = 26.4 Hz), 133.40 (4C, Phm 3JPC = 19 Hz), 128.90 (2C,
Php).
8
C.G. Martínez-De-León, et al.
3.3.2. General procedure for the preparation of ligands 2–5
(2-indolyl)diphenilphosphine 1 and hexane (5 mL) were placed into
a degassed Schlenk. Aryl azide was added into the Schlenk under ni-
trogen atmosphere. Nitrogen gas was generated immediately; the re-
sulting mixture was stirred for 1 h and a precipitate formed. Then, the
crude reaction was filtered through cannula and the cream precipitate
was dried in vacuum.
3.3.3. Compound [2-C8H6N(Ph2P = NC6H4SCH3)] 2
Phosphine 1 (200 mg, 0.664 mmol) and 109 mg (0.664 mmol) of
N3C6H4SMe. Yield 371 mg (98%). M.p. 220–222 °C. Anal. Calc. For
C27H23N2P1S1 (438.1): C 73.95; H 5.29; N 6.39. Found: C 74.01; H 5.32;
N 6.33. MS (FAB+) 438 m/z (M+) 19%. IR (ν, cm−1): 1258.3 (νPN). 31P
NMR (162 MHz, CDCl3, 20 °C): δ −7.7; 1H NMR (400 MHz, CDCl3,
20 °C): δ 9.69 (br, NH), 6.78 (d, H2, 3JH2P = 3.6 Hz) 7.61 (d, H4,
3
JH4H5 = 8 Hz), 7.26 (dd, 1H5, 3J H5H4, = 8 Hz, 3JH5H6 = 7.2 Hz), 7.12
(dd, H6, 3J H6H5,=7.2 H6H7 = 8 Hz), 7.42–7.47 (H7), 6.437 (d, H10,
3
JH10H11 = 8.8 Hz), 6.71–6.74 (H11), 6.71–6.74 (H12), 7.04 (m, H13),
2.47 (s, 3H, SMe), 7.81–7.87 (m, 4H, Pho), 7.42–7.47 (m, 4H, Phm),
7.51–7.55 (m, 2H, Php); 13C NMR (100 MHz, CDCl3, 20 °C): δ 132.4 (d,
C1, 1J C1P = 2 Hz), 112.0 (d, C2, 2JC2P = 15 Hz) 128.5 (s, C3), 121.7 (s,
C4), 120.7 (s, C5), 124.4 (s, C6), 112.3 (s, C7), 138.2 (d, C8, 3J
3
C1P = 8.3 Hz), 147.0 (s, C9), 119.7 (d, C10, JC10P = 9.3 Hz), 118.8 (s,
C11), 124.6 (C12), 123.7 (s, C13), 133.6 (s, C14, 3JC14P = 22.6 Hz), 14.6
(s, C15, SMe), 130.9 (d, 2C, Phipso, 1J = 100 Hz), 132.6 (d, 4C, Pho,
2
J = 10.8 Hz), 128.8 (d, 4C, Phm, 3J = 12.5 Hz), 132.2 (d, 2C, Php,
4
J = 2.9 Hz).
3.3.4. Compound [2-C8H6N(Ph2P = NC6H4SC6H5)] 3
Phosphine 1 500 mg (1.66 mmol) and 377 mg (1.66 mmol) of
N3C6H4SPh. Yield 764 mg (92%). M.p. 158–159 °C. Anal. Calc. For
C32H25N2P1S1 (500.59): C 76.78; H 5.03; N 5.60. Found: C 76.84; H
5.05; N 5.54. MS (FAB+) 501 m/z (M+) 43%. IR (ν, cm−1): 1275.1
(νPN). 31P NMR (162 MHz, CDCl3, 20 °C): δ −6.8; 1H NMR (400 MHz,
CDCl3, 20 °C): δ 9.29 (br, NH), 6.71 (d, H2, 3JH2P = 4 Hz), 7.59 (d, H4,
3
JH4H5 = 8 Hz), 7.12 (dd, H5, 3J H5H4, = 8 Hz, 3JH5H6 = 8 Hz),
7.25–7.29 (H6), 7.36–7.41(H7), 6.58 (d, H10, 3JH10H11 = 8 Hz), 6.65
(dd, H11,3J H11H10, = 8 Hz, 3JH11H12 = 8 Hz), 6.90 (dd, H12, 3J H12H11,
= 8 Hz, 3JH12H13 = 8 Hz), 7.17–7.21 (H13), 7.36–7.42 (m, 2H, SPho),
7.26–7.29 (m, 2H, SPhm), 7.17–7.21 (m, H, SPhp), 7.74–7.79 (m, 4H,
PPho), 7.44–7.48 (m, 4H, PPhm), 7.54–7.57 (m, 2H, PPhp); 13C NMR
(100 MHz, CDCl3, 20 °C): δ 131.2 (d, C1, 1J C1P = 11 Hz), 111.8 (d, C2,
2
JC2P = 16 Hz), 128.4 (s, C3, 3JC3P = 13 Hz), 121.7 (s, C4), 120.6 (s, C5),
124.4 (s, C6), 112.3 (d, C7), 138.1 (d, C8, 3J C8P = 9 Hz), 149.9 (s, C9),
121.1 (d, C10, 3JC10P = 10 Hz), 118.5 (s, C11), 128.1 (C12), 126.2 (s,
C13), 132.05 (C14, 3JC14P = 11 Hz), 137,1 (s, 1C, SPhipso), 130.26 (s, 2C,
SPho), 129.1 (s, 2C, SPhm), 132.1 (s, 1C, SPhp), 129.7 (d, 2C, PPhipso,
1
J = 99 Hz), 132.6 (d, 4C, PPho, 2J = 10.7 Hz), 128.8 (d, 4C, PPhm,
3
J = 12 Hz), 132.3 (d, 2C, PPhp, 4J = 3 Hz).
3.3.5. Compound [2-C8H6N(Ph2P = NC6H4SeCH3)] 4
106 mg of phosphine 1 (0.352 mmol) and 75 mg (0.352 mmol) of
N3C6H4SeMe. Yield 136 mg (91%). M.p. 208–210 °C. Anal. Calc. For
C27H23N2P1Se1 (486.08): C 62.12; H 5.45; N 6.59. Found: C 62.17; H
5.49; N 6.55. MS (FAB+) 487 m/z (M+) 15%. IR (ν, cm−1): 1303.0
(νPN). 31P NMR (162 MHz, CDCl3, 20 °C): δ −7.6; 1H NMR (400 MHz,
CDCl3, 20 °C): δ 9.53 (br, NH), 6.80 (H2), 7.61 (d, H4, 3JH4H5 = 8 Hz),
7.26 (dd, H5, 3J H5H4, = 8 Hz, 3JH5H6 = 7.2 Hz), 7.09–7.14 (H6),
7.09–7.14 (H7) 6.41 (d, H10, 3JH10H11 = 6.4 Hz) 6.91–6.77 (H11)
6.91–6.77 (H12) 7.42–7.46 (H13), 2.28 (s, 3H, SeMe) 7.82–7.87 (m, 4H,
Pho) 7.42–7.46 (m, 4H, Phm) 7.51–7.53 (m, 2H, Php); 13C NMR
(100 MHz, CDCl3, 20 °C): δ 132.4 (d, C1, 1J C1P = 3 Hz), 112.4 (d, C2,
2
JC2P = 16 Hz), 128.4 (s, C3, 3JC3P = 12 Hz), 121.8 (s, C4), 120.8 (s, C5),
124.6 (s, C6), 112.3 (s, C7), 138.3 (d, C8, 3J C1P = 5.3 Hz), 148.3 (s, C9),
119.3 (d, C10, 3JC10P = 15 Hz), 119.0 (s, C11), 125.4 (s, C12), 126.2 (s,
C13), 133.5 (s, C14, 3J C14P = 15 Hz), 4.5 (s, C15, SeMe), 130.8 (d, 2C,
9
Inorganica Chimica Acta 495 (2019) 118945
Phipso, 1J = 102 Hz), 132.6 (d, 4C, Pho, 2J = 10.4 Hz), 128.9 (d, 4C,
Phm, 3J = 12.5 Hz), 132.3 (d, 2C, Php, 4J = 2.9 Hz).
3.3.6. Compound [2-C8H6N(Ph2P = NC6H4SeC6H5)] 5
300 mg of phosphine 1 (0.995 mmol) and 273 mg (0.995 mmol) of
N3C6H4SePh. Yield 545 mg (93%). M.p. 262–264 °C. Anal. Calc. For
C32H25N2P1Se1 (548.0): C 70.20; H 4.60; N 5.12. Found: C 70.23; H
4.62; N 5.13. MS (FAB-H)+ 548 m/z (M+) 20%. IR (ν, cm−1): 1274.4
(νPN). 31P NMR (162 MHz, CDCl3, 20 °C): δ −7.0; 1H NMR (400 MHz,
CDCl3, 20 °C): δ 9.47 (br, NH), 6.59 (s, H2), 7.61 (d, H4, 3JH4H5 = 8 Hz),
7.12 (dd, H5, 3JH5H4 = 8 Hz, 3JH5H6 = 7 Hz), 7.27 (H6), 7.42 (H7), 6.49
(d, H10 3JH10H11 = 7.2 Hz), 6.54 (dd, H11, 3JH11H10 = 7.2 Hz,
3
JH11H12 = 8 Hz), 6.88 (dd, H12, 3JH12H11 = 8 Hz, 3JH12H13 = 8 Hz),
6.78 (m, H13), 7.64–7.72 (m, 2H, SePho), 7.27–7.35 (m, 2H, SePhm),
7.52–7.54 (m, 1H, SePhp), 7.80–7.85 (m, 4H, PPho), 7.41–7.47 (m, 4H,
PPhm), 7.64–7.72 (m, 2H, PPhp); 13C NMR (100 MHz, CDCl3, 20 °C): δ
129.3 (d, C1, 1JPC1 = 6 Hz), 112.4 (d, C2, 2JPC = 20.4 Hz), 128.5 (s, C3),
121.8 (s, C4), 120.8 (s, C5), 124.6 (s, C6), 112.2 (s, C7), 148.7 (s, C8),
150.7 (s, C9), 120.7 (C10, 3JPC = 10.8 Hz), 119.0 (s, C11), 129.5 (s, C12),
126.8 (s, C13,), 130.3 (d, C14, 3JPC14 = 34 Hz), 130.7 (s, 1C, SePhipso),
135.6 (s, 2C, SePho), 127.9 (s, 2C, SePhm), 129.5 (s, 1C, SePhp), 131.2
(d, 2C, PPhipso, 1J = 93 Hz) 132.6 (d, 4C, PPho, 2J = 11 Hz) 128.9 (d,
4C, PPhm, 3J = 13 Hz) 132.4 (s, 2C, PPhp).
3.3.7. General procedure for the preparation of complexes 6–9
1 equivalent of Cl2Pd(MeCN)2 was added to a dry 1,2-dicloroethane
solution of the corresponding iminophosphorane (5 mL) and Na3PO4 in
excess under a nitrogen atmosphere. The solution was refluxed for 2 h.
The solvent was removed under vacuum and the orange solid residues
were purified by flash chromatography (CH2Cl2/Hexane, 70:30).
3.3.8. Compound [PdCl{2-C8H5N(Ph2P = NC6H4SCH3- κ3-NNS)}] 6
58 mg of iminophosphorane 2 (0.132 mmol) and 34 mg
(0.132 mmol) of (MeCN)2PdCl2. Yield mg 81 (%). M.p. 258–260 °C
(dec.). Anal. Calc. For C27H22N2P1S1Cl1Pd1 (578.0): C 55.97; H 3.83; N
4.83. Found: C 56.01; H 3.87; N 4.80. MS (FAB+) 579 m/z (M+) 20%.
IR (ν, cm−1): 1258.6 (νPN). 31P NMR (162 MHz, CDCl3, 20 °C): δ 31.9;
1
H NMR (500 MHz, CDCl3, 20 °C): δ 6.62 (s, H2), 7.48 (d, H4,
3
JH4H5 = 8 Hz), 6.96–6.91 (H5), 7.14 (dd, 1H6, 3J H6H5 = 7.5 Hz, 3J
H6H7 = 8 Hz), 8.71 (d, H7, 3J H7H6 = 8 Hz), 6.64 (d, H10,
3
JH10H11 = 8.5 Hz), 6.91–6.95 (H11), 6.80 (dd, H12, 3
J
3 3
H12H11 = 7.5 Hz, J H12H13 = 8 Hz), 7.30 (d, H13, J H13H12 = 8 Hz), 2.85
(s, 3H, SMe), 7.78–7.88 (m, 4H, Pho), 7.50–7.55 (m, 4H, Phm),
7.61–7.68 (m, 2H, Php); 13C NMR (125 MHz, CDCl3, 20 °C): δ 136.0 (s,
C1), 110.7 (d, C2, 2JC2P = 28 Hz), 129.5 (s, C3), 120.4 (s, C4), 119.1 (s,
C5), 123.0 (s, C6), 118.0 (s, C7), 149.2 (s, C8), 153.3 (s, C9), 119.4 (d,
C10, 3JC10P = 8 Hz), 130.5 (s, C11), 120.8 (s, C12), 133.2 (s, C13), 126.2
(s, C14), 28.2 (s, 1C, SMe), 129.5 (s, 2C, Phipso), 133.3 (d, 4C, Pho,
2
JCP = 13 Hz), 129.6 (d, 4C, Phm, 3JCP = 12 Hz), 133.9 (d, 2C, Php,
4
JCP = 7 Hz).
3.3.9. Compound [PdCl{2-C8H5N(Ph2P = NC6H4SC6H5- κ3-NNS)}] 7
29 mg of compound 3 (0.0578 mmol) and 15 mg of (MeCN)2PdCl2
(0.0578 mmol). Yield 25 mg (67%). Anal. Calc. For
C32H24N2P1S1Cl1Pd1 (640.01): C 59.92; H 3.77; N 4.37. Found: C,
59.89; H 3.73; N 4.40. El M.p. 139–141 °C (dec.). MS (FAB+) 641 m/z
(M−H)+ 35%. IR (ν, cm−1): 1278.6 (νPN). 31P NMR (162 MHz, CDCl3,
20 °C): δ 33.1; 1H NMR (400 MHz, CDCl3, 20 °C): δ 6.61 (d, H2,
3
JH2P = 2 Hz), 7.46 (d, H4, 3JH4H5 = 8 Hz), 6.92 (dd, H5, 3JH5H4 = 8 Hz,
3
JH5H6 = 8 Hz), 7.10 (dd, 1H, H6, 3JH6H5 = 8 Hz, 3JH6H7 = 8 Hz), 8.69
(d, H7, 3JH7H6 = 8 Hz), 6.73–6.78 (H10), 6.97 (dd, H11, 3JH11H10 = 8 Hz,
3
JH11H12 = 8 Hz), 6.73–6.78 (H12), 7.22 (d, H13, 3JH13H12 = 8 Hz),
7.58–7.61 (m, 2H, SPho), 7.27–7.36 (m, 2H, SPhm), 7.27–7.36 (m,1H,
SPhp), 7.82–7.91 (m, 4H, PPho), 7.51–7.58 (m, 4H, PPhm), 7.63–7.70
(m, 2H, PPhp); 13C NMR (100 MHz, CDCl3, 20 °C): δ 136.3 (d, C1, 1J
2
C1P = 18 Hz), 110.9 (d, C2, JC2P = 29 Hz), 129.7 (s, C3), 120.1 (s, C4),
C.G. Martínez-De-León, et al.
119.2 (s, C5), 122.9 (s, C6), 118.2 (s, C7) 149.0 (s, C8), 154.0 (s, 1C9),
119.5 (d, 1C10, 3JC10P = 8 Hz), 131.0 (s, C11), 130.0 (C12), 121.9 (s,
C13), 125.0 (d, C14, 3JC14P = 16 Hz), 134.1 (s, 1C, SPhipso), 130.6 (s, 2C,
SPho), 129.8 (s, 2C, SPhm), 134.9 (s,1C, SPhp) 129.8 (d, 2C, PPhipso),
133.2 (d, 4C, PPho, 2J = 12 Hz), 129.6 (d, 4C, PPhm, 3J = 12 Hz), 134.0
(d, 2C, PPhp, 4J = 3 Hz).
3.3.10. Compound [PdCl{2-C8H5N(Ph2P = NC6H4SeCH3- κ3-NNSe)}] 8
20 mg (0.041 mmol)of iminophosphorane 4 and 11 mg
(0.041 mmol) of (MeCN)2PdCl2. Yield 18 mg (72%). M.p. 158–160 °C
(dec.). Anal. Calc. For C27H22N2P1Se1Cl1Pd1 (625.94): C, 51.78; H 3.54;
N 4.47. Found: C, 51.80; H 3.51; N 4.48. MS (FAB+) 626 m/z (M+)
20%. IR (ν, cm−1): 1261.3 (νPN). 31P NMR (162 MHz, CDCl3, 20 °C): δ
33.9; 1H NMR (400 MHz, CDCl3, 20 °C): δ 6.60 (s, H2), 7.47–7.54 (H4),
6.90–6.96 (H5), 7.14 (dd, 1H6, 3J H6H5 = 7 Hz,3J H6H7 = 8.8 Hz), 8.70
(d, H7,3J H7H6 = 8.8 Hz), 6.66 (d, H10, 3JH10H11 = 8.4 Hz), 6.90–6.96
(H11), 6.773 (H12), 7.35 (H13, 3J H13H12 = 9 Hz), 2.72 (s, 3H, SeMe),
7.78–7.87 (m, 4H, Pho), 7.47–7.55 (m, 4H, Phm), 7.59–7.67 (m, 2H,
Php); 13C NMR (100 MHz, CDCl3, 20 °C): δ 134.2 (s, C1,1JC1P = 3 Hz),
110.3 (d, C2, 2JC2P = 28 Hz), 128.8 (s, C3, 3JC3P = 13 Hz), 120.8 (s, C4),
119.1 (s, C5), 122.8 (s, C6), 117.9 (s, C7), 149.0 (d, C8, 3J
3
C8P = 15.9 Hz), 154.1 (s, C9), 120.1 (d, C10, JC10P = 9 Hz), 130.2 (s,
C11), 120.7(s, C12), 134.9 (s, C13), 126.7 (s, C14, 3JC14P = 20 Hz), 14.3
(s, C, SeMe), 132.3 (s, 1C, Phipso, 1J CP = 51 Hz), 132.2 (s, 1C, *Phipso,
1
J CP = 51 Hz), 133.3 (d, 2C, Pho, 2JCP = 10 Hz), 133.2 (d, 2C, *Pho,
2
JCP = 10 Hz), 129.58 (d, 2C, Phm, 3JCP = 12 Hz), 129.55 (d, 2C, *Phm,
3
JCP = 12 Hz), 133.83 (d, 1C, Php, 4JCP = 7 Hz), 133.80 (d, 1C, *Php,
4
JCP = 7 Hz).
3.3.11. Compound [PdCl{2-C8H5N(Ph2P = NC6H4SeC6H5- κ3-NNSe)}] 9
21 mg (0.038 mmol) of 5 and 10 mg of (MeCN)2PdCl2
(0.038 mmol). It was obtained as red solid. Yield 18 mg (70%). M.p.
217–219 °C (dec.). Anal. Calc. For C32H24N2P1Se1Cl1Pd1 (687.35): C
55.84; H 3.51; N 4.07. Found: C 55.88; H 3.49; N 4.08. MS (FAB+)
688 m/z (M−H)+ 40%. IR (ν, cm−1): 1263.7 (νPN). 31P NMR
(162 MHz, CDCl3, 20 °C): δ 34.1; 1H NMR (400 MHz, CDCl3, 20 °C): δ
6.59 (s, H2) 7.46 (d, H4, 3JH4H5 = 8 Hz), 6.93 (dd, H5, 3JH5H4 = 8 Hz,
3
JH5H6 = 8 Hz), 7.11 (dd, 1H, H6, 3JH6H5 = 8 Hz, 3JH6H7 = 8 Hz), 8.71
(d, H7, 3JH7H6 = 8 Hz), 6.74 (H10, 3JH10H11 = 8 Hz), 6.96 (dd, H11,
3
JH11H10 = 8 Hz, 3JH11H12 = 8 Hz), 6.78 (dd, H12, 3JH12H11 = 8 Hz,
3
JH12H13 = 8 Hz), 7.32–7.37 (H13), 7.63–7.67 (m, 2H, SePho),
7.26–7.32 (m, 2H, SePhm), 7.25–7.32 (m, 1H, SePhp), 7.80–7.87 (m,
4H, PPho), 7.48–7.55 (m, 4H, PPhm), 7.63–7.67 (m, 2H, PPhp); 13C
NMR (100 MHz, CDCl3, 20 °C): δ 135.8 (C1), 110.4 (d, C2,
2
JC2P = 28 Hz), 130.0 (s, C3), 120.2 (s, C4), 119.1 (s, C5), 122.8 (s, C6),
118.0 (s, C7), 149.4 (s, C8), 154.9 (s, C9), 120.4 (d, C10, 3JC10P = 9 Hz),
130.7 (s, C11), 120.9 (C12), 136.8 (s, C13), 120.6 (s, C14,), 130.9 (s, 1C,
SePhipso), 131.0 (s, 2C, SePho), 130.1 (s, 2C, SePhm), 129.6 (s,1C,
SePhp), 129.7 (d, 2C, PPhipso), 133.3 (d, 2C, PPho, 2J = 11 Hz), 133.1
(d, 2C, *Pho, 2JCP = 10 Hz), 129.6 (d, 2C, Phm, 3JCP = 8 Hz), 129.5 (d,
2C, *Phm, 3JCP = 6 Hz), 133.87 (d, 1C, Php), 133.81 (d, 1C, *Php).
3.3.12. General procedure for the preparation of cations 10–12
The nucleophile was added to a solution of 6 in anhydrous CH2Cl2
(4 mL). After 20 min of stirring at room temperature, NaPF6 in excess
was added. 14 h after, the precipitated salts were filtered off over celite
and the solvent was evaporated to dryness, affording as oranges pow-
ders. The solids were purified by flash chromatography (CH2Cl2/THF,
97:03).
3.3.13. Compound [PdNEt3{2-C8H5N(Ph2P = NC6H4SCH3- κ3-NNS)}]
PF6 10
11 mg (0.019 mmol) of complex 6 and 5 mg (0.049 mmol) of NEt3.
Yield 13 mg (87%). M.p. 90–92 °C (dec.). Anal. Calc. For
C33H35F6N3P2Pd1S1 (787.01): C 59.92; H 3.77; N 4.37. Found: C 59.86;
H 3.73; N 4.41. MS (FAB+) 642 m/z (M−H)+ 8%. IR (ν, cm−1): 1260.2
10
Inorganica Chimica Acta 495 (2019) 118945
(νPN). 31P NMR (162 MHz, CDCl3, 20 °C): δ 32 (s, P]N), 146 (septet,
PF6); 1H NMR (500 MHz, CDCl3, 20 °C): δ 6.63–6.65 (H2), 7.48 (d, H4,
3
JH4H5 = 8 Hz), 6.92–6.95 (H5), 7.13 (dd, H6, 3J H6H5 = 7.5 Hz,3J
3
H6H7 = 8.5 Hz), 8.68 (d, H7 J H7H6 = 9 Hz), 6.63–6.65 (H10), 6.92–6.95
(1H11), 6.81 (dd, 1H12, 3J H12H11, H12H13 = 8 Hz), 7.31 (d, 1H13, 3J
H13H12 = 8 Hz), 2.85 (s, 3H, SMe), 7.78–7.87 (m, 4H, Pho), 7.50–7.57
(m, 4H, Phm), 7.62–7.69 (m, 2H, Php), 3.10 (q, 6H, NEt3), 1.29 (t, 9H,
NEt3); 13C NMR (125 MHz, CDCl3, 20 °C): δ 136.1 (s, C1,
1
JC2P = 159.5 Hz), 110.8 (d, C2, 2JC2P = 28 Hz), 129.6 (s, C3), 120.4 (s,
C4), 119.3 (s, C5), 123.0 (s, C6), 117.9 (s, C7), 148.9 (d, C8,
3
JC8P = 15.3 Hz), 153.4 (s, C9), 119.5 (d, C10, 3JC10P = 5 Hz), 130.6 (s,
C11), 121.4 (s, C12), 133.2 (s, 1C13), 125.9 (d, C14, 3JC14P = 15 Hz), 28.1
(s, 1C, SMe), 129.6 (2C, Phipso,), 133.1 (d, 4C, Pho, 2JCP = 13 Hz), 129.7
(d, 4C, Phm, 3JCP = 14 Hz), 133.8 (d, 2C, Php, 4JCP = 7 Hz), 47.7 (s, 3C,
NEt3), 9.0 (s, 3C, NEt3).
3.3.14. Compound [PdC5H5N{2-C8H5N(Ph2P = NC6H4SCH3- κ3-NNS)}]
PF6 11
15 mg (0.026 mmol) of complex 6 and 4 mg (0.050 mmol) of
Pyridine. Yield 16.5 mg (83%). M.p. 160–162 °C (dec.). Anal. Calc. For
C32H27F6N3P2Pd1S1 (767.03): C 50.04; H 3.54; N 5.47. Found: C 49.83;
H 3.49; N 5.51. MS (FAB+) 623 m/z (M−PF6)+ 21%. IR (ν, cm−1):
1259.2 (νPN). 31P NMR (162 MHz, CDCl3, 20 °C): δ 34 (s, P]N), 146
(septet, PF6); 1H NMR (500 MHz, CDCl3, 20 °C): δ 6.74 (s, H2), 7.51 (d,
H4, 3JH4H5 = 8 Hz), 6.86 (H5), 6.69 (H6), 5.22 (d, H73J H7H6 = 8.5 Hz),
6.67 (d, H10, 3JH10H11 = 8.5 Hz), 6.99 (H11), 6.89 (H12), 7.38 (d, H13, 3J
H13H12 = 7.5 Hz), 2.69 (s, 3H, SMe), 7.80–7.85 (m, 4H, Pho), 7.57–7.59
(m, 4H, Phm), 7.69–7.75 (m, 2H, Php), 9.02 (br, 1H, py), 9.01 (br, 1H,
py), 8.17–8.20 (2H, py), 7.77–7.80 (m, 1H, py); 13C NMR (125 MHz,
CDCl3, 20 °C): δ 134.9 (s, 1C1), 110.7 (d, C2, 2JC2P = 28 Hz), 129.0 (s,
C3), 121.4 (s, C4), 119.1 (s, C5), 123.2 (s, C6), 113.3 (s, C7), 144.6 (s,
1C8), 151.8 (s, C9), 119.5 (d, 1C10, 3JC10P = 8 Hz), 130.8 (s, C11), 121.6
(s, C12), 133.2 (s, C13), 122.4 (s, C14), 26.9 (s, 1C, SMe), 129.4 (s, 2C,
Phipso), 132.7 (d, 4C, Pho), 129.6 (d, 4C, Phm) 132.8 (d, 2C, Php), 153.3
(s, 2C, Py), 134.0 (s, 2C, Py), 140.8 (s, 1C, Py).
3.3.15. Compound [PdPC18H15{2-C8H5N(Ph2P = NC6H4SCH3- κ 3-
NNS)}]PF6 12
15 mg (0.026 mmol) of complex 6 and 6.7 mg (0.036 mmol) of
PPh3. Yield 23 mg (93%). Anal. Calc. For C45H37F6N2P3Pd1S1 (950.08):
C 56.82; H 3.92; N 2.95. Found: C 56.80; H 3.89; N 2.96. M.p.
128–130 °C. MS (FAB+) 806 m/z (M−PF6)+ 24%. IR (ν, cm−1): 1274.5
(νPN). 31P NMR (162 MHz, CDCl3, 20 °C): δ 29 (s, P]N), 24 (s,PPH3),
146 (septet, PF6); 1H NMR (500 MHz, CDCl3, 20 °C): δ 6.78 (dd, H2,
0.5 Hz, 3 Hz), 7.36 (d, H4, 3JH4H5 = 8 Hz), 6.62 (dd, H5,3J H5H4,
3 3
H5H6 = 7.5 Hz), 6.20 (dd, H6, J H6H5, = 7.5 Hz, JH6H7 = 8 Hz), 6.32
(d, H7,3J H7H6 = 8 Hz), 6.68 (d, H10, 3JH10H11 = 8.5 Hz), 7.04 (dd, H11,
3
J H11H10, = 8.5 Hz, 3J H11H12 = 7.5 Hz), 6.85 (dd, H12, 3J
3 3
H12H11 = 7.5 Hz, J H12H13 = 8 Hz), 7.23 (d, 1H13, J H13H12 = 8 Hz),
4
1.95 (d, 3H, SMe, JH15P = 1 Hz), 7.97–7.91 (m, 4H, Pho), 7.59–7.62
(m, 4H, Phm), 7.73–7.66 (m, 2H, Php), 7.75–7.79 (m, 6H, PPh3),
7.42–7.46 (m, 6H, PPh3), 7.50–7.56 (m, 3H, PPh3); 13C NMR (125 MHz,
CDCl3, 20 °C): δ 137.1 (d, C1, 1JC1P1 = 156.8 Hz), 114.137 (d, C2,
2
JC2P1 = 27 Hz), 129.7 (s, C3), 121.029 (s, C4), 118.84 (s, C5), 121.93
(s, C6), 117.5 (s, C7),146.3 (C8,3JC2P = 13 Hz), 151.88 (s, C9), 119.87
(d, C10, 3JC10P1 = 8 Hz), 132.17 (s, C11), 122.46 (s, C12), 133.46 (s, C13),
125.34 (dd, C14, 3JC2P1 = 16 Hz, 3JC14P2 = 7 Hz), 28.77 (s, 1C, SMe),
131.7 (d, 2C,Phipso, 1JCP1 = 53 Hz), 132.71 (d, 4C, Pho, 2JCP1 = 10 Hz),
129.94 (d, 4C, Phm,3JCP1 = 13 Hz), 130.24 (d, 2C, Php, 4JCP1 = 14 Hz),
128.282 (d, 3C, PPh3, Phipso, 1JCP2 = 54 Hz), 134.947 (d, 6C, PPh3, Pho,
2
JCP2 = 12 Hz), 129.628 (d, 6C, PPh3, Phm, 3JCP2 = 11 Hz), 133.148 (d,
3C, PPh3, Php, 4JC23P2 = 2 Hz).
3.3.16. Compound [Pd(PPh2CH2CH2PPh2- κ2-PP){2-C8H5N(Ph2P =
NC6H4SCH3-κ2-NN)}]BF4 13
10.3 mg (0.036 mmol) of dppe was added to a solution of 6 (15 mg,
C.G. Martínez-De-León, et al.
0.026 mmol) in anhydrous CH2Cl2 (5 mL). After 20 min of stirring at
room temperature, NaBF4 was added in excess. 14 h after, the pre-
cipitated salts were filtered off through celite® and the solution was
concentrated to small volume under vacuum, then 2 mL of Et2O were
added. After 16 h, yellow crystals were obtained. Yield 19.5 mg (73%).
M.p. 204–206 °C. Anal. Calc. For C53H46B1F4N2P3Pd1S1 (1028.17): C
67.55; H 4.92; N 2.97. Found: C 67.46; H 4.92; N 2.98 MS (FAB+)
942 m/z (M−PF6) 30%. IR (ν, cm−1): 1260.8 (νPN). 31P NMR
(202.4 MHz, CDCl3, 20 °C): δ 34.8 (s, P]N), 61.41 (dppe,
3
JP2P3 = 13 Hz), 61.70 (dppe, 3JP3P2 = 13 Hz); 1H NMR (500 MHz,
CDCl3, 20 °C): δ 6.58 (s, H2), 7.26–7.38 (H4), 6.65–6.71 (H5), 6.41 (dd,
H6, 3J H6H5, = 7.5 Hz, 3JH6H7 = 8.5 Hz), 6.78 (d, H7, 3J H7H6 = 8.5 Hz),
6.48–6.55 (H10), 6.48–6.55 (H11), 6.48–6.55 (H12), 6.11 (d, H13, 3J
H13H12 = 7.5 Hz), 2.02 (s, 3H, SMe) 8.60–8.64 (m, 2H, Pho), 7.76–7.85
(m, 5H, Phm, Php, *Phm), 7.95–8.00 (m, 2H, *Pho) 7.90–7.94 (m, 1H,
*Php), 2.92 (2H, CH2CH2, dppe), 1.96 (2H, CH2CH2, dppe), 7.58–7.62
(m, 2H, Pho, dppe), 7.44–7.52 (m, 1H, Php, dppe), 7.41–7.52 (m, 2H,
Pho, dppe), 7–26–7.38 (m, 4H, 2Pho, dppe), 7.09–7.21 (m, 7H, 4Phm,
3Php, dppe), 7.00–7.04 (m, 2H, Phm, dppe), 6.65–6.71 (m, 2H, Ph0,
dppe); 13C NMR (125 MHz, CDCl3, 20 °C): δ 125.0 (d, 1C1,
1
JC1P1 = 117.5 Hz), 111.3 (d, C2, 2JC2P1 = 26 Hz), 131.0 (d, C3,
3
JC3P1 = 8.7 Hz), 121.1 (s, C4), 118.6 (s, C5), 121.32 (s, C6), 117.6 (s,
C7), 147 (d, C8, 3JC8P1 = 21 Hz), 143.5 (d, C9, 2JC9P1 = 2.5 Hz), 126.1
(d, C10, 3JC10P1 = 5 Hz), 124.50 (C11), 124.16 (C12), 124.0 (C13,
4
JC13P1 = 2.5 Hz), 137.5 (d, C14, 3JC14P1 = 11 Hz), 14.69 (s, 1C, SMe),
127.6 (d, 1C,Phipso 1JC16P1 = 50.7 Hz), 135.9 (d, 2C, Ph0,
2
JCP1 = 11.2 Hz), 129.9 (d, 4C, Phm, 3JCP1 = 12.5 Hz), 130.3 (d, 1C,
Php, 3JCP1 = 2.5 Hz), 127.4 (d, 1C,*Phipso 1JC16P1 = 49.8 Hz), 133.9 (d,
2C, *Pho, 2JCP1 = 11.2 Hz), 133.8 (d, 1C, *Php, 3JCP1 = 2.5 Hz), 30.7
(dd, 1C, CH2, dppe, 1JCP2 = 38 Hz, 2JCP3 = 16 Hz), 29.9 (dd, 1C, CH2,
dppe, 1JCP2 = 35 Hz, 2JCP3 = 12 Hz), 133.6 (d, 4C, Phipso, dppe,
1
JCP1 = 150 Hz), 133.9 (d, 2C, Pho, dppe, 2JCP1 = 10 Hz), 133.3 (d, 1C,
Php, dppe, 4JCP1 = 2.5 Hz), 133.2 (d, 1C, Php, dppe), 128.8–128.6 (7C,
Ph, dppe), 132.0 (d, 2C, Pho, dppe, 2JCP1 = 10 Hz), 131.7 (d, 2C, Ph0,
3
JCP1 = 10 Hz), 131.2(d, 1C,Php), 134.8 (d, 2C, Pho, 2JCP1 = 11.2 Hz),
129.5 (d, 2C, Phm, dppe, 2JCP1 = 11.5 Hz).
3.3.17. Compound [Pd(PPh3){2-C8H5N(Ph2P = NC6H4SCH3-κ3-NNS)}]
BF4 14
Compound 13 (14 mg, 0.013 mmol) was placed into a Schlenk and
dissolved with dry CH2Cl2, O2(g) was bubbled through the solution for
30 min and then stirred for 7 days. After that, the solvent was removed
under a reduced pressure and the residual solid was washed twice with
Et2O (2 × 4 mL) to eliminate dppeO2. The solid was dissolved in
CH2Cl2 (5 mL) and the PPh3 (3.6 mg, 0.013 mmol) was added. The
crude reaction mixture was filtered off through celite. Finally, the vo-
latiles were removed under vacuum giving an orange powder. Yield
63% (7.6 mg). M.p. 158–160 °C.
IR (ν, cm−1): 1276.2 (νPN). 31P NMR (162 MHz, CDCl3, 20 °C): δ
30.9 (s, P]N), 27.3 (s, PPh3); 1H NMR (500 MHz, CDCl3, 20 °C) δ 6.77
(d, H2, 3JHP = 2.5 Hz), 7.36 (d, H4, 3JH4H5 = 8 Hz), 6.62 (dd, H5, 3J
3 3
H5H4, H5H6 = 7.5 Hz), 6.20 (dd, H6, J H6H5, = 7.5 Hz, JH6H7 = 8 Hz),
3 3
6.32 (d, H7, J H7H6 = 8 Hz), 6.67 (d, H10, JH10H11 = 9 Hz), 7.03 (dd,
H11, 3J H11H10, = 9 Hz, 3J H11H12 = 8 Hz), 6.87 (dd, H12, 3J
3 3
H12H11 = 8 Hz, J H12H13 = 8 Hz), 7.27 (d, H13, J H13H12 = 8 Hz), 1.99
4
(d, 3H, SMe, JH15P = 1.5 Hz), 7.91–7.94 (m, 4H, Pho), 7.58–7.61 (m,
4H, Phm), 7.63–7.72 (m, 2H, Php), 7.75–7.79 (m, 6H, PPh3), 7.43–7.46
(m, 6H, PPh3), 7.53–7.55 (m, 3H, PPh3); 13C NMR (125 MHz, CDCl3,
20 °C): δ 131.6 (d, C1, 1JC1P1 = 51 Hz), 114.09 (d, C2,
2 [3]
JC2P1 = 26.7 Hz), 129.7 (s, C3), 121.02 (s, C4),118.88 (s, C5), 121.92
(s, C6), 117.53 (s, C7), 146.3 (C8, 3JC8P1 = 15 Hz), 151.8 (C9), 119.78
(d, C10, 3JC10P1 = 8 Hz), 132.12 (s, C11), 122.52 (s, C12), 133.4 (s, C13),
125.4 (dd, C14, 3JC2P1 = 16.5 Hz, 3JC14P2 = 7.5 Hz), 28.8 (s, 1C, SMe),
137.6 (d, 2C, Phipso, 1JCP1 = 156.7 Hz), 132.3 (d, 4C, Pho,
2
JCP1 = 9 Hz), 129.92 (d, 4C, Phm, 3JCP1 = 12.3 Hz), 130.2 (d, 2C, Php,
4 34 (9) (2015) 1627–1634.
JCP1 = 13 Hz), 128.32 (d, 3C, PPh3, Phipso, 1JCP2 = 53.7 Hz), 134.98
11
Inorganica Chimica Acta 495 (2019) 118945
(d, 6C, PPh3, Pho, 2JCP2 = 11 Hz), 129.64 (d, 6C, PPh3, Phm,
3
JCP2 = 11 Hz), 133.15 (d, 3C, PPh3, Php, 4JCP2 = 2.6 Hz).
4. Conclusion
In summary, using the Staudinger reaction between the new 2-in-
dolyldiphenylphosphine and different aryl azides functionalized with a
thioether or selenoether moiety, four novel unsymmetrical ligands
N,N,X (X = S, Se) based on iminophosphoranes have been conveniently
synthesized. The selenoether derivatives are the first two examples of
an iminophosphorane containing a selenoether group. Reactions of all
ligands with dichlorobis(acetonitrile) palladium (II) gave the corre-
sponding N,N,S and N,N,Se non-symmetrical Pd(II) pincer complexes in
good yields. The molecular structures of the methylthioether ligand and
all the pincer complexes were unequivocally determined by single X-ray
diffraction experiments, showing no significant structural differences
between compounds containing sulfur or selenium donors. The me-
thylthioether N,N,S complex may be reacted with neutral ligands to
give typical cationic palladacycles without compromising the pincer
structure. The most remarkable feature described herein is the struc-
tural evidence for a true hemilabile coordination behavior of the me-
thylthioether donor when the corresponding pincer complex was
treated with dppe. A strong intramolecular interaction between the
iminic nitrogen and the sulfur atom holds the chalcogene ligand very
close to the metal center. Reversible coordination is clearly observed
when the pincer structure is reformed after abstraction of dppe from the
metal center upon oxidation. Hemilability of both selenoether and
thioether donors in the remaining complexes was unambiguously con-
firmed using 31P NMR to monitor the same sequence of reactions.
Application of these unsymmetrical pincer complexes in catalytic pro-
cesses is actually under progress.
Supplementary data for compounds (2), (6), (7), (8), (9), (11), (12)
and (13) have been deposited at the Cambridge Crystallographic Data
Centre. Copies of this information are available free of charge on re-
quest from The Director, CCDC, 12 Union Road, Cambridge, CB2 1EZ,
UK (Fax: +44-1223-336-033; e-mail deposit@ccdc.cam.ac.uk or www:
http://www.ccdc.cam.ac.uk) quoting the deposition numbers CCDC
1906407-1906414.
Declaration of Competing Interest
none.
Acknowledgments
We gratefully acknowledge CONACYT for the financial support of
this research (CB2009/134528 and CB2010/154732) and the Ph. D.
scholarship for C.G.MdL (276535). We also greet the technical support
of Mr. Marco Antonio Leyva Ramírez.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.ica.2019.05.044.
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