Coordination of P(X)-modified (X = O, S) N-aryl-carbamoylmethylphosphine oxides and sulfides with Pd(II) and Re(I) ions: Facile formation of 6,6-membered pincer complexes featuring atropisomerism

Article abstract of DOI:10.1016/j.poly.2012.12.025

Direct acetylation of (thio)phosphorylated anilines 1a,b with in situ generated Ph₂P(O)CH₂C(O)Cl or sequential treatment of 1a,b with chloroacetyl chloride and Ph₂PSNa resulted in novel oligodentate ligands, namely, P(X)-m

Full text of DOI:10.1016/j.poly.2012.12.025

Polyhedron 51 (2013) 168–179
Contents lists available at SciVerse ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Coordination of P(X)-modified (X = O, S) N-aryl-carbamoylmethylphosphine
oxides and sulfides with Pd(II) and Re(I) ions: Facile formation of
6,6-membered pincer complexes featuring atropisomerism
⇑
V.Yu. Aleksenko, E.V. Sharova, O.I. Artyushin, D.V. Aleksanyan , Z.S. Klemenkova, Yu.V. Nelyubina,
P.V. Petrovskii 1, V.A. Kozlov, I.L. Odinets 1
A.N. Nesmeyanov Institute of Organoelement Compounds, 28 Vavilov Street, Moscow 119991, Russia
a r t i c l e i n f o
a b s t r a c t
Article history:
Direct acetylation of (thio)phosphorylated anilines 1a,b with in situ generated Ph2P(O)CH2C(O)Cl or
sequential treatment of 1a,b with chloroacetyl chloride and Ph2PSNa resulted in novel oligodentate
ligands, namely, P(X)-modified carbamoylmethylphosphine oxides (CMPO) and sulfides (CMPS) 2a–d.
Received 25 September 2012
Accepted 21 December 2012
Available online 7 January 2013
In reactions with Re(CO)5Br (in the presence of Et3N) and (PhCN)2PdCl2 these ligands afforded
j
3-XNY
(X,Y = O,S) Re(I) (4a,d) and Pd(II) (6b–d) pincer complexes with two fused six-membered metallocycles,
owing to ready metallation at the amide nitrogen atom. In the absence of a base, the interaction of 2a
with the same rhenium precursor yielded ten-membered
nated only by phosphoryl groups. According to the NMR spectroscopy data, the complexes obtained form
stable atropisomers in solution at room temperature. The solid state structures of compounds 2a,b and
resulting metallocycles were characterized by X-ray crystallography.
Keywords:
Tridentate ligands
Pincer complexes
Rhenium
j
3-OO metallocycle 5 with Re(I) ion coordi-
Palladium
Ó 2013 Elsevier Ltd. All rights reserved.
1. Introduction
could serve as a useful directing group for metallation at the amide
nitrogen atom of carbamoylmethyl(thio)phosphoryl moiety, there-
Organophosphorus compounds amount to the most important
ligands in inorganic and organometallic chemistry, playing an
indispensable role both in homogeneous catalysis and different
metal separation processes. In particular, various phosphoryl-
containing substances found wide application in the recovery of
rare-earth elements from acidic radioactive liquid wastes [1]. The
main advances in this field over more than semicenturary history
pertain to the development of bidentate ligands, namely, car-
by, resulting in a pincer-type tridentate monoanionic framework.
Pincer complexes comprise a unique class of organometallic com-
pounds that receives growing attention in catalysis, materials sci-
ence and many other fields [5,6]. Unfailing interest to these
derivatives stems from the presence of multiple sites for directed
structural modifications offering ample opportunities for fine-tun-
ing of their steric and electronic properties. While most of organo-
phosphorus pincer-type ligands relate to trivalent phosphorus
derivatives (phosphines, phosphinites, phosphites and so on), re-
cently we have shown that thiophosphoryl-containing ligands bear-
ing the four-coordinated phosphorus center can successfully
compete in catalytic performance with their P(III) counterparts [7].
Herein we report on the facile synthesis of novel tridentate
ligands by the modular assembling of ortho-(thio)phosphorylated
anilines with CMPO(S) precursors which provide upon complexa-
tion with Re(I) and Pd(II) precursors ONO, SNO, and SNS donor sets
due to the N–H bond activation of a CMPO(S) fragment, resulting in
6,6-membered pincer complexes.
bamoylmethylphosphine oxides (CMPO) of general formula R1
2-
P(O)CH2C(O)NR2R3 [2] which were proved to be the most
preferable extractants in terms of availability, cost, and extraction
efficiency. While a priority was continuously placed on CMPO and
related phosphoryl-containing derivatives, their thiophosphoryl
analogs have received far less attention [3].
Carbamoylmethylphoshoryl derivatives usually serve as neutral
bidentate ligands bounding to a metal center through the oxygen
atoms of amide and phosphoryl groups [4]. It is natural to assume
that the introduction of ancillary donating arm(s) may strongly
affect the coordination behavior of modified CMPO compounds.
Thus, the condensation of ortho-phosphorylated aniline and its thio-
analog with phosphorylacetic acid derivatives would lead to oligod-
entate ligands in which the P@X (X = O, S) group of aniline fragment
2. Results and discussion
2.1. Synthesis of ligands
⇑
Corresponding author. Tel.: +7 499 135 9356.
E-mail address: aleksanyan.diana@gmail.com (D.V. Aleksanyan).
Deceased.
The key phosphorylated aniline 1a [8] and its thioanalog 1b [9]
are readily accessible from 2-diphenylphosphinoaniline [10] by
1
0277-5387/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.poly.2012.12.025

V.Yu. Aleksenko et al. / Polyhedron 51 (2013) 168–179
169
oxidation with H2O2 and addition of elemental sulfur, respectively.
To anchor a CMPO(S) fragment on the aniline scaffold, two different
syntheticapproaches have been developed, depending on the nature
of the substituent X in the P@X group of a carbamoylmethyl moiety
(Scheme 1). The first route (compounds 2a,b) consisted in the acyla-
tion of the starting anilines 1a,b with diphenylphosphorylacetic acid
chloride generated in situ from the corresponding acid using PCl3 as a
mild chlorinating agent via the general procedure previously devel-
oped in our laboratory [11]. The second approach used for the syn-
thesis of CMPS derivatives 2c,d was based on the reaction of
starting anilines 1a,b with chloroacetyl chloride followed by the
treatment of the resulting chloroacetyl derivatives 3a,b with sodium
diphenylthiophosphinite. The methods employed (Scheme 1) affor-
ded the desired ligands 2a–d in moderate to good yields (55–79%).
The structures of ligands 2a–d as well as intermediate deriva-
tives 3a,b were unambiguously confirmed based on the multinu-
clear NMR (31P, 1H, and 13C) and IR spectral data. The 31P NMR
spectra of 2a–d show two singlet signals in the regions typical
for these classes of organophosphorus compounds. Thus, the sig-
nals of the phosphorus resonances of phosphoryl group in
ArP(O)Ph2 (2a,c) and carbamoylmethyl (2a,b) fragments were ob-
served at ꢀ37 and 27–28 ppm, respectively, while in the case of
thiophosphoryl derivatives (2b–d) the signals of P@S groups were
manifested in a narrow range from 38 to 40 ppm independent from
the nature of an additional substituent in the –P(S)Ph2 moiety. The
presence of a great number of phenyl rings in the molecules of
these acetamides complicates the interpretation of 1H NMR spectra
in the region typical for aromatic proton signals, however, the sig-
nals of the hydrogen atoms of an amide group and doublet signals
of the protons of a methylene unit can be easily identified: dNH
9.92–11.29, dCH2 3.04–3.61 ppm (2JHP ꢀ 14–15 Hz). The 13C NMR
spectral data of compounds 2a–d are also well consistent with
the proposed structures: e.g., dCH2 41–45 ppm (1JPC = 47–63 Hz),
dC(O)NH2 ꢀ 163 ppm (2JPC ꢀ 5 Hz). Moreover, unlike the proton
spectra, the signals of the carbon atoms of a central benzene ring,
as a rule, do not overlap with those of CPh-atoms of peripheral phe-
nyl moieties (see Section 4). The IR spectra of crystalline samples of
2a–d demonstrate the characteristic stretching vibrations of the
lower frequency region than that for CH2P(S)Ph2 fragment (cf. 614/
637 and 649 cmꢁ1, respectively, in the case of SNS ligand 2d). Note
that the observation of several bands corresponding to stretching
of the P@O bond as well as broadening of the amide group charac-
teristic vibrations are likely to be connected with the formation of
intra- and intermolecular hydrogen bonds.
According to the X-ray diffraction data, ligands 2a (the crystal-
losolvate with water and ethanol, 0.5 each per one molecule of the
product) and 2b possess quite typical geometrical parameters for
the molecules of this type (Fig. 1). Note that the pseudo-torsion
angle O(1)P(1)C(2)C(1) in the molecule of 2a comprises 34.0(1)°.
Such a position of the P@O bond respective to the benzene core
in the ArP(O)Ph2 fragment is apparently governed by the intramo-
lecular H–bond with the NH group (Fig. 1; N(1)–H(1N) 0.92 Å,
H(1N)ꢂ ꢂ ꢂO(1) 1.98 Å, N(1)ꢂ ꢂ ꢂO(1) 2.782(2) Å, NHO 145(1)°). In 2b,
the same value for the P(1)@S(1) group, which is not such a conve-
nient proton-acceptor as P@O one, is 64.3(1)°.
The CMP-coordination arm in the molecules of 2a and 2b is geo-
metrically very similar to that in non-functionalized N-aryl-
carbamoylmethylphosphine oxides, Ph2P(O)CH2C(O)NHAr [11],
the most pronounced difference being the values of the angle
O(2)P(2)C(1)C(2) equal to 57.3(1) and 63.6(1)° in 2a and 2b,
respectively, and 16–30° in the molecule of Ph2P(O)CH2C(O)NHAr
or its bis-CMP analog 1,3-[Ph2P(O)CH2C(O)NH]2C6H4 [11], also
due to the differences in the H-bonding patterns. Thus, the P@O
group of a CMPO fragment in 2b is involved in the intramolecular
H-bond with the only NH group in a molecule (Fig. 2; N(1)–H(1N)
0.91 Å, H(1N)ꢂ ꢂ ꢂO(2) 2.06 Å, N(1)ꢂ ꢂ ꢂO(2) 2.7996(17) Å, NHO
138(1)°). In the crystal of 2a, out of the two symmetry-identical
molecules of the ligand in a unit cell, the P@O group of a CMPO
moiety forms the H-bond with the hydrate water molecule
through the P(2)@O(2) bond (O(1W)ꢂ ꢂ ꢂO(2) 2.65(1) Å,
OHO ꢀ 165°), while the other P@O group form hydrogen bond with
ethanol molecule (O(1S0)ꢂ ꢂ ꢂO(1) 2.80(1) Å, OHO ꢀ 145°) and the
intramolecular H-bond with the amide hydrogen (N(1)–H(1N)
0.92 Å, H(1N)ꢂ ꢂ ꢂO(1) 1.98, N(1)ꢂ ꢂ ꢂO(1) 2.782(2) Å, NHO 145(1)°).
Therefore, the pattern of H-bonds in 2a and 2b ensure the cisoid
disposition of the P@X groups, which was expected for their com-
plexes only (vide infra).
carbonyl group (m m(NH)
(C@O) 1677–1690 cmꢁ1) and N–H bond (
3200–3300 cmꢁ1), whereas the absorption bands typical for the
secondary amides and associated mainly with the deformational
vibrations of N–H bond are observed in the range from 1500 to
1540 cmꢁ1. The position of absorption bands corresponding to
the phosphoryl and thiophosphoryl group vibrations depends on
the nature of an additional substituent at the phosphorus atom
(aryl or alkyl). Thus, the absorption bands of phosphoryl group of
Various weak interactions such as C–Hꢂ ꢂ ꢂX (X = O in 2a and
X = O, S in 2b), C–Hꢂ ꢂ ꢂ
p
and Hꢂ ꢂ ꢂH as well as Oꢂ ꢂ ꢂ
p in 2b hold the
molecules in these crystals.
2.2. Synthesis of complexes
While studying the complexation features of the ligands de-
rived, it was found that the reaction of 2a,d with rhenium penta-
carbonyl bromide in toluene solution under reflux in the
presence of triethylamine indeed readily proceeds as the metalla-
tion at the nitrogen atom of an amide fragment accompanied by
a
CMPO moiety are observed at 1198/1203 (2a) and 1202
(2b) cmꢁ1, while
(P@O) of triarylphosphine oxide moiety – at
1160/1167 (2a) and 1153/1167 (2c) cmꢁ1. Analogously, in the case
m
of thiophosphoryl derivatives:
m
(P@S) for ArP(S)Ph2 appears in the
X
PPh2
Ph2P(O)CH2COOH/PCl3
NHC
O
PPh2
O
X
PPh2
X = O (2a) 55%
X = S (2b) 69%
NH2
X
X
X = O (1a)
X = S (1b)
PPh2
PPh2
ClCH2C(O)Cl
Ph2PSNa
Cl
NHC
O
NHC
O
PPh2
S
X = O (3a) 87%
X = S (3b) 99%
X = O (2c) 79%
X = S (2d) 77%
Scheme 1. Synthesis of (thio)phosphoryl-substituted carbamoylmethylphosphine oxides 2a,b and sulfides 2c,d.

170
V.Yu. Aleksenko et al. / Polyhedron 51 (2013) 168–179
Fig. 1. General view of compound 2a in representation of atoms by thermal ellipsoids (p = 30%). Either water molecule or ethanol molecule (both disordered by two positions)
is present in the asymmetric part of a unit cell. Hereinafter the H(C) atoms are omitted for clarity.
Fig. 2. General view of compound 2b in representation of atoms by thermal ellipsoids (p = 50%).
Ph
Ph
Ph
O
Ph
O
the coordination of both of the (thio)phosphoryl donating groups
to give
3-ONO and SNS pincer complexes 4a,d in good to high
P
P
X
Re(CO)5Br
Et3N, C6H5CH3, reflux, 1.5 h
X
j
Re(CO)3
X
yields (Scheme 2). Thus, unlike the known CMPO derivatives, in
these cases the mutual disposition of donating groups facilitates
the coordination of a carbamoyl moiety via the nitrogen atom
rather than the oxygen one. Note that the compounds obtained
represent the rare examples of pincer complexes with two six-
membered fused metallocycles. Interestingly, in the absence of a
NH
X
N
PPh2
PPh2
X = O (4a) 81%
X = S (4d) 72%
2a,d
Re(CO)5Br
C6H5CH3, reflux, 1.5 h
Et3N, C6H5CH3
reflux, 3 h
Ph
j
2-OO
Ph
O
base, P(O)-modified CMPO derivative 2a adopts a neutral
P
O
bidentate coordination mode without participation of a carbamoyl
moiety, bounding to the metal ion via oxygen atoms of both phos-
phoryl groups to give ten-membered metallocycle 5 (Scheme 2).
The latter can be readily transformed into the above mentioned
complex 4a under the action of Et3N (in toluene under reflux for
3 h, 31P NMR monitoring), and, therefore, is likely to be considered
as an intermediate in the reaction with the base. It should be noted
that the basicity of triethylamine is evidently not enough to
abstract proton from the above ligands. Obviously, it facilitates
the formation of complexes with the deprotonated ligands, being
Re(CO)3Br
NH
O
PPh2
5
Scheme 2. Synthesis of Re(I) complexes 4a,d and 5.
more thermodynamically stable than those with the neutral ligand
form, via formation of Et3Nꢂ ꢂ ꢂH–N hydrogen bond and shifting the
equilibrium position due to trapping of HBr.

V.Yu. Aleksenko et al. / Polyhedron 51 (2013) 168–179
171
Ph
Ph
Ph
O
Ph
P
P
X
X
Cl
(PhCN)2PdCl2, CH2Cl2, rt, 12 h
Pd
NH
Y
N
Y
PPh2
PPh2
O
2b-d
X = S, Y = O (6b) 81%
X = O, Y = S (6c) 75%
X = Y = S (6d) 97%
Scheme 3. Synthesis of Pd(II) pincer complexes 6b–d.
Furthermore, under the action of (PhCN)2PdCl2 in dichloro-
methane at room temperature acetamides 2b–d readily underwent
the cyclopalladation (Scheme 3). Note that unlike rhenium deriva-
tives, in these cases the addition of triethylamine promoted the
reduction of the palladated species, evident from the liberation of
palladium black, rather than facilitated the cyclopalladation itself.
The propensity of platinum group metals to the coordination of
various organothiophosphorus compounds owing to the presence
of the ‘‘soft’’ sulfur atom is well known [12] and explains the ease
of formation of bis(phosphine sulfide) derivative 6d. Moreover, the
fact that ONO ligand 2a appeared to be completely inactive in this
reaction also could be expected. In this respect, the coordination
behavior of hybrid SNO-derivatives 2b,c, bearing simultaneously
phosphoryl and thiophosphoryl functions, was the most interest-
Fig. 3. General view of complex 4a in representation of atoms by thermal ellipsoids
(p = 30%).
groups by the Re and Pd atoms. The value of
DdP for the P@O group,
ing. Both of them were found to form
j
3-SNO pincer complexes
as a rule, is higher than that for the P@S moiety, varying within the
ranges 6.5–17.8 and 1.0–8.3 ppm, respectively. Therewith, the small-
est coordination shift was observed for bis(thiophosphorylated)
derivatives 4d and 6d. Further evidence for the coordination of both
of these donor centers can be derived from the bathochromic shift of
the absorption bands corresponding to the stretching vibrations of
the P@O and P@S groups in the IR spectra of the complexes obtained
by 13–53 and ꢀ50 cmꢁ1 in the case of rhenium derivatives 4a,d, 5
and ꢀ44–65 and 36–84 cmꢁ1 for palladocycles 6b–d, respectively.
The lack of coordination of an amide fragment in the case of complex
5 is confirmed by the presence of NH proton signal in the 1H NMR
spectrum (dH = 10.59 ppm) and characteristic vibrations of a free
amide group in the IR spectrum (at 1529 and 3287 cmꢁ1). In con-
trast, the absence of both NH proton signals in the 1H NMR spectra
and absorption bands at 1500–1540 and 3200–3300 cmꢁ1 in the IR
spectra of 4a,d, 6b–d give strong evidence of the occurrence of met-
allation at the amide nitrogen atom. This is accompanied by a strong
concomitant shift of the C@O group stretching vibrations to the re-
with two six-membered fused palladocycles. But whereas the
cyclopalladation of 2b proceeds smoothly, affording 6b in 80%
yield, the yield of its counterpart 6c was less than 50%. It is natural
to assume that in the case of hemilabile ligands 2b,c, the metalla-
tion is preceded by the formation of j
1-S species, in which the li-
gand bounds to the palladium atom via sulfur donor center of
either ArP(S)Ph2 (2b) or CMPS fragment (2c), rather than biden-
tately coordinated intermediate. Therewith, the disposition of the
‘‘soft’’ sulfur center in a flexible carbamoylmethylphosphine sulfide
fragment in 2c affords much more labile j
1-S predecessor than in
the case of ligand 2b featuring a rigid phenylene spacer between
the P@S pendant arm and carbamoyl group. Thus, the cyclopallada-
tion of 2c was complicated by the formation of an inactive mono-
dentately S-coordinated complex
(
31P NMR monitoring)
accompanied by the precipitation of PdCl2. Moreover, the starting
ligand was partially recovered after chromatographic purification.
This can be explained by the transformation of initially formed
1-S
l-Cl [LPdCl2]2 species into L2PdCl2 complex, as known from
gion of lower frequencies (
D
ꢀ 70–90 cmꢁ1). Note that the position
j
of C„O carbonyl absorption bands in the IR spectra of 4a and its pre-
decessor 5 indicates their stronger bonding in the case of 4a with the
deprotonated form of the ligand compared to molecular complex 5
(see Section 4). Several features of the 13C NMR spectra of the com-
plexes obtained merit discussion. Thus, the signals of carbamoyl car-
bon atoms in the 13C NMR spectra of 4a,b and 5b–d are deshielded
upon complexation by 1.9–6.4 ppm with almost 1.5-fold increase
of the 2JPC value. A strong downfield shift is observed for the C1 car-
bon atom of the central phenyl ring, being directly bound to the car-
the literature [13], or simply decomposition of these intermediates
on silica gel. None of such complications was detected in the case
of hybrid derivative 2b. Hence, the coordination of the sulfur atom
of P@S group serves as a key factor for further metallation of the
N–H bond and disposition of these groups in a ligand backbone in-
deed dictates the easiness of the formation of j
2-SN anionic inter-
mediates. Note that compounds 6b,c are rare examples of
cyclometallated derivatives of platinum group metals with the
coordinated P@O moiety.
bamoyl moiety (
atoms are also indicative of complex formation (e.g.,
D
dC1 = 7.2–13.7 ppm). The signals of other carbon
dC6
The complexes obtained are white (rhenium derivatives 4a,d,5)
and orange (palladium complexes 6b–d) crystalline solids, ther-
mally stable up to 165 °C as well as air and moisture resistant.
The realization of j2-OO coordination in 5 and j3-XNY (X = S and/
or O) coordination in 4a,d, 6b–d is supported by the NMR and IR
spectral data, as well as X-ray diffraction analysis. Thus, a down-
field shift2 of the phosphorus resonances in the 31P NMR spectra
of all the complexes compared to the signals of free ligands 2a–d
unequivocally confirms the coordination of both (thio)phosphoryl
D
=
4.0–6.5 ppm). Note that each peripheral phenyl ring at both of the
phosphorus atoms was found to be distinguishable, giving rise to
four sets of ipso-, ortho-, meta-, and para-C atom signals instead of
two sets in the case of starting ligands 2a–d. The proton signals of
a methylene unit, as another prochiral grouping, also appeared
nonequivalently in the 1H NMR spectra of j3-XNY complexes 4a,d,
6b–d. Moreover, the same was observed even in the case of
ten-membered metallocycle 5. The dissymmetrization process that
renders these prochiral groups diastereotopic consists in the stabil-
ization of twisted conformations of fused six-membered metallocy-
cles, resulting in atropisomers that do not interconvert at room
2
Only in the case of complex 6d, the signal of the phosphorus atom of
carbamoylmethylphosphine sulfide moiety appeared to be upfield shifted relative
to the signal of the free ligand by 0.08 ppm.

172
V.Yu. Aleksenko et al. / Polyhedron 51 (2013) 168–179
The conformation of the resulting six-membered metallocycles
in 4a is a half-chair with the deviation of the atoms N(1) and C(2)
by 0.88(1) and ꢁ0.57(1) Å and a boat with the atoms Re(1) and
C(20) deviated by 0.89(1) and 0.64(1) Å. In 4d, their conformations
are the same, although somewhat distorted; the deviations of the
above atoms are 0.86(3) and ꢁ0.59(1) Å for the metallocycle with
the P(1)@S(1) bond and 1.16(3) and 0.59(3) Å for that with
P(2)@S(2) bond.
In the crystals of 4a and 4d, the molecules of the complexes are
assembled into the 3D framework by means of C–Hꢂ ꢂ ꢂ
and Hꢂ ꢂ ꢂH contacts as well as C–Hꢂ ꢂ ꢂS ones in 4d and interactions
C–Hꢂ ꢂ ꢂ and Clꢂ ꢂ ꢂ with the solvate dichloromethane species in 4a.
p
, C–Hꢂ ꢂ ꢂO,
p
p
As for complex 5 (Fig. 5) with two independent molecules in a
crystal, the coordination of the rhenium atom by bromine instead
of the ligand nitrogen atom only slightly affects its octahedral
environment. In this case, however, the presence of NH group al-
lows for the formation of intramolecular H-bonds that are different
in two independent molecules of the complex. Thus, the first one is
additionally stabilized by two N–Hꢂ ꢂ ꢂO hydrogen bonds (N(1)–
H(1N) 0.88 Å, H(1N)ꢂ ꢂ ꢂO(1) 2.08 Å, N(1)ꢂ ꢂ ꢂO(1) 2.846(8) Å,
NHO(1) 145(1)° and N(1)–H(1N) 0.88 Å, H(1N)ꢂ ꢂ ꢂO(2) 2.49 Å,
N(1)ꢂ ꢂ ꢂO(2) 3.049(8) Å, NHO 122(1)°), while in the second mole-
cule (see Fig. S1 in Supplementary material) there are one N–
Fig. 4. General view of complex 4d in representation of atoms by thermal ellipsoids
(p = 50%).
Hꢂ ꢂ ꢂO
(N(1A)–H(1NA)
0.89 Å,
H(1NA)ꢂ ꢂ ꢂO(1A)
2.05 Å,
temperature, as was observed for other 6,6-membered pincer
complexes (vide infra).
N(1A)ꢂ ꢂ ꢂO(1A) 2.784(9) Å, NHO 139(1)°) and one N–Hꢂ ꢂ ꢂBr
(N(1A)–H(1NA) 0.89 Å, H(1NA)ꢂ ꢂ ꢂBr(1A) 2.83 Å, N(1A)ꢂ ꢂ ꢂBr(1A)
3.576(7) Å, NHBr 142(1)°) H-bond. This is accompanied by the dif-
ferences in the disposition of the phenyl moieties, so that the above
O(1)P(1)C(2)C(1) and O(2)P(2)C(1)C(2) torsion angles are 26.9(8)°
and 19.9(8)° in the molecule shown on Fig. 5 and 39.6(7)° and
25.9(7)° in the second one.
The solid-state structures of complexes 4a,d (Figs. 3 and 4), 5
(Fig. 5), and 6b–d (Figs. 6–8) were studied by X-ray diffraction
analysis. According to its results, in all cases the metal (rhenium
or palladium) ion is bonded with both P@O(S) groups and in the
case of complexes 4a,d, 6b–d (with the deprotonated ligands) also
with the nitrogen atom of an amide fragment.
In a crystal, the molecules of complex 5 are assembled into the
In 4a (Fig. 3), which is a crystallosolvate with three chloroform
species per two independent molecules of the complex (those hav-
ing nearly the same geometrical parameters), and 4d (Fig. 4), the
coordination caused only slight elongation of the P@O bonds to
ꢀ1.51 Å [4,14] and P@S ones to ꢀ2.00 Å [15], with the values of
the above torsion angles X(1)P(1)C(2)C(1) and X(2)P(2)C(1)C(2)
here being 50.1(1)° and 43.7(1)° in 4a and 64.2(3)° and 43.0(3)°
in 4d. In both cases the rhenium atom has nearly ideal octahedral
environment.
3D framework by means of numerous C–Hꢂ ꢂ ꢂ
p
, C–Hꢂ ꢂ ꢂO, C–Hꢂ ꢂ ꢂBr
and Hꢂ ꢂ ꢂH contacts.
In 6b–d (Figs. 6–8), the geometrical parameters of the pallado-
cyclic moiety are rather expected for the fused 6,6-membered pin-
cer complexes [16]. In all cases, the Pd(1) atom is characterized by
a square-planar configuration (within 0.03(1)–0.06(1) Å) [17]. The
metallocycles in these complexes all have a boat conformation
(Figs. 6–8); the atoms Pd(1) and C(20) in one deviating by
1.08(1) and 0.67(1) Å (6b), 1.20(1) and 0.67(1) Å (6c), 1.39(1) and
Fig. 5. General view of complex 5 in representation of atoms by thermal ellipsoids (p = 30%). Only one independent molecule of the complex is shown.

V.Yu. Aleksenko et al. / Polyhedron 51 (2013) 168–179
173
Fig. 6. General view of complex 6b in representation of atoms by thermal ellipsoids (p = 50%).
Fig. 7. General view of complex 6c in representation of atoms by thermal ellipsoids (p = 50%).
0.59(1) Å (6d) and the atoms N(1) and P(2) in the other by 0.69(1)
and 0.76(1) (6b), 0.75(1) and 0.63(1) Å (6c), 0.82(1) and 0.78(1) Å
(6d).
representative example of complex 6c). In the related octahedral
rhenium complexes 4a,d with the deprotonated forms of ligands
2a,d bound in a facial manner, the metal center serves as a stereo-
genic center (see Fig. S3 in Supplementary material for a represen-
tative example of complex 4d). In general, pincer complexes with
two six-membered fused metallacycles are quite uncommon com-
pared to their 5,5-membered counterparts and, unlike the com-
plexes from the present, are based on symmetrical ligands [5,6].
Atropisomerism is an intrinsic feature of such systems owing to
a possibility of the existence of left- and right-handed twisted
forms. Depending on the structure of complexes, the interconver-
sion between two atropisomers can be either rapid on the NMR
time scale at room temperature [18] or complicated, as in our
case, due to a high rotational barrier, resulting in metallacycles
conformationally stable up to 110 °C [19]. Furthermore, most of
the solid samples submitted to X-ray diffraction analysis were also
racemates, with only one example of PCP rhodium complex
spontaneously crystallized in a single enantiomeric form [18c].
Note that the synthesis of 6,6-membered metallacycles comprises
In the palladium derivatives, the values of the above torsion an-
gles S(1)P(1)C(2)C(1) and S(2)P(2)C(1)C(2) are nearly the same for
complexes 6b and 6c with
69.7(1)° in the former and 59.4(1) and 74.3(1)° in the latter), being
j
3-SNO coordination (58.5(1) and
slightly different from those in
j
3-SNS complex 6d (60.3(1) and
98.0(1)°, respectively).
In the crystals 6b–d, the molecules are held together only by
weak but numerous contacts C–Hꢂ ꢂ ꢂO, C–Hꢂ ꢂ ꢂ
p
and C–Hꢂ ꢂ ꢂCl as
well as Hꢂ ꢂ ꢂH in 6c and 6d.
Note that the individual molecules of complexes 4a,d and 6b–d
are virtually chiral due to the fully unsymmetrical surrounding of
the metal center, although all the crystals are comprised of both
enantiomers. As for the nature of chirality generated, in palladium
derivatives 6b–d highly constrained system of two fused six-
membered rings gives rise to left- and right-handed twisted atrop-
isomeric forms (see Fig. S2 in Supplementary material for a

174
V.Yu. Aleksenko et al. / Polyhedron 51 (2013) 168–179
Fig. 8. General view of complex 6d in representation of atoms by thermal ellipsoids (p = 50%).
the transmetallation, e.g., of (COD)PdCl2 with the corresponding
non-metallated silver or mercury complexes
opposite polarities. The numeration for carbon atoms of the central
benzene ring in the descriptions of the 13C NMR spectral data of all
the compounds is in agreement with IUPAC nomenclature used for
ligands 2a–d. The same principle of numbering was used for
description of the solid-state molecular structures characterized
by X-ray crystallography.
Column chromatography was carried out using Merck silica gel
60 (230–400 mesh ASTM). IR spectra were recorded on a Magna-
IR750 Fourier spectrometer (Nicolet), resolution 2 cmꢁ1, 128 scans.
The assignment of absorption bands in the IR spectra was made
according to Ref. [21] Melting points were determined with MPA
120 EZ-Melt Automated Melting Point Apparatus and were
uncorrected.
[18b,19a,19c,19d,19f], oxidative addition of low-valent metal pre-
cursors to C2-halogentaed ligands [19b], and direct cyclopallada-
tion under rather severe conditions (prolonged heating at
elevated temperatures) [18a,18d,18e,19e]. Taking into account
the ease of formation of complexes 4a,d and 6b–d (in the case of
palladium derivatives, direct cyclopalladation smoothly proceeds
at room temperature) and stability of atropisomers in solution at
room temperature, there is a realistic possibility of resolving the
racemic mixtures, which in case of rhenium derivatives could give
rise to chiral-at-metal compounds.
3. Conclusions
4.2. 2-(Diphenylphosphoryl)aniline 1a
A 35% aq. solution of hydrogen peroxide (10 mL) was slowly
dropwise added to a solution of 2-phosphinylaniline (20 g, mol)
in 100 mL of chloroform. The resulting reaction mixture was stir-
red for 1.5 h at room temperature and 1 h at 50 °C, and after cool-
ing to room temperature washed with water. The organic layer was
separated, dried over anhydrous Na2SO4, and evaporated to dry-
ness. The resulting residue was crystallized upon addition of hex-
ane and dried in vacuo to give 19.0 g (90%) 1a as a white
crystalline solid. Mp: 228–230 °C (cf. 227–228 °C).1 31P{1H} NMR
(121.49 MHz, CDCl3, d/ppm): 35.57.
To summarize the results presented, simple modular assem-
bling procedures of the available building-blocks, ortho-(thio)phos-
phorylated anilines and diphenyl(thio)phosphorylacetic acid
derivatives, afford a series of oligondentate ligands 2a–d with do-
nor centers of variable nature, therewith, offering ample opportu-
nities for fine-tuning of their electronic and steric properties. The
ligands derived readily underwent N–H bond activation in the
reactions with Re(I) and Pd(II) precursors to give
j
3-XNY pincer
complexes with two fused six-membered metallocycles. In solu-
tion at room temperature the complexes obtained exist in stable
atropisomeric forms, and now the investigations are ongoing to re-
solve enantiomers.
4.3. General procedure for the synthesis of chloroacetamides 3a,b
A solution of triethylamine (0.6 mL, 4.3 mmol) and the corre-
sponding ortho-(thio)phosphorylated aniline (1a or 1b) (3.4 mmol)
in 10 mL of chloroform was slowly dropwise added under an argon
atmosphere to a stirred solution of chloroacetyl chloride (0.45 g,
4.0 mmol) in 7 mL of CHCl3, cooled with an ice-salt bath to 0 °C.
The reaction mixture was stirred at 0–5 °C for 30 min and left un-
der ambient conditions overnight. The resulting mixture was
washed with water (2 ꢃ 10 mL). The organic layer was separated,
dried over anhydrous Na2SO4, and evaporated to dryness. The res-
idue obtained was purified by column chromatography on silica
gel (eleunt: CH2Cl2 (3a), hexane–acetone (7:3) (3b)) to give 3a,b
as white crystalline solids.
4. Experimental
4.1. General remarks
If not noted otherwise, all manipulations were carried out with-
out taking precautions to exclude air and moisture. THF was dis-
tilled over sodium/beznophenone ketyl and dichloromethane was
distilled from P2O5. 2-(Diphenylthiophosphoryl)aniline 1b [9] and
Ph2P(S)H [20] were obtained according to the literature proce-
dures. All other chemicals and solvents were used as purchased.
NMR spectra were recorded on Bruker Avance-300 and Bruker
Avance-400 spectrometers, and the chemical shifts (d) were inter-
nally referenced by the residual solvent signals relative to tetra-
4.3.1. 2-Chloro-N-[2-(Diphenylphosphoryl)phenyl]acetamide 3a
Yield: 1.1 g (87%). Mp: 92–93 °C. 31P{1H} NMR (121.49 MHz,
CDCl3, d/ppm): 36.05. 1H NMR (400.13 MHz, CDCl3, d/ppm, J/Hz):
methylsilane (1H and 13C) or externally to H3PO4 31P). The 13C
(
NMR spectra were registered using the JMODECHO mode; the sig-
nals for the C atoms bearing odd and even numbers of protons have
3
3
4.02 (s, 2 H, CH2), 7.01 (dd, 1 H, H–C3, JHH = 7.6, JPH = 13.8),

V.Yu. Aleksenko et al. / Polyhedron 51 (2013) 168–179
175
3
4
2
7.08 (dt, 1 H, H–C4, JHH = 7.4, JPH = 2.4), 7.48–7.60 (m, 7 H, HAr),
3JPC = 12.6), 131.10 (d, o-C in P(O)(C6H5)2, JPC = 9.8), 131.30 (d,
3
3
1
7.64 (dd, 4 H, o-H in P(O)(C6H5)2, JHH = 7.6, JPH = 12.3), 8.47 (dd,
ipso-C in CH2P(O)(C6H5)2, JPC = 100.3), 131.76 (d, ipso-C in
1 H, H–C6, JHH = 8.4, JPH = 4.3), 11.51 (br. s, 1 H, NH). 13C{1H}
ArP(O)(C6H5)2, JPC = 108.9), 131.85 (d, p-C in P(O)(C6H5)2,
3
4
1
2
NMR (100.61 MHz, CDCl3, d/ppm, J/Hz): 42.96 (s, CH2), 118.94 (d,
4JPC = 2.9), 132.03 (d, o-C in P(O)(C6H5)2, JPC = 10.1), 132.45 (d, p-
1
3
4
2
C2, JPC = 100.6), 122.39 (d, C6, JPC = 12.1), 123.53 (d, C4,
C in P(O)(C6H5)2, JPC = 3.0), 132.55 (d, C3, JPC = 10.9), 133.11 (d,
3JPC = 12.2), 128.64 (d, m-C in P(O)C6H5, JPC = 12.2), 130.97 (d,
C5, JPC = 2.0), 143.68 (s, C1), 163.28 (d, C@O, JP,C = 4.9). IR (KBr,
3
4
2
1
ipso-C in P(O)(C6H5)2, JPC = 105.3), 131.91 (d, o-C in P(O)(C6H5)2,
m
/cmꢁ1): 513(m), 522(m), 548(s), 694(s), 709(m), 718(m),
2JPC = 8.8), 132.44 (s, p-C in P(O)(C6H5)2), 132.60 (d, C3,
746(m), 830(w), 961(w), 997(w), 1027(w), 1071(w), 1102(m),
1120(s), 1133(m), 1160(m) and 1167(m) (both P@O in ArP(O)Ph2),
1198(m) and 1203(m) (both P@O in CH2P(O)Ph2), 1263(w),
1309(br, m), 1438(vs), 1458(w), 1484(w), 1533(br, m) (NHCO),
1583(m), 1608(br, m), 1690(br, m) (C@O), 2922(w), 3054(w),
3174(w), 3239(br, w) (NH). Anal. Calc. for C32H27NO3P2: C, 71.77;
H, 5.08; N, 2.62. Found: C, 71.64; H, 5.04; N, 2.64%.
2JPC = 10.1), 133.23 (d, C5, JPC = 1.3), 142.88 (d, C1, JPC = 2.7),
4
2
165.16 (s, C@O). IR (KBr,
m
/cmꢁ1): 513(m), 546(vs), 692(m),
719(m), 726(m), 737(m), 752(w), 763(m), 775(m), 804(w),
1071(w), 1079(w), 1099(w), 1119(m), 1133(w), 1137(w),
1156(m), 1160(sh, m) (P@O), 1166(m) (P@O), 1252(w), 1271(w),
1307(s), 1400(w), 1408(w), 1438(s), 1452(m), 1485(w), 1535(br,
s) (NHCO), 1582(s), 1605(br, m), 1678(br, s) (C@O), 3025(w),
3153(br, w) (NH). Anal. Calc. for C20H17ClNO2P: C, 64.96; H, 4.63;
N, 3.79. Found: C, 65.04; H, 4.57; N, 3.74%.
4.4.2. 2-(Diphenylphosphoryl)-N-[2-(diphenylthiophosphoryl)phenyl]-
acetamide 2b
Yield: 1.9 g (69%). Mp: 215–216 °C. 31P{1H} NMR (161.98 MHz,
4.3.2. 2-Chloro-N-[2-(diphenylthiophosphoryl)phenyl]acetamide 3b
Yield: 1.3 g (99%). Mp: 192–193 °C (EtOAc). 31P{1H} NMR
(161.98 MHz, CDCl3, d/ppm): 39.51. 1H NMR (400.13 MHz, CDCl3,
CDCl3, d/ppm): 27.45 (CH2P(O)(C6H5)2), 39.82 (ArP(S)(C6H5)2). 1H
NMR (400.13 MHz, CDCl3, d/ppm, J/Hz): 3.04 (d,
2 H, CH2,
3
3
2JPH = 14.6), 6.75 (dd, 1 H, H–C3, JHH = 7.8, JPH = 14.4), 7.02 (t, 1
3
3
d/ppm, J/Hz): 3.70 (s, 2 H, CH2), 6.86 (dd, 1 H, H–C3, JHH = 7.9,
H, H–C4, JHH = 7.6), 7.39–7.55 (m, 13 H, HAr), 7.61 (dd, 1 H, H–
3JPH = 14.3), 7.14 (dt, 1 H, H–C4, JHH = 7.6, JPH = 2.2), 7.48–7.53
C6, JHH = 8.0, JPH = 5.0), 7.68 (dd, 4 H, o-H in ArP(S)(C6H5)2,
3
4
3
4
3
(m, 4 H, HAr), 7.58–7.63 (m, 3 H, HAr), 7.78 (dd, 4 H, o-H in
P(S)(C6H5)2, JHH = 7.9, JPH = 13.7), 7.98 (dd, 1 H, H–C6, JHH = 7.9,
4JPH = 4.8), 10.22 (br. s, 1 H, NH). IR (KBr, /cmꢁ1): 515(m),
3JPH = 13.8, JHH = 7.7), 7.77 (dd, 4 H, o-H in CH2P(O)(C6H5)2,
3JPH = 12.1, JHH = 7.6), 9.94 (br. s,
1
H, NH). 13C{1H} NMR
3
3
3
3
1
m
(75.47 MHz, CDCl3, d/ppm, J/Hz): 40.63 (d, CH2, JPC = 61.6),
123.13 (d, C2, JPC = 85.5), 124.48 (d, C4, JPC = 12.1), 126.03 (d,
C6, JPC = 7.0), 128.48 (d, m-C in P(X)(C6H5)2, JPC = 12.5), 128.66
(d, m-C in P(X)(C6H5)2, JPC = 12.8), 130.70 (d, ipso-C in ArP(S)(C6-
H5)2, JPC = 86.2), 131.12 (d, o-C in P(X)(C6H5)2, JPC = 9.9), 131.66
(d, ipso-C in CH2P(O)(C6H5)2, JPC = 108.0), 132.01 (d, overlapping
signals of p-C in P(O)(C6H5)2 and P(S)(C6H5)2, JPC = 2.9), 132.03
(d, C3, JPC = 7.7), 132.13 (d, o-C in P(X)(C6H5)2, JPC = 11.0),
1
3
523(m), 613(w) (P@S), 634(m) (P@S), 692(m), 714(s), 733(w),
749(w), 757(m), 761(w), 776(m), 1101(m), 1129(w), 1272(w),
1293(w), 1309(w), 1408(w), 1436(s), 1456(w), 1481(w), 1506(br,
s) (NHCO), 1570(m), 1573(m), 1682(br, m) (C@O), 2941(w),
2993(w), 3053(w), 3079(w), 3289(br, w) (NH). Analytically pure
sample was obtained by recrystallization from EtOAc. Anal. Calc.
for C20H17ClNOPS: C, 62.26; H, 4.44; N, 3.63. Found: C, 62.28; H,
4.51; N, 3.63%.
3
3
3
1
1
1
4
2
2
4
2
132.60 (d, C5, JPC = 2.6), 140.36 (d, C1, JPC = 4.4), 162.85 (d, C@O,
2JPC = 4.8). IR (KBr, /cmꢁ1): 516(m), 519(sh, m), 539(w), 545(w),
m
4.4. General procedure for the synthesis of ligands 2a,b
614(w) and 636(m) (both P@S), 690(m), 694(m), 707(m), 719(s),
725(m), 746(m), 752(m), 844(w), 999(w), 1026(w), 1072(w),
1101(m), 1121(m), 1128(w), 1172(m), 1182(w), 1202(m) (P@O),
1226(w), 1245(w), 1290(w), 1309(w), 1390(w), 1437(s), 1481(w),
1505(s) (NHCO), 1566(w), 1573(w), 1590(w), 1688(s) (C@O),
3023(w), 3051(w), 3208(br, w) (NH). Anal. Calc. for C32H27NO2P2-
Sꢂ0.25 CH2Cl2: C, 67.62; H, 4.84; N, 2.45. Found: C, 67.50; H, 4.76;
N, 2.33%.
A solution of PCl3 (0.33 g, 2.4 mmol) in 4 mL of dichloromethane
was slowly dropwise added to a stirred solution of diphenylphos-
phorylacetic acid (1.56 g, 6.0 mmol) in 10 mL of CH2Cl2 at 0–5 °C
under an argon atmosphere. After stirring for 5 h at room temper-
ature, the resulting solution was cooled again to 0 °C with an ice-
salt bath, and then a solution of the corresponding aniline (1a or
1b) (4.8 mmol) and triethylamine (0.17 mL, 1.2 mmol) in 5 mL of
CH2Cl2 was added. The resulting reaction mixture was stirred for
0.5 h at 0 °C and left overnight. The solution obtained was sequen-
tially washed with 20 mL of diluted hydrochloric acid (1 mL conc.
HCl/10 mL H2O), water (2 ꢃ 15 mL), saturated aqueous solution
of NaOH (15 mL), and again with water (2 ꢃ 15 mL). The organic
layer was separated, dried over anhydrous Na2SO4, and evaporated
to dryness. The resulting residue was purified by column chroma-
tography on silica gel (eluent in both cases CH2Cl2/MeOH (10:1)) to
give 2a,b as white crystalline solids.
4.5. General procedure for the synthesis of ligands 2c,d
A 60% dispersion of NaH in mineral oil (0.1 g, 2.5 mmol) was
portionwise added to a solution of Ph2P(S)H (0.5 g, 2.3 mmol) in
5 mL of THF under vigorous stirring and argon atmosphere. The
reaction mixture was stirred for 15 min, then a solution of the cor-
responding chloroacetamide (3a or 3b) (2.3 mmol) in 10 mL of THF
was added. The resulting mixture was stirred for 2 h at 40 °C and
left overnight. The solvent was removed in vacuo, the residue
was dissolved in CHCl3 and washed with water. The organic layer
was separated, dried over anhydrous Na2SO4, and evaporated to
dryness. The resulting residue was purified by column chromatog-
raphy on silica gel (eluent: hexane–acetone (7:3) (2c), CH2Cl2–
MeOH (10:1) (2d)) to give 2c,d as white crystalline solids.
4.4.1. 2-(Diphenylphosphoryl)-N-[2-(diphenylphosphoryl)phenyl]-
acetamide 2a
Yield: 1.4 g (55%). Mp: 168–169 °C. 31P{1H} NMR (161.98 MHz,
CDCl3, d/ppm): 27.83 (CH2P(O)(C6H5)2), 36.96 (ArP(O)(C6H5)2). 1H
NMR (400.13 MHz, CDCl3, d/ppm, J/Hz): 3.46 (d,
2 H, CH2,
2JPH = 14.5), 6.92–7.00 (m, 2 H, HAr), 7.37–7.49 and 7.56–7.61 (both
4.5.1. N-[2-(Diphenylphosphoryl)phenyl]-2-(diphenylthiophosphoryl)-
acetamide 2c
3
m, 11 H + 6 H, HAr), 7.81 (dd, 4 H, o-H in P(O)(C6H5)2, JPH = 12.1,
3
4
3JHH = 8.2), 8.30 (dd, 1 H, H–C6, JHH = 8.4, JPH = 4.4), 11.29 (br. s,
Yield: 1.0 g (79%). Mp: 184–185 °C. 31P{1H} NMR (161.98 MHz,
1 H, NH). 13C{1H} NMR (75.47 MHz, CDCl3, d/ppm, J/Hz): 41.68 (d,
CDCl3, d/ppm): 36.84 (ArP(O)(C6H5)2), 38.65 (CH2P(S)(C6H5)2). 1H
1
1
CH2, JPC = 62.9), 116.77 (d, C2, JPC = 100.6), 122.18 (d, C6,
NMR (400.13 MHz, CDCl3, d/ppm, J/Hz): 3.61 (d,
2JPH = 14.1), 6.94–7.02 (m, 2 H, HAr), 7.38–7.50 (m, 11 H, HAr
7.56–7.63 (m, 6 H, HAr), 7.88 (dd, 4 H, o-H in P(X)(C6H5)2,
2 H, CH2,
3JPC = 7.2), 122.94 (d, C4, JPC = 12.6), 128.37 (d, m-C in
)
3
P(O)(C6H5)2, 3JPC = 12.4), 128.61 (d, m-C in P(O)(C6H5)2,

176
V.Yu. Aleksenko et al. / Polyhedron 51 (2013) 168–179
3
3
4
1
3
3JPH = 13.5, JHH = 7.5), 8.35 (dd, 1 H, H–C6, JHH = 8.3, JPH = 4.4),
121.34 (d, C2, JPC = 101.6), 123.21 (d, C4, JPC = 13.6), 127.81 (d,
11.29 (br. s, 1 H, NH). 13C{1H} NMR (75.47 MHz, CDCl3, d/ppm, J/
Hz): 44.78 (d, CH2, JPC = 48.9), 117.12 (d, C2, JPC = 100.3), 122.39
ipso-C in ArP(O)C6H5, JPC = 111.1), 128.00 (d, m-C in P(O)C6H5,
1
1
1
3
3JPC = 13.9), 128.66 (d, m-C in P(O)C6H5, JPC = 12.5), 128.74 (d, m-
3
3
3
3
(d, C6, JPC = 8.0), 123.02 (d, C4, JPC = 12.9), 128.40 (d, m-C in
C in P(O)C6H5, JPC = 12.8), 128.76 (d, C6, JPC = 8.4), 128.94 (d,
P(X)(C6H5)2, 3JPC = 12.6), 128.63 (d, m-C in P(X)(C6H5)2,
ipso-C in ArP(O)C6H5, JPC = 112.2), 129.03 (d, ipso-C in CH2P(O)C6-
1
3JPC = 12.6), 131.30 (d, ipso-C in ArP(O)(C6H5)2, JPC = 106.0),
H5, 1JPC = 108.9), 129.14 (d, m-C in P(O)C6H5, 3JPC = 12.8), 129.66 (d,
1
2
1
131.37 (d, o-C in P(X)(C6H5)2, JPC = 10.9), 131.49 (d, p-C in
P(X)(C6H5)2, JPC = 3.2), 132.02 (d, o-C in P(X)(C6H5)2, JPC = 10.1),
132.18 (d, ipso-C in CH2P(S)(C6H5)2, JPC = 83.6), 132.40 (d, p-C in
ipso-C in CH2P(O)C6H5, JPC = 92.1), 130.58 (d, o-C in P(O)C6H5,
2JPC = 10.6), 131.02 (d, o-C in P(O)C6H5, JPC = 11.4), 132.08 (d, o-C
4
2
2
1
2
2
in P(O)C6H5, JPC = 11.4), 132.42 (d, C3, JPC = 11.7), 132.43 (d, p-C
in P(O)C6H5, JPC = 2.6), 132.58 (d, p-C in P(O)C6H5, JPC = 2.9),
132.67 (d, o-C in P(O)C6H5, JPC = 10.3), 132.88 (d, p-C in
P(O)C6H5, JPC = 2.9), 132.95 (d, p-C in P(O)C6H5, JPC = 2.9), 133.61
(d, C5, JPC = 2.2), 157.42 (s, C1), 167.54 (d, C@O, JP,C = 7.3),
193.92 (s, CO), 195.68 (s, CO), 195.74 (s, CO). IR (RBr,
523(w), 536(w), 553(s), 569(m), 630(w), 689(m), 695(m), 723(m),
736(w), 747(m), 760(w), 808(w), 820(w), 845(w), 979(w),
998(w), 1027(w), 1068(m), 1093(m), 1130(s) (P@O in ArP(O)Ph2),
1140(m), 1150(s) (P@O in CH2P(O)Ph2), 1266(w), 1327(br, m),
1393(w), 1437(s), 1464(w), 1486(w), 1568(sh, w), 1579(m),
1603(s) (C@O), 1856(vs) (CO), 1868(vs) (CO), 1903(vs) (CO),
1910(vs) (CO), 2017(vs) (CO), 2853(w), 2922(w), 2959(w),
3056(w). Anal. Calc. for C35H26NO6P2Re: C, 52.24; H, 3.26; N,
1.74. Found: C, 52.57; H, 3.56; N, 1.68%.
4
2
4
4
P(X)(C6H5)2, JPC = 2.9), 132.61 (d, C3, JPC = 10.6), 133.15 (d, C5,
4JPC = 2.0), 143.57 (d, C1, JPC = 2.9), 163.04 (d, C@O, JPC = 4.9). IR
2
2
2
4
4
(KBr,
m
/cmꢁ1): 519(m), 547(s), 598(w), 648(w) (P@S), 692(s),
4
2
711(s), 739(m), 747(m), 769(sh, w), 791(w), 961(w), 998(w),
1027(w), 1070(w), 1076(w), 1102(m), 1120(m), 1134(m),
1153(m) and 1167(m) (both P@O), 1268(w), 1311(br, s),
1410(w), 1437(vs), 1457(w), 1483(w), 1507(w), 1540(br, m)
(NHCO), 1583(s), 1609(br, m), 1684(br, m) (C@O), 2918(w),
3055(w), 3180(br, w) (NH), 3250(br, w) (NH). Anal. Calc. for C32H27-
NO2P2S: C, 69.68; H, 4.93; N, 2.54. Found: C, 69.49; H, 5.01; N,
2.44%.
m
/cmꢁ1):
4.5.2. 2-(Diphenylthiophosphoryl)-N-[2-(diphenylthiophosphoryl)-
phenyl]acetamide 2d
Yield: 1.0 g (77%). Mp: 215–216 °C. 31P{1H} NMR (121.49 MHz,
CDCl3, d/ppm): 38.25 (CH2P(S)(C6H5)2), 40.07 (ArP(S)(C6H5)2). 1H
4.6.2. Complex 4d
NMR (400.13 MHz, CDCl3, d/ppm, J/Hz): 3.24 (d,
2
H, CH2,
Yield: 75 mg (68%). Mp: >240 °C (decomp.). 31P{1H} NMR
(121.49 MHz, CDCl3, d/ppm): 40.40 (CH2P(S)(C6H5)2), 41.45
(ArP(S)(C6H5)2). 1H NMR (300.13 MHz, CDCl3, d/ppm, J/Hz): 3.76
2JPH = 14.0), 6.78 (dd, 1 H, H–C3, JHH = 7.8, JPH = 14.3), 7.03 (t, 1
3
3
3
H, H–C4, JHH = 7.7), 7.44–7.55 (m, 13 H, HAr), 7.64–7.69 (m, 5 H,
3
3
2
2
H
Ar), 7.84 (dd, 4 H, o-H in P(S)(C6H5)2, JPH = 13.6, JHH = 8.2), 9.92
(dd,
1
H, CH2, JPH = 10.2, JHH = 14.7), 3.92 (dd,
1
H, CH2,
(br. s, 1 H, NH). 13C{1H} NMR (100.61 MHz, CDCl3, d/ppm, J/Hz):
2JPH = 17.0, 2JHH = 14.7), 6.64 (dd,
1
H, H–C3, 3JHH = 8.0,
1
1
43.71 (d, CH2, JPC = 47.4), 122.91 (d, C2, JPC = 85.2), 124.39 (d,
3JPH = 15.1), 6.89–7.04 (m, 4 H, HAr), 7.31–7.39 (m, 5 H, HAr),
3
3
C4, JPC = 12.0), 125.91 (d, C6, JPC = 6.8), 128.29 (d, m-C in
7.47–7.69 (m, 14 H, HAr). 13C{1H} NMR (75.47 MHz, CDCl3, d/ppm,
3
3
1
1
P(S)(C6H5)2, JPC = 12.6), 128.47 (d, m-C in P(S)(C6H5)2, JPC = 12.9),
J/Hz): 43.30 (d, CH2, JPC = 45.3), 121.81 (d, C2, JPC = 85.8), 123.47
(d, C4, JPC = 13.1), 126.28 (d, ipso-C in ArP(S)C6H5, JPC = 88.9),
127.29 (d, m-C in P(S)C6H5, JPC = 13.8), 128.19 (d, ipso-C in
ArP(S)C6H5, JPC = 85.1), 128.72 (d, m-C in P(S)C6H5, JPC = 12.4),
128.84 (d, m-C in P(S)C6H5, JPC = 12.8), 129.04 (d, m-C in
P(S)C6H5, JPC = 12.8), 129.81 (d, C6, JPC = 8.6), 129.92 (d, ipso-C
1
3
1
130.59 (d, ipso-C in ArP(S)(C6H5)2, JPC = 85.8), 131.15 (d, o-C in
P(S)(C6H5)2, JPC = 10.8), 131.45 (d, p-C in P(S)(C6H5)2, JPC = 3.1),
2
4
3
1
1
3
131.71 (d, ipso-C in CH2P(S)(C6H5)2, JPC = 83.4), 131.80 (d, p-C in
4
2
3
P(S)(C6H5)2, JPC = 3.1), 131.94 (d, C3, JPC = 9.2), 131.98 (d, o-C in
2
4
3
3
P(S)(C6H5)2, JPC = 11.1), 132.43 (d, C5, JPC = 2.2), 140.19 (d, C1,
2JPC = 4.3), 162.29 (d, C@O, JPC = 5.2). IR (KBr,
m
/cmꢁ1): 515(m),
in CH2P(S)C6H5, JPC = 84.8), 130.19 (d, ipso-C in CH2P(S)C6H5,
2
1
2
530(w), 535(w), 614(w) and 637(m) (both P@S in ArP(S)Ph2),
649(w) (P@S in CH2P(S)Ph2), 692(s), 711(s), 721(m), 740(m),
750(m), 758(w), 800(w), 841(w), 998(w), 1025(w), 1071(w),
1102(m), 1130(w), 1247(w), 1290(w), 1310(w), 1392(w),
1436(vs), 1481(w), 1500(m) (NHCO), 1574(w), 1591(w), 1677(s)
(C@O), 2852(w), 2922(w), 3055(w), 3250(br, w) (NH). Anal. Calc.
for C32H27NOP2S2: C, 67.71; H, 4.79; N, 2.47; S, 11.30. Found: C,
67.71; H, 4.83; N, 2.49; S, 11.37%.
1JPC = 78.5), 130.98 (d, o-C in P(S)C6H5, JPC = 11.1), 131.02 (d, o-C
2
2
in P(S)C6H5, JPC = 11.1), 131.62 (d, C3, JPC = 9.7), 131.86 (d, p-C
in P(S)C6H5, JPC = 2.8), 132.18 (d, p-C in P(S)C6H5, JPC = 3.1),
132.52–132.75 (overlapping signals of two p-C + one o-C in
4
4
2
P(S)C6H5), 133.28 (d, o-C in P(S)C6H5, JPC = 10.0), 133.84 (d, C5,
4JPC = 2.2), 158.08 (s, C1), 168.93 (d, C@O, JPC = 7.3), 189.62 (s,
2
3
3
CO), 192.44 (d, CO, JPC = 2.4), 192.55 (d, CO, JPC = 6.9). IR (RBr, m/
cmꢁ1): 525(m), 532(m), 550(w), 588(m) (P@S in ArP(S)Ph2),
604(m) (P@S in CH2P(S)Ph2), 622(w), 625(w), 647(w), 689(s),
698(m), 709(m), 741(m), 746(m), 759(m), 810(w), 837(w),
885(w), 979(m), 998(w), 1028(w), 1072(w), 1101(s), 1118(m),
1133(w), 1261(w), 1318(br, s), 1387(w), 1438(s), 1462(m),
1481(w), 1559(m), 1580(m), 1604(s) (C@O), 1877(vs) (CO),
1900(vs) (CO), 2014 (vs) (CO), 2962(w), 3062(w). Anal. Calc. for C35-
H26NO4P2ReS2ꢂ0.33 CHCl3: C, 48.41; H, 3.03; N, 1.60. Found: C,
48.41; H, 3.13; N, 1.42%.
4.6. General procedure for the synthesis of Re(I) complexes 4a,d
A solution of Re(CO)5Br (51 mg, 0.126 mmol), triethylamine
(17.5
lL, 0.126 mmol), and the corresponding ligand (2a or 2b)
(0.126 mmol) in 10 mL of toluene was refluxed for 1.5 h. After cool-
ing to room temperature, the solvent was removed in vacuo and
the resulting residue was purified by column chromatography on
silica gel (eluent CHCl3) to give 5a,b as white crystalline solids.
4.7. Synthesis of complex 5
4.6.1. Complex 4a
Yield: 83 mg (82%). Mp: >264 °C (decomp.). 31P{1H} NMR
(121.49 MHz, CDCl3, d/ppm): 45.59 (CH2P(O)(C6H5)2), 45.94
Ar(P(O)(C6H5)2). 1H NMR (300.13 MHz, CDCl3, d/ppm, J/Hz): 3.43
A solution of Re(CO)5Br (52 mg, 0.127 mmol) and ligand 2a
(68 mg, 0.127 mmol) in 10 mL of toluene was refluxed for 1.5 h.
After cooling to room temperature, the solvent was removed in va-
cuo and the resulting residue was crystallized from diethyl ether.
The desired product was collected by filtration and dried under
vacuum (white crystalline solid). Yield: 111 mg (99%). Mp:
>165 °C (decomp.). 31P{1H} NMR (161.98 MHz, CDCl3, d/ppm):
43.35 (CH2P(O)(C6H5)2), 46.18 (ArP(O)(C6H5)2). 1H NMR
2
2
(dd,
1 H, CH2, JPH = 4.1, JHH = 15.1), 4.07 (dd, 1 H, CH2,
2JPH = 19.3, 2JHH = 15.1), 6.81 (dd,
1
H, H–C3, 3JHH = 7.5,
3JPH = 14.3), 6.99–7.05 (m, 3 H, HAr), 7.14–7.25 (m, 3 H, HAr),
7.31–7.46 (m, 5 H, HAr), 7.51–7.66 (m, 12 H, HAr). 13C{1H} NMR
1
(100.61 MHz, CDCl3, d/ppm, J/Hz): 40.84 (d, CH2, JPC = 58.3),

V.Yu. Aleksenko et al. / Polyhedron 51 (2013) 168–179
177
2
(400.13 MHz, CDCl3, d/ppm, J/Hz): 3.33 (dd, 1 H, CH2, JPH = 5.4,
H
Ar). 13C{1H} NMR (100.61 MHz, CDCl3, d/ppm, J/Hz): 46.13 (d,
CH2, JPC = 43.8), 123.48 (d, C4, JPC = 13.2), 126.19 (d, ipso-C in
2JHH = 14.2), 4.92 (dd, 1 H, CH2, JPH = 22.3, JHH = 14.2), 6.99 (dd,
2
2
1
3
3
3
3
1
1
1 H, H–C3, JPH = 15.6, JHH = 7.8), 7.07 (dt, 1 H, H–C4, JHH = 7.8,
CH2P(S)C6H5, JPC = 80.3), 126.49 (d, C2, JPC = 102.3), 126.62 (d,
4JPH = 3.1), 7.35–7.63 (m, 16 H, HAr), 7.71 (t,
1
1
H, H–C5,
H, H–C6,
m
ipso-C in ArP(O)C6H5, JPC = 111.5), 126.90 (d, ipso-C in CH2P(S)-
C6H5, JPC = 86.2), 128.50 (d, m-C in P(X)C6H5, JPC = 13.5), 128.64
(d, m-C in P(X)C6H5, JPC = 13.2), 128.87 (d, C6, JPC = 7.3), 129.04
1
3JHH = 7.9), 7.77–7.86 (m,
4
H, HAr), 8.20 (dd,
1
3
4
3
3
3JHH = 7.9, JPH = 4.9), 10.59 (br. s, 1 H, NH). IR (RBr,
/cmꢁ1):
1
513(w), 528(m), 550(m), 692(m), 708(w), 722(m), 734(w),
744(m), 750(m), 838(w), 998(w), 1028(w), 1072(w), 1106(m),
1122(m), 1147(m) and 1158(m) (P@O in ArP(O)Ph2), 1171(m)
and 1185(m) (P@O in CH2P(O)Ph2), 1255(w), 1297(m), 1388(w),
1438(s), 1461(w), 1485(w), 1529(m), 1578(m), 1590(w),
1598(w), 1696(m) (C@O), 1877(vs) (CO), 1883(vs) (CO), 1896(vs)
(CO), 1902(vs) (CO), 2020(vs) (CO), 2895(w), 2952(w), 3059(w),
3287(w) (NH). Anal. Calc. for C35H27BrNO6P2Re: C, 47.47; H, 3.07;
Br, 9.02; N, 1.58; P, 7.10. Found: C, 47.37; H, 2.97; Br, 9.02; N,
1.47; P, 7.14%.
(d, ipso-C in ArP(O)C6H5, JPC = 108.4), 129.24 (d, m-C in P(X)C6H5,
3JPC = 12.8), 129.35 (d, m-C in P(X)C6H5, JPC = 12.8), 131.78 (d, o-
3
2
2
C in P(X)C6H5, JPC = 11.0), 131.80 (d, o-C in P(X)C6H5, JPC = 11.0),
132.04 (d, o-C in P(X)C6H5, JPC = 11.0), 132.27 (d, C3, JPC = 11.0),
2
2
4
132.59 (d, p-C in P(X)C6H5, JPC = 2.9), 133.00 (d, o-C in P(X)C6H5,
2JPC = 10.6), 133.07 (d, p-C in P(X)C6H5, JPC = 2.9), 133.25 (d, p-C
4
4
4
in P(X)C6H5, JPC = 3.3), 133.28 (d, p-C in P(X)C6H5, JPC = 2.9),
4
2
134.06 (d, C5, JPC = 1.8), 150.73 (d, C1, JPC = 1.5), 164.92 (d, C@O,
2JPC = 6.2). IR (RBr, /cmꢁ1): 516(w), 550(m), 564(s) (P@S),
m
582(w), 691(m), 717(m), 732(m), 747(m), 751(m), 836(w),
893(w), 988(w), 998(w), 1026(w), 1056(m), 1085(w), 1105(m),
1123(s) (P@O), 1193(w), 1267(w), 1311(w), 1347(m), 1375(w),
1437(s), 1462(m), 1483(w), 1562(w), 1580(m), 1615(vs) (C@O),
2850(w), 3054(w). Analytically pure sample was obtained upon
4.8. General procedure for the synthesis of Pd(II) complexes 6b–d
A solution of (PhCN)2PdCl2 (66 mg, 0.172 mmol) in 5 mL of
dichloromethane was slowly dropwise added to a solution of the
corresponding ligand (2b, 2c or 2d) (0.172 mmol) in 5 mL of
CH2Cl2. The reaction mixture was left under ambient conditions
for 12 h, then the solvent was removed in vacuo and the resulting
residue was purified by column chromatography on silica gel
(eluent CHCl3) to give 6b–d as orange crystalline solids.
recrsytallization from CH2Cl2–he[ane (1:2). Anal. Calc. for C32H26
-
ClNO2P2PdS: C, 55.51; H, 3.78; N, 2.02. Found: C, 55.14; H, 3.67;
N, 1.93%.
4.8.3. Complex 6d
Yield: 111 mg (91%). Mp: >285 °C (decomp.). 31P{1H} NMR
(121.49 MHz, CDCl3, d/ppm): 38.17 (CH2P(S)(C6H5)2), 41.04
(ArP(S)(C6H5)2). 1H NMR (400.13 MHz, CDCl3, d/ppm, J/Hz): 3.28
4.8.1. Complex 6b
Yield: 95 mg (80%). Mp: >230 °C (decomp.). 31P{1H} NMR
(161.98 MHz, CDCl3, d/ppm): 37.70 (CH2P(O)(C6H5)2), 47.23
(ArP(S)(C6H5)2). 1H NMR (400.13 MHz, CDCl3, d/ppm, J/Hz): 3.00
(dd, 1 H, CH2, JPH = 9.5, JHH = 13.3), 3.73 (dd, 1 H, CH2,
2
2
2JPH = 17.0, 2JHH = 13.3), 6.80 (dd,
1
H, H–C3, 3JHH = 7.7,
3JPH = 14.0), 7.02 (dt, 1 H, H–C4, JHH = 7.6, JPH = 3.6), 7.18 (dd, 1
3
4
2
2
3
4
(d,
1
H, CH2, JHH = 14.6), 3.84 (dd,
1
H, CH2, JHH = 14.6,
H, H–C6, JHH = 7.5, JPH = 5.2), 7.45–7.57 (m, 11 H, HAr), 7.61–
2JPH = 19.7), 6.73–6.78 (m,
2
H, HAr), 7.00 (dt,
1
H, H–C4,
7.67 (m, 4 H, HAr), 7.74 (dd, 2 H, o-H in P(S)C6H5, JHH = 7.8,
3
3JHH = 7.7, JPH = 3.2), 7.40 (t, 1 H, H–C5, JHH = 7.6), 7.50–7.67 (m,
3JPH = 14.7), 7.81 (dd, 2 H, o-H in P(S)C6H5, JHH = 7.9, JPH = 13.7),
4
3
3
3
3
3
3
14 H, HAr), 7.73–7.76 (dd, 2 H, o-H in P(X)C6H5, JHH = 7.8,
7.93 (dd, 2 H, o-H in P(S)C6H5, JHH = 7.7, JPH = 14.2). 13C{1H}
3JPH = 14.8), 7.80–7.90 (m, 4 H, HAr). 13C{1H} NMR (100.61 MHz,
NMR (100.61 MHz, CDCl3, d/ppm, J/Hz): 46.61 (d, CH2,
1
3
1
CDCl3, d/ppm, J/Hz): 43.73 (d, CH2, JPC = 57.2), 123.11 (d, ipso-C
in ArP(S)C6H5, JPC = 85.1), 123.52 (d, C4, JPC = 13.2), 124.24 (d,
C2, JPC = 86.6), 126.41 (d, ipso-C in ArP(S)C6H5, JPC = 88.8),
127.55 (d, ipso-C in CH2P(O)C6H5, JPC = 104.7), 127.61 (d, ipso-C
1JPC = 44.0), 123.52 (d, C4, JPC = 13.2), 124.23 (d, C2, JPC = 84.7),
1
3
1
126.58 (d, ipso-C in ArP(S)C6H5, JPC = 87.3), 127.19 (d, ipso-C in
1
1
1
ArP(S)C6H5, JPC = 88.4), 127.75 (d, ipso-C in CH2P(S)C6H5,
1
1
1JPC = 82.2), 128.26 (d, ipso-C in CH2P(S)C6H5, JPC = 81.4), 128.67
1
3
in CH2P(O)C6H5, JPC = 104.9), 128.66 (d, m-C in P(X)C6H5,
(d, m-C in P(S)C6H5, JPC = 13.6), 129.09 (d, m-C in P(S)C6H5,
3JPC = 13.6), 128.82 (d, m-C in P(X)C6H5, JPC = 12.4), 129.05 (d, m-
3JPC = 12.5), 129.14 (d, m-C in P(S)C6H5, JPC = 12.8), 129.26 (d, m-
3
3
3
3
3
C
in P(X)C6H5, JPC = 13.6), 129.18 (d, m-C in P(X)C6H5,
C in P(S)C6H5, JPC = 13.2), 130.31 (d, C6, JPC = 8.1), 131.45 (d, C3,
3
2
2
3JPC = 12.8), 130.05 (d, C6, JPC = 8.1), 131.07 (d, C3, JPC = 8.8),
2JPC = 9.2), 131.75 (d, o-C in P(S)C6H5, JPC = 11.00), 131.96 (d, o-C
2
2
2
131.16 (d, o-C in P(X)C6H5, JPC = 10.6), 131.60 (d, o-C in
P(X)C6H5, JPC = 10.3), 132.03 (d, o-C in P(X)C6H5, JPC = 11.7),
in P(S)C6H5, JPC = 11.7), 132.00 (d, o-C in P(S)C6H5, JPC = 11.4),
2
2
4
132.64 (d, p-C in P(S)C6H5, JPC = 3.3), 132.87 (d, p-C in P(S)C6H5,
4
4
132.91 (d, p-C in P(X)C6H5, JPC = 2.6), 133.04 (s, p-C in P(X)C6H5),
4JPC = 3.3), 133.05 (d, p-C in P(S)C6H5, JPC = 2.9), 133.28 (d, p-C in
2
4
2
133.17 (s, p-C in P(X)C6H5), 133.48 (d, o-C in P(X)C6H5, JPC = 9.9),
P(S)C6H5, JPC = 2.9), 133.48 (d, o-C in P(S)C6H5, JPC = 10.3),
4
4
2
133.53 (s, p-C in P(X)C6H5), 133.94 (d, C5, JPC = 2.2), 151.14 (d,
134.09 (d, C5, JPC = 2.2), 151.14 (d, C1, JPC = 4.4), 165.56 (d,
2
2
2
C1, JPC = 3.7), 165.25 (d, C@O, JPC = 6.6). IR (RBr,
m
/cmꢁ1):
C@O, JPC = 6.6). IR (RBr, m
/cmꢁ1): 525(m), 548(m), 586(s) (P@S in
510(m), 517(s), 552(w), 594(m) (P@S), 619(w), 633(w), 691(m),
712(m), 723(w), 746(m), 752(m), 761(m), 795(w), 841(w),
982(w), 998(w), 1028(w), 1065(w), 1080(w), 1107(m), 1126(m),
1137(s) (P@O), 1163(w), 1189(w), 1264(w), 1329(s), 1378(w),
1437(s), 1462(m), 1483(w), 1560(w), 1576(m), 1590(w), 1616(vs)
(C@O), 2852(w), 2922(w), 3057(w). Anal. Calc. for C32H26ClNO2P2
PdS: C, 55.51; H, 3.78; N, 2.02. Found: C, 55.06; H, 3.64; N, 1.96%.
CH2P(S)(C6H5)2, 601(m) (P@S in ArP(S)(C6H5)2), 621(w), 633(w),
688(s), 703(m), 716(m), 745(s), 841(w), 892(w), 983(w), 988(w),
1027(w), 1071(w), 1104(s), 1186(w), 1265(w), 1314(w), 1337(br,
m), 1379 (w), 1437(s), 1462(m), 1481(w), 1577(m), 1609(s)
(C@O), 2910(w), 3054(w). Anal. Calc. for C32H26ClNOP2PdS2: C,
54.25; H, 3.70; N, 1.98. Found: C, 54.35; H, 3.88; N, 1.91%.
4.9. Crystal structure determination and data collection
4.8.2. Complex 6c
Yield: 55 mg (46%). Mp:>230 °C (decomp.). 31P{1H} NMR
(121.49 MHz, CDCl3, d/ppm): 43.30 (ArP(O)(C6H5)2), 46.90
(CH2P(S)(C6H5)2). 1H NMR (300 MHz, CDCl3, d/ppm, J/Hz): 3.45
Single crystals suitable for X-ray experiments were obtained by
recrystallization from ethanol (2a) or acetonitrile (2b) or slow dif-
fusion of hexane into CH2Cl2 (5, 6d) or CHCl3 (4a, 4d, 6b, 6c) solu-
tions. X-ray diffraction experiments were carried out with a SMART
1000 CCD diffractometer for compound 2a and with a SMART
APEX2 CCD diffractometer for 2b and complexes 4a, 4d, 5, 6b, 6c,
2
2
(dd,
1 H, CH2, JPH = 8.5, JHH = 14.0), 4.14 (dd, 1 H, CH2,
2
3
4
2JPH = 17.9, JHH = 14.0), 6.77 (dd, 1 H, H–C3, JHH = 7.7, JPH = 4.2),
3
3
6.86 (dd, 1 H, H–C6, JHH = 8.0, JPH = 13.4), 7.06 (dt, 1 H, H–C4,
4
3JHH = 7.7, JPH = 2.5), 7.41–7.65 (m, 17 H, HAr), 7.84–7.89 (m, 4 H,
and 6d, using graphite monochromated Mo Ka radiation

178
V.Yu. Aleksenko et al. / Polyhedron 51 (2013) 168–179
Table 1
Crystal data and structure refinement parameters for 2a, 2b, 4a, 4d, 5, 6b, 6c, and 6d.
2a
2b
4a
4d
5
6b
6c
6d
Empirical formula
Formula weight
T (K)
C33H31NO4P2 C32H27NO2P2S C73H55Cl9N2O12P4Re2 C35H26NO4P2ReS2 C35H26BrNO6P2Re C32H26ClNO2P2PdS C32H26ClNO2P2PdS C32H26ClNOP2PdS2
567.53
100
551.55
100
1967.52
296
836.83
100
884.62
100
692.39
100
692.39
100
708.45
100
Crystal system
Space group
Z
triclinic
P1
2
monoclinic
P21/n
4
monoclinic
P21/n
4
monoclinic
P21/n
4
monoclinic
P21/n
8
monoclinic
Cc
triclinic
P1
2
monoclinic
P21/c
4
ꢀ
ꢀ
4
a (Å)
b (Å)
c (Å)
11.5340(7) 15.6006(9)
11.6240(7) 9.5574(6)
12.0915(8) 18.4115(11) 18.5059(10)
16.6737(10)
24.8693(14)
13.5079(7)
12.5963(6)
18.7405(9)
–
98.3320(10)
–
3155.0(3)
1.762
41.27
10.7141(14)
17.032(2)
36.494(5)
–
97.676(2)
–
6599.6(15)
1.781
50.37
20.989(5)
10.319(2)
16.737(6)
–
124.833(3)
–
2975.4(14)
1.546
9.22
10.5238(14)
11.8007(16)
13.2223(18)
83.239(3)
66.574(2)
70.724(2)
1422.1(3)
1.617
10.3137(4)
13.3546(6)
21.9310(10)
–
92.8430(10)
–
3017.0(2)
1.560
9.76
a
(°)
62.690(1)
89.856(2)
82.338(1)
–
–
b (°)
97.3710(10) 99.2510(10)
–
c
(°)
–
V (Å3)
1424.40(15) 2722.5(3)
7573.9(7)
1.725
36.57
Dcalc (g cmꢁ1
)
1.323
1.92
1.346
2.68
Linear absorption
(cmꢁ1
F(000)
2hmax (°)
l
9.65
)
596
58
1152
58
3864
56
1648
58
3448
52
1400
60
700
58
1432
58
Reflections
21150
27954
73889
24651
61306
30322
16911
23507
measured
Independent
reflections
7564
7226
5814
18263
11680
8367
6950
12950
9461
8509
7175
7516
5935
7990
6772
Observed reflections 5272
[I > 2 (I)]
r
Parameters
R1
wR2
403
343
924
406
830
362
361
361
0.0543
0.1393
0.999
0.0384
0.1011
0.999
0.0641
0.1902
1.320
0.0266
0.0586
1.006
0.0504
0.1323
1.014
0.0469
0.0953
1.005
0.0381
0.0850
1.003
0.0291
0.0715
1.007
Goodness-of-fit
(GOF)
D
q
/
max Dqmin (e Åꢁ3) 0.519/
0.492/ꢁ0.372 4.325/ꢁ2.666
1.244/ꢁ1.079
2.502/ꢁ1.887
0.493/ꢁ0.912
0.733/ꢁ0.800
0.504/ꢁ0.426
ꢁ0.586
(c) T.Ya. Medved’, M.K. Chmutova, N.P. Nesterova, O.E. Koiro, N.E. Kochetkova,
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(k = 0.71073 Å,
x-scans) at RT (4a) and 100 K (others). The struc-
tures were solved by direct method and refined by the full-matrix
least-squares against F2 in anisotropic approximation for non-
hydrogen atoms. Hydrogen atoms of OH groups in 2a and of NH
groups in both 2a and 2b were found in difference Fourier synthe-
sis; the H(C) atom positions were calculated. All hydrogen atoms
were refined in isotropic approximation in riding model. Crystal
data and structure refinement parameters for 2a, 2b, 4a, 4d, 5,
6b, 6c, and 6d are given in Table 1. All calculations were performed
using the SHELXTL software [22].
Acknowledgement
[6] (a) M. Albrecht, G. van Koten, Angew. Chem., Int. Ed. 40 (2001) 3750;
(b) J.T. Singleton, Tetrahedron 59 (2003) 1837;
(c) M.E. van der Boom, D. Milstein, Chem. Rev. 103 (2003) 1759;
(d) D. Morales-Morales, Rev. Soc. Quím. Méx. 48 (2004) 338;
(e) J. Dupont, C.S. Consorti, J. Spencer, Chem. Rev. 105 (2005) 2527;
(f) I. Moreno, R. SanMartin, B. Inés, M.T. Herrero, E. Domínguez, Curr. Org.
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The authors are grateful to the Russian Foundation for Basic Re-
search (Grant 12-03-00793-a) for the financial support.
Appendix A. Supplementary material
(g) I. Moreno, R. SanMartin, B. Inés, F. Churruca, E. Domínguez, Inorg. Chim.
Acta 363 (2009) 1903;
(h) J.M. Serrano-Becerra, D. Morales-Morales, Curr. Org. Synth. 6 (2009) 169;
(i) J.-L. Niu, X.-Q. Hao, J.-F. Gong, M.-P. Song, Dalton Trans. 40 (2011) 5135;
(j) N. Selander, K.J. Szabó, Chem. Rev. 111 (2011) 2048.
CCDC 883555–883562 contain the supplementary crystallo-
graphic data for compounds 2a,b, 4a,d, 5, and 6b–d. These data
can be obtained free of charge via http://www.ccdc.cam.ac.uk/con-
ts/retrieving.html, or from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223-
336-033; or e-mail: deposit@ccdc.cam.ac.uk. Supplementary data
associated with this article can be found, in the online version, at
http://dx.doi.org/10.1016/j.poly.2012.12.025.
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