Thiophosphoryl-Functionalized enaminoketones: Synthesis, structure, and complexing properties towards transition metal ions

Article abstract of DOI:10.1016/j.jorganchem.2013.12.010

P(X)-functionalized enaminoketones (X = O, S) 1a,b have been readily obtained by the condensation of o-(thio)phosphorylated anilines with sodium salt of benzoylacetaldehyde. The ligands derived exist in solution in the expected ketamino tautomeric form, b

Full text of DOI:10.1016/j.jorganchem.2013.12.010

Accepted Manuscript
(Thio)phosphoryl-functionalized enaminoketones: Synthesis, structure, and
complexing properties towards transition metal ions
Diana V. Aleksanyan, Valentina Yu. Aleksenko, Yulia V. Nelyubina, Zinaida S.
Klemenkova, Vladimir A. Kozlov
PII:
S0022-328X(13)00862-0
10.1016/j.jorganchem.2013.12.010
JOM 18395
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 1 October 2013
Revised Date: 4 December 2013
Accepted Date: 5 December 2013
Please cite this article as: D.V. Aleksanyan, V.Y. Aleksenko, Y.V. Nelyubina, Z.S. Klemenkova, V.A.
Kozlov, (Thio)phosphoryl-functionalized enaminoketones: Synthesis, structure, and complexing
properties towards transition metal ions, Journal of Organometallic Chemistry (2014), doi: 10.1016/
j.jorganchem.2013.12.010.
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ACCEPTED MANUSCRIPT
P(X)-modified enaminoketones as novel ligands

ACCEPTED MANUSCRIPT
X
O
( )n
O
N
N
PPh2
X
M
O
M = Cu, Ni
( )n
NH
O
PPh2
NH2
O
X
ONa
O
Ph
X = O, S; n = 0, 1
M = Pd, Re
Ln
N
M
O
Ph

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1
(Thio)phosphoryl-functionalized enaminoketones: Synthesis, structure, and complexing
properties towards transition metal ions
Diana V. Aleksanyan,* Valentina Yu. Aleksenko, Yulia V. Nelyubina, Zinaida S. Klemenkova,
Vladimir A. Kozlov
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul.
Vavilova 28, Moscow, 119991 Russia
*Corresponding author. Tel.: +7 499 135 9356; e-mail address: aleksanyan.diana@ineos.ac.ru
P(X)-functionalized enaminoketones (X=O, S) 1a,b have been readily obtained by the
condensation of o-(thio)phosphorylated anilines with sodium salt of benzoylacetaldehyde. The
ligands derived exist in solution in the expected ketamino tautomeric form, but, unlike typical
enaminoketones, tend to exist as cis-isomers in polar media, favored by the formation of the
strong P=O…HN intramolecular hydrogen bond. This six-membered hydrogen-bonded ring is
also observed in the solid structure of 1a, which, nevertheless, features a trans-configuration of
the enaminoketone fragment. Independent from the isomeric composition, the ligands obtained
readily form κ3-X,N,O (X = O, S) complexes with a range of transition metal ions (Re(I), Pd(II),
Cu(II), and Ni(II)) adopting in all cases the cis-configuration. The structures of the novel
compounds are confirmed using multinuclear NMR and IR spectroscopy as well as X-ray
crystallography.
Key words: Enaminoketones, Tridentate ligands, Transition metals, X-ray diffraction
1. Introduction
Enaminoketones bearing the N–R1C=CR2–CR3=O conjugated fragment (R1–3 = H, Alk, Ar)
are extensively studied as useful precursors in organic synthesis,1 especially for the creation of
various heterocycles,1c,2 and promising candidates in drug development.2b,3 Furthermore, these
readily available monoanionic bidentate chelating ligand systems, capable of forming
unsymmetrical metal complexes owing to the presence of different donor centers, are also of
unfailing interest in coordination and organometallic chemistry as convenient models for
investigation of metal binding modes,4 high-performance catalysts,5 CVD precursors4b,6 and so
on.7 Compared to bidentate ligands, the number of enaminoketones with an additional
coordination site, leading on complexation to tridentate structures, is rather limited,5g,j–l,6,8 being
represented for the most part by derivatives of 1,3-diketones. The structural features of these
ligands are poorly explored, although they may have a considerable impact on their complexing
features.

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Recently we have shown that o-(thio)phosphorylated anilines can be used as convenient
basic blocks for the synthesis of oligodentate ligands via simple modular assembling with a
range of carbonyl derivatives,9 affording P(X)-modified carbamoylmethylphosphine oxides and
sulfides10 and salicylaldimines11 which demonstrate interesting coordination behaviour upon
interaction with different metal precursors. The complexes obtained feature promising
catalytic11,12 and luminescent properties.13 Following up this project, it seems interesting to
involve o-(thio)phosphorylated anilines in the synthesis of P(X)-functionalized enaminoketones
using benzoylacetaldehyde as a carbonyl component.
Herein, we report on the synthesis of enaminoketones functionalized with (thio)phosphoryl
groups which serve as tridentate monoanionic ligands upon complexation with transition metals.
A special emphasis is placed on the structural peculiarities of the novel compounds both in
solution and in the solid state.
2. Results and Discussion
2.1. Synthesis and characterization of ligands
Target (thio)phosphorylated enaminoketones 1a,b have been readily obtained in good
yields by the condensation of sodium salt of benzoylacetaldehyde with o-(thio)phosphoryl-
substituted anilines in aqueous alcohol followed by treatment with acetic acid (Scheme 1).
(Thio)phosphorylated anilines, the key precursors, were synthesized according to the earlier
published procedures.10
Ph
Ph
Ph
P
Ph
X
P
O
X
CH3COOH
+
NH
O
Ph
ONa
NH2
Ph
X = O (1a) 78%
X= S (1b) 58%
Scheme 1. Synthesis of (thio)phosphoryl-functionalized enaminoketones 1a,b.
As is known, primary and secondary acyclic enaminoketones can undergo prototropic
rearrangements resulting in enolimino (I), ketamino (II), and ketimino (III) tautomeric forms
(Scheme 2). The spectral (NMR, UV-vis, IR) and X-ray diffraction studies for different
enaminoketones suggested that the ketamino form II describes the ground state of such
derivatives best of all.2b In the case of compounds 1a,b, the absence of an absorption band
corresponding to the enol hydroxyl group stretching vibrations in the IR spectra as well as the
absence of signals of the OH-group and methylene unit protons in the 1H NMR spectra also give

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evidence of the ketamino tautomeric form both in solution and in the solid state. Note that the
related phosphine-substituted derivative exists in the ketimino tautomeric form.5g,8a
R1
R1
R1
N
OH
NH
O
N
O
R2
R2
R2
I
II
III
Scheme 2.
Furthermore, owing to the restricted rotation around the C=C double bond, enaminoketones
can exist as two geometric isomers (Scheme 3).
R1 NH
H
O
R2
R1
N
C(O)R2
Z
E
Scheme 3.
The interconversion between cis- and trans-forms in solution is facilitated by the
conjugation of the system and, in the case of enaminoketones 1a,b, additionally by the absence
of a bulky substituent at the NH–C carbon atom. As a rule, apolar media favor the formation of
the cis-isomer, which is stabilized by the intramolecular hydrogen bond, while in polar solvents,
capable of forming intermolecular hydrogen bonds, a contribution of the trans-form enhances.
However, the introduction of the ancillary (thio)phosphoryl groups completely changes this
tendency (Table 1). According to the NMR spectral data, a mixture of both geometric isomers of
enaminoketones 1a,b is observed in solvents of various polarity (CDCl3, CD3OD and (CD3)2SO).
This can be readily deduced from the characteristic signal patterns in their 1H NMR spectra (see
1
Table 1 and the experimental section). Thus, the H NMR spectra of 1a,b show two doublet
signals of the HC–C(O) group proton at 5.71–6.03 and 6.23–6.60 ppm with the corresponding
coupling constants of 7.5–8.4 and 12.5–12.8 Hz, which can be related to the cis- and trans-
isomers, respectively. Moreover, a pair of doublet signals is observed also for the NH-protons: at
10.04–10.98 (trans-form) and 11.82–12.79 (cis-form) ppm. Although the assignment of signals
of the second methine proton in the case of cis-isomers is complicated by overlapping with the
aromatic resonances, the signals of the N–CH fragment proton corresponding to the trans-isomer
can be readily identified as virtual triplets at ca. 8 ppm. Therewith, the high values of 3JHH (11.3–
13.3 Hz) evidence for a transoid arrangement of the NH and N–CH protons in all cases. Note
that due to a rapid and complete H/D exchange in CD3OD, the signals of the acidic NH-protons
were not detected and those of the N–CH group proton converted into doublets. The 31P NMR
1
spectra of 1a,b demonstrate two singlet signals. According to the isomer ratios in the H NMR

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spectra, the lower field signals (in the range of 29.9–33.8 for 1a and 38.5–39.3 ppm for 1b) were
attributed to the cis-form, while the higher field ones (35.3–38.3 (1a) and 38.9–39.7 (1b) ppm)
were assigned to the trans-form. The high field resonances of the NH-protons of both isomeric
forms in the 1H NMR spectra of 1a,b imply the involvement of these H-atoms in hydrogen bonds
in all cases (compare 10–13 ppm for compounds 1a,b with typical values of 4–8 ppm2b). Taking
this into account, a difference in the chemical shifts of the phosphorus atoms for the cis- and
trans-forms can be tentatively explained by the different hydrogen bonding patterns, which are
likely to involve the (thio)phosphoryl group only in the case of the trans-form and carbonyl
group in addition to the (thio)phosphoryl one in the case of the cis-form (bifurcated hydrogen
bond). Thus, the P=O...HN hydrogen-bonded ring seems to be a key structural feature of these
systems. Unlike typical enaminoketones, the cis-forms of compounds 1a,b predominate over the
expected trans-isomers in polar media (Table 1). Presumably, the introduction of the
(thio)phosphoryl group, acting as the hydrogen bond donor, leads to the higher polarization of
the carbonyl group compared to nonfunctionalized enaminoketones, and this effect is more
pronounced for the cis-form, which may explain the stability of cis-isomers of 1a,b,2 in polar
media. As for apolar media, the trans-isomer of P(O)-substituted enaminoketone 1a appeared to
be more stable in chloroform and even in benzene,1 while both geometric isomers of its
thiophosphorylated analog 1b are present in almost equal amounts (Table 1). Interestingly, in the
case of P(O)-substituted enaminoketone 2 with the elongated phosphoryl arm, which was
synthesized in a similar manner starting from 2-[(diphenylphosphoryl)methyl]aniline,14 the cis-
isomer prevail both in polar and apolar media. Apparently, these results, being in contradiction
with the known examples, require further investigations.
O
PPh2
NH
O
Ph
2
Table 1. Selected NMR spectral data of compounds 1a,b,2
Compound Solvent
1H NMR: δ/ppm (3JHH/Hz)
HC–C(O) NH
31P{1H} NMR:
δ/ppm (content/%)
1
The contents of cis- and trans-isomers of enaminoketone 1a in C6D6 comprise 15 and 85%,
respectively.

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5
cis
trans
cis
trans
cis
trans
CDCl3
(CD3)2SO
CD3OD
31.10 (25) 37.60 (75) 5.99 (8.4)
29.85 (70) 35.30 (30) 6.03 (8.4)
33.77 (85) 38.34 (15) 5.90 (8.4)
6.60 (12.8)
6.60 (12.6)
6.47 (12.5)
12.79 (13.3) 10.94 (12.8)
12.45 (12.1) 10.98 (13.2)
1a
1b
2
n/o
n/o
CDCl3
(CD3)2SO
CD3OD
38.93 (45) 39.65 (55) 5.71 (8.2)
38.49 (84) 38.85 (16) 5.92 (7.5)
39.27 (82) 39.81 (18) 5.74 (8.2)
6.35 (12.7)
6.42 (12.8)
6.23 (12.8)
11.82 (11.3) 10.04 (12.7)
11.81 (12.3) 9.71 (12.8)
n/o
n/o
CDCl3
(CD3)2SO
CD3OD
29.42 (73) 35.81 (27) 5.87 (7.6)
29.09 (60) 33.07 (40) 6.11 (7.8)
33.51 (74) 36.77 (26) 6.07 (7.7)
6.55 (12.6)
6.44 (12.5)
6.55 (12.1)
12.41 (11.5) 10.29 (br s)
12.37 (12.2) 10.30 (8.9)
n/o
n/o
n/o not observed
The IR spectra of solid samples of enaminoketones 1a,b,2 (KBr pellets) show the
characteristic absorption bands of the P=X group stretching vibrations at 1184–1197 (X = O) and
637 cm–1 (X = S), intensive absorption bands of the C=C and C=O bonds at 1541–1583 and
1617–1654 cm–1, respectively, and the low-intensity absorption bands in the range of 3150–3250
cm–1 typical for the NH group stretching vibrations.
The X-ray diffraction data for ligand 1a showed that the intramolecular hydrogen bond
between the P=O and N–H groups, assumed in solution, is indeed realized in the crystalline state
(N…O 2.7525(16) Å, NHO 147(1)°), while the enaminoketone moiety adopted the trans-
configuration (Fig. 1, Tables A. 1 and 2 in supplementary material). This confirms an essential
role of the phosphoryl pendant arm in the structural features of these systems. Note that the
molecule of 1a has high planarity: both benzene rings at the ends of the enaminoketone fragment
do not significantly deviate from its mean plane (the corresponding dihedral angles are 9.9(2)°
and 8.1(2)° for the C(1)–C(6) and C(10)–C(15) rings, respectively. In a crystal, the molecules of
1a are assembled into a 3D-framework through a series of weak intermolecular interactions.
Those include C–H…O, C–H…π, and π…π contacts with the shortest C…O and C…C
separations being 3.289(1), 3.758(1), and 3.212(1) Å, respectively.

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Fig. 1 General view of ligand 1a in representation of atoms via thermal ellipsoids (p = 50%).
Dashed line represents the hydrogen bond.
2.2. Synthesis and characterization of complexes
Independent from the isomeric composition, enaminoketones 1a,b,2 readily form
complexes with a range of transition metal ions, serving in all cases as tridentate monoanionic
ligands, i.e., adopting the cis-configuration. Thus, the reaction of 1a,b and 2 with rhenium
pentacarbonyl bromide in toluene solution under reflux in the presence of Et3N proceeds as the
metallation at the amide nitrogen atom accompanied by the coordination of carbonyl and
(thio)phosphoryl groups to give κ3-X,N,O (X = O, S) complexes 3a,b and 4 in high yields (83–
88%) (Scheme 4). Of note is the ease of formation of complex 4 bearing fused six- and seven-
membered metallocycles. The cyclopalladation of thiophosphoryl-substituted enaminoketone 1b
can be readily accomplished under action of (PhCN)2PdCl2 in dichloromethane solution at room
temperature. The yield of complex 5 (70%) is good enough compared to other hybrid palladium
pincer complexes bearing the oxygen donor centers and having two fused six-membered
metallocycles.10 Finally, the interaction of phosphorylated enaminoketones 1a and 2 with copper
and nickel acetates in alcohol solution under reflux afforded κ3-O,N,O complexes 6–8 of (L–
H)2M composition in 75–95% yields. Note that the synthesis of Cu(II) complexes 6,7 was
accomplished only in the presence of triethylamine, while Ni(II) complex 8 can be smoothly
obtained in the absence of a base.

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Ph
O
Ph
Ph Ph
( )n
X
( )n
( )n
Ph
M
P
P
PPh2
X
O
Ln
[M]
[M]/Et3N
N
N
M
NH
O
O
O
N
O
P
Ph
( )n
Ph
Ph
Ph
Ph
1a,b,2
M = Re, Ln=(CO)3:
M = Cu:
n = 0, X = O (3a) 88%
n = 0, X = S (3b) 83%
n = 1, X = O (4) 88%
M = Pd, L = Cl:
n = 0, X = O (6) 88%
n = 1, X = O (7) 95%
M = Ni:
n = 0, X = O (8) 75%
n = 0, X = S (5) 70%
Scheme 4. Synthesis of transition metal complexes
of (thio)phosphorylated enaminoketones 1a,b,2.
The complexes obtained are yellow (3a,b,4,8), red (5), and green (6,7) crystalline solids,
thermally stable up to 150ºC as well as air and moisture resistant. The realization of κ3-X,N,O (X
= O, S) coordination was deduced from the multinuclear NMR (1H and 31P) and IR spectral data
as well X-ray diffraction analysis. Thus, a shift of the phosphorus resonances in the 31P NMR
spectra of Re(I) and Pd(II) complexes 3–5 compared to the signals of the free ligands
unequivocally confirms the coordination of the (thio)phosphoryl groups. Therewith, the value of
ꢀδP and direction of the shift depend on the substituent X in the P=X moiety and nature of metal
ion and deuterated solvent (downfield shift by 7.7–11.0 ppm for P(O)-functionalized complexes
and upfield or downfield shift by 0.4–2.4 ppm in the case of phosphine sulfide derivatives).
Although Cu(II) and Ni(II) complexes 6–8 are paramagnetic (no NMR spectra were observed),
the coordination of (thio)phosphoryl groups in these particular cases as well as for the other
complexes is supported by the lower frequency displacement of absorption bands corresponding
to the P=X bond stretching vibrations in the IR spectra, comprising 10–76 cm–1 and 33–37 cm–1
for phosphoryl- and thiophosphoryl-containing metallocycles, respectively. The absence of both
1
NH-group proton signals in the H NMR spectra of compounds 3–5 and absorption bands at
3100–3200 cm–1 in the IR spectra of all the complexes confirm the occurrence of metallation at
the amide nitrogen atom. Furthermore, a strong bathochromic shift of the C=O group stretching
vibrations (ꢀ = 35–65 cm–1) accompanied by the concomitant low-frequency displacement of the
C=C bond absorption bands (ꢀ = 27–71 cm–1) evidences for the coordination of the
enaminoketone moiety. The coordination of the N–CH=CH–C=O fragment is also reflected in
the 1H NMR spectra of complexes 3–5 by the downfield shift of the HC–C(O) and N–CH proton
signals with transformation of the latter into doublets (see the experimental section). The 13C
NMR spectra of complexes 3–5 also fit well the suggested structures. It is worth mentioning that
compounds 3a,b and 4 form stable atropisomers in solution at room temperature (evidenced by
separation of the signals of prochiral groupings) like the related Re(I) complexes of P(X)-

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modified (X = O, S) carbamoylmethylphosphine oxides and sulfides.10 The identity of the
complexes derived was also supported by the elemental analysis data.
The single-crystal X-ray diffraction experiments performed for complexes 3a, 3b, 5, and 6
also confirm the realization of κ3-X,N,O-coordination (X = O, S) of the deprotonated ligand form
in all cases (Figs 2–5). The complexation is accompanied by the expected changes in the
geometry of P(X)-modified enaminoketones (see Table A. 1 in supplementary material for the
selected bond lengths and angles). Thus, the P=O bond lengthens from 1.4995(10) Å in 1a to
1.514(2) Å in its rhenium complex 3a, although no elongation is observed for its copper
counterpart 6 (vide infra). The covalent bonds in the N–CH=CH–C=O fragment of 3a and 6
become alternatively shorter/longer compared to 1a, indicating the delocalization of the negative
charge over the deprotonated enaminoketone backbone (Table A. 1). In complexes 3b and 5, the
main bond lengths are also within the normal values. The coordination also affects the molecule
planarity: the dihedral angles between the C(1)–C(6) and C(10)–C(15) benzene rings and the
enaminoketone moiety increases to 27.5(2)–60.5(5)° and 12.6(6)–29.1(2)°, respectively.
In both of the rhenium complexes 3a and 3b, the metal atom has nearly ideal octahedral
environment. Palladocycle 5 features the square-planar geometry around the metal center. The
copper ion in 6 has a coordination mode of [4+2] formed by two symmetry-equivalent O(2) and
N(1) atoms (as there is an inversion center at the position of the metal atom) in a nearly ideal
square-planar environment and additionally by two O(1) atoms with the resulting Cu–O line
almost perpendicular to this plane (83.4(2)°). Therewith, the Cu–O distances for the oxygen
atoms in the equatorial and axial positions are 1.9490(11) and 2.4580(11) Å, respectively. Note
that the P=O bond was unexpectedly shorter than that in the free ligand (1a) (1.4988(11) and
1.4995(10) Å, respectively), suggesting that the Cu(1)–O(1) bond is weaker than the
intramolecular hydrogen bond in 1a.
The conformations of the resulting metallocycles vary from a flattened envelope (C(O)-
containing metallocycle in 3b) to a distorted boat (P(S)-containing metallocycle in 5). Among all
the complexes X-rayed in this study, those with palladium and copper were obtained as
crystallosolvates with Et2O and CHCl3 (5) and methanol (6). In the latter case (Fig. 5), the
solvate molecule forms rather strong hydrogen bond with the phosphoryl group (O…O
2.7796(17) Å, OHO 167(1)°) (Table A. 2). This is the strongest intermolecular interaction in the
crystals of 3a, 3b, 5, and 6; others include C–H…O, C–H…π, and π…π (3a), or O…π (3b), or
Cl… π and C–H…Cl (5).

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9
Fig. 2. General view of complex 3a in representation of atoms by thermal ellipsoids (p = 50%).
Hereinafter, the H(C) atoms are omitted for clarity.
Fig. 3. General view of complex 3b in representation of atoms by thermal ellipsoids (p = 50%).
Fig. 4. General view of complex 5 in representation of atoms by thermal ellipsoids (p = 50%).
Solvate Et2O and CHCl3 molecules are not shown.

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10
Fig. 5. General view of complex 6 in representation of atoms by thermal ellipsoids (p = 50%).
Dashed line represents the hydrogen bond.
3. Conclusions
Simple condensation of o-(thio)phosphorylated anilines with sodium enolate of
benzoylacetaldehyde afforded novel oligodentate ligands, namely, P(X)-functionalized
enaminoketones (X=O, S). The compounds obtained show interesting structural behavior both in
solution and in the solid state and readily form stable complexes with a range of transition metal
ions (Re(I), Pd(II), Cu(II), and Ni(II)), adopting in all cases X,N,O-coordination mode (X = O,
S).
4. Experimental
4.1. General remarks
All manipulations were carried out without taking precautions to exclude air and moisture.
Dichloromethane was distilled from P2O5. 2-(Diphenylphosphoryl)aniline and its thioanalog
were obtained from 2-diphenylphosphinoaniline according to the literature procedures.10 2-
[(Diphenyl)phosphorylmethyl]aniline was derived by the reduction of the nitro-substituted
predecessor easily available, in turn, by the Arbuzov reaction between o-nitrobenzyl bromide
and Ph2POEt.14 Benzoylacetaldehyde sodium salt was synthesized by the Claisen condensation
of acetophenone with ethyl formate under action of sodium ethoxide analogous to the procedure
described in ref.15 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 (δ) were internally referenced by the residual solvent signals relative to
tetramethylsilane (1H and 13C) or externally to H3PO4 (31P). For simplicity, the integral

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intensities of the proton signals for the trans- and cis-isomers of ligands 1a,b,2 in the description
of the 1H NMR spectral data are given irrespective of the real contents of the isomers, which, in
turn, can be found in Table 1. The 13C NMR spectra were registered using the JMODECHO
mode; the signals for the C atoms bearing odd and even numbers of protons have opposite
1
polarities. The numeration of carbon atoms of the central benzene ring in the descriptions of H
and 13C NMR spectral data for ligands 1a,b,2 and complexes 3–5 is in agreement with IUPAC
nomenclature for the ligands. The same principle of numbering was used to describe 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 Nicolet Magna-IR750 FT-spectrometer, resolution 2 cm–
1, 128 scans. The assignment of absorption bands in the IR spectra was made according to ref.16
Melting points were determined with a MPA 120 EZMelt Automated Melting Point Apparatus
and were uncorrected.
4.2. General procedure for the synthesis of (thio)phosphorylated enaminoketones 1a,b
A solution of sodium enolate of benzoylacetaldehyde (1.30 g, 7.65 mmol) in 20 mL of
water was added to a stirred solution of the corresponding aniline (7.65 mmol) in 30 mL of
Н2О/С2Н5ОН (1:1) mixture. The resulting reaction mixture was treated with acetic acid (1.38 g,
23.0 mmol), and the desired product was extracted with dichloromethane. The organic phase was
separated, dried over anhydrous Na2SO4, evaporated to dryness, and purified by silica gel
column chromatography (eluent СНСl3 (1a), CH2Cl2/hехane (20:1) (1b)) to give
enaminoketones 1a,b as yellow crystalline solids.
4.2.1. 3-{[2-(Diphenylphosphoryl)phenyl]amino}-1-phenylprop-2-en-1-one 1а
Yield: 2.52 g (78%). Mp: 201–202°С. 31P{1H} NMR (121.49 MHz, CDCl3, δ/ppm): 31.10
1
(25%, cis), 37.60 (75%, trans). H NMR (300.13 MHz, CDCl3, δ/ppm, J/Hz): δ 5.99 (d, 1Н,
3
3
HC–C(O) (cis), JHH = 8.4), 6.60 (d, 1Н, HC–C(O) (trans), JHH = 12.8), 6.98–7.10 (m, 3Н, HAr
(1H (cis) + 2H (trans))), 7.15–7.26 (m, 2Н, HAr (cis)), 7.28–7.34 (m, 1Н, HAr (cis)), 7.43–7.59
(m, 10Н, HAr (6H (cis) +4H (trans))), 7.63–7.73 (m, 16Н, HAr (10H (trans) + 6H (cis))), 7.77–
7.83 (m, 3H, HAr (2H (cis) + 1H (trans))), 7.97–8.02 (m, 4H, HAr (2H (cis) + 2H (trans))), 8.30
3
3
(vt, 1Н, N–CH (trans), JHH = 12.8), 10.94 (d, 1Н, NH (trans), JHH = 12.8), 12.79 (d, 1Н, NH
3
(cis), JHH = 13.3 Hz). IR (KBr, ν/cm–1): 514(m), 544(s), 665(w), 697(m), 711(w), 724(m),
744(m), 755(w), 783(w), 813(w), 890(w), 981(w), 1000(vw), 1023(w), 1038(w), 1065(vw),
1074(vw), 1094(vw), 1117(m), 1129(w), 1145(w), 1158(w), 1167(w), 1177(w), 1197(m)
(ν(Р=О)), 1223(w), 1265(s), 1293(m), 1308(m), 1437(m), 1455(m), 1526(w), 1553(s) (ν(С=С)),
1583(m), 1606(m), 1654(s) (ν(С=О)), 3052(w), 3152(w), 3203(w), 3254(br, vw) (both ν(NH)).
Anal. Calcd for C27H22NO2P: C, 76.58; H, 5.24; N, 3.31. Found: C, 76.56; H, 5.31; N, 3.22%.

ACCEPTED MANUSCRIPT
12
4.2.2. 3-{[2-(Diphenylthiophosphoryl)phenyl]amino}-1-phenylprop-2-en-1-one 1b
31
Yield: 1.95 g (58%). Mp: 148–150°С. P{1H} NMR (161.98 MHz, CDCl3, δ/ppm): 38.93
1
(45%, cis), 39.65 (55%, trans). H NMR (400.13 MHz, CDCl3, δ/ppm, J/Hz): 5.71 (d, 1Н, HC–
C(O) (cis), 3JHH = 8.2), 6.35 (d, 1Н, HC–C(O) (trans), 3JHH = 12.7), 6.76 (dd, 1Н, Н(С3) (trans),
3
3
3
3JHH = 7.7, JHP = 14.7), 6.91 (dd, 1H, N–CH (cis), JHH = 8.2, JHH = 11.3), 6.97 (t, 1Н, HAr
(trans), 3JHH = 7.5), 7.03–7.04 (m, 2Н, HAr (cis)), 7.20 (dd, 1Н, Н(С6) (trans), 3JHH = 7.8, 4JHP
5.2), 7.34–7.56 (m, 21H, HAr (11H (cis) + 10H (trans))), 7.68 (dd, 4Н, o-Н in P(S)Ph2 (trans),
=
3
3
3JHH = 7.7, JHP = 13.8), 7.80 (d, 2H, o-H in C(O)Ph (cis), JHH = 7.7), 7.85 (dd, 4Н, o-Н in
3
3
P(S)Ph2 (cis), JHH = 7.4, 3JHP = 13.7), 7.88 (d, 2H, o-H in C(O)Ph (trans), JHH = 7.5), 7.99 (vt,
1Н, N–CH (trans), 3JHH = 12.7), 10.04 (d, 1Н, NH (trans), 3JHH = 12.7), 11.82 (d, 1Н, NH (cis),
3JHH = 11.3). IR (KBr, ν/cm–1): 520(m), 614(w), 637(m) (ν(P=S)), 688(m), 713(m), 718(m),
739(w), 760(m), 819(vw), 992(w), 1021(m), 1040(w), 1065(w), 1094(m), 1145(w), 1179(w),
1210(m), 1232(s), 1274(m), 1278(m), 1351(w), 1437(s), 1454(s), 1482(w), 1499(w), 1541(s)
(ν(C=C)), 1567(m), 1580(s), 1597(w), 1617(m) and 1627(s) (both ν(С=О)), 2851(vw), 2920(w),
3063(w), 3153(br, vw) (ν(NH)). Anal. Calcd for C27H22NOPS: C, 73.78; H, 5.05; N, 3.19.
Found: C, 73.69; H, 5.04; N, 3.14%.
4.3. Synthesis of 3-({2-[(diphenylphosphoryl)methyl]phenyl}amino)-1-phenylprop-2-en-1-
one 2
A solution of 2-[diphenylphosphoryl)methyl]aniline (2.53 g, 8.24 mmol) in chloroform (20
mL) was saturated with HCl. The solvent was removed in vacuo to give crude 2-
[(diphenylphosphoryl)methyl]anilinium chloride in quantitative yield.
A
solution of
benzoylacetaldehyde sodium salt (1.40 g, 8.24 mmol) in 20 mL of water was added to a stirred
solution of the above salt in 30 mL of Н2О/С2Н5ОН (1:1) mixture. The resulting precipitate was
filtered off and purified by silica gel column chromatography (eluent: СНСl3/acetone (20:1)) to
give 2.88 g of 2 as a yellow crystalline solid. Yield: 80%. Mp: 210–212°С. 31P{1H} NMR
1
(161.98 MHz, CDCl3, δ/ppm): 29.42 (73%, cis), 35.81 (27%, trans). H NMR (400.13 MHz,
2
2
CDCl3, δ/ppm, J/Hz): δ 3.71 (d, 2H, CH2 (trans), JHP = 13.2), 3.77 (d, 2H, CH2 (cis), JHP
=
13.3), 5.87 (d, 1Н, HC–C(O) (cis), 3JHH = 7.6), 6.55 (d, 1Н, HC–C(O) (trans), 3JHH = 12.6), 6.71
(d, 1H, H(C6) (trans), 3JHH = 7.3), 6.84 (t, 1H, H(C4) (trans), 3JHH = 7.4), 6.99–7.08 (m, 3Н, HAr
(cis)), 7.18–7.28 (m, 3Н, HAr (trans)), 7.35–7.57 (m, 19Н, HAr (11H (cis) + 8H (trans))), 7.71
3
3
(dd, 4Н, o-Н in P(O)Ph2 (trans), JHH = 7.6, JHP = 11.6), 7.79 (dd, 4Н, o-H in P(O)Ph2 (cis),
3
3JHH = 7.7, JHP = 11.5), 7.94–7.97 (m, 4Н, HAr (2H (cis) + 2H (trans))), 8.11 (vt, 1Н, N–CH
(trans), 3JHH = 12.6), 10.29 (br s, 1Н, NH (trans)), 12.41 (d, 1Н, NH (cis), 3JHH = 11.5). IR (KBr,
ν/cm–1): 513(w), 523(w), 594(w), 694(m), 721(m), 741(w), 745(m), 751(m), 771(w), 850(w),
859(w), 1020(w), 1043(w), 1071(w), 1105(w), 1120(w), 1184(m) (ν(Р=О)), 1240(m), 1285(m),

ACCEPTED MANUSCRIPT
13
1359(w), 1437(m), 1465(m), 1491(w), 1507(w), 1559(m), 1589(m) (ν(С=С)), 1604(w), 1631(s)
(ν(С=О)), 2941(w), 3053(w), 3209(br, vw) (ν(NH)). Anal. Calcd for C28H24NO2P: C, 76.87; H,
5.53; N, 3.20. Found: C, 76.94; H, 5.45; N, 3.16%.
4.4. General procedure for the synthesis of Re(I) complexes 3a,b,4
A solution of Re(CO)5Br (60 mg, 0.148 mmol), triethylamine (21 µL, 0.148 mmol), and
the corresponding ligand (0.148 mmol) in 10 mL of toluene was refluxed for 1.5 h. After cooling
to room temperature, the solvent was removed in vacuo, and the residue was purified by silica
gel column chromatography (eluent СН2Cl2 (3a,b), CHCl3 (4)) to give complexes 3a,b,4 as
yellow crystalline solids.
4.4.1. [κ3-O,N,O-(L–H)Re(I)] 3a
Yield: 90 mg (88%). Mp: >260°С (decomp.). 31Р{1H} NMR (161.98 MHz, CDCl3, δ/ppm):
42.13. 1Н NMR (400.13 MHz, CDCl3, δ/ppm, J/Hz): 5.38 (d, 1Н, HС–С(O), 3JHH = 6.6), 7.00 (d,
3
3
3
1Н, N–CH, JHH = 6.6), 7.02 (dd, 1H, H(C3), JHH = 7.4, JHP = 13.7), 7.14 (dt, 2Н, m-H in
3
4
3
4
P(O)Ph, JHH = 7.7, JHP = 3.5), 7.22 (dt, 1H, H(C4), JHH = 7.4, JHP = 3.1), 7.27–7.33 (m, 3Н,
HAr), 7.36–7.47 (m, 4Н, HAr), 7.56 (dt, 2Н, m-H in P(O)Ph, 3JHH=7.8, 4JHP = 3.4), 7.66–7.71 (m,
3
4Н, HAr), 7.82 (d, 2Н, o-H in C(O)Ph, JHH=7.6). 13С{1H} NMR (100.61 MHz, CDCl3, δ/ppm,
3
3
J/Hz): 95.48 (s, HC–C(O)), 120.65 (d, С6, JС = 6.9), 124.77 (d, С4, JС = 13.1), 127.03 (d,
P
P
ipso-С in P(O)Ph, 1JСP = 112.4), 127.14 (s, m-С in C(O)Ph), 127.33 (d, С2, 1JСP = 105.5), 128.06
(s, о-С in C(O)Ph), 128.38 (d, ipso-С in P(O)Ph, 1JСP = 114.1), 128.53 (d, m-С in P(O)Ph, 3JС
=
P
3
13.1), 128.98 (d, m-С in P(O)Ph, JС = 12.7), 130.38 (s, p-С in C(O)Ph), 131.41 (d, о-С in
P
2
2
4
P(O)Ph, JС = 10.7), 132.03 (d, С3, JС = 11.0), 132.26 (d, p-С in P(O)Ph, JС = 3.1), 132.50
P
P
P
(d, о-С in P(O)Ph, 2JСP = 10.7), 133.33 (d, p-С in P(O)Ph, 4JСP = 2.7), 134.57 (d, С5, 4JСP = 2.1),
2
138.80 (s, ipso-С in C(O)Ph), 158.87 (s, N–CH), 160.19 (d, С1, JС = 2.7), 177.29 (s, С=О),
P
196.99 (s, СО), 197.89 (s, 2СО). IR (КBr, ν/cm–1): 529(w), 545(m), 563(m), 691(m), 712(m),
731(m), 746(w), 758(w), 767(w), 838(w), 945(w), 999(w), 1026(w), 1068(m), 1088(w), 1121(m)
and 1131(m) (both ν(P=O)), 1184(w), 1260(w), 1278(w), 1308(w), 1340(s), 1409(s), 1441(m),
1452(m), 1460(m), 1484(m), 1514(s) (ν(С=С)), 1562(m), 1570(m), 1590(m) (С=О), 1864(vs)
(ν(CO)), 1892(vs) (ν(CO)), 2011(vs) (ν(СО)), 3076(vw). Anal. Calcd for С30Н21NO5PRe: С,
52.02; Н, 3.06; N, 2.02. Found: С, 52.17; Н, 2.96; N, 1.81%.
4.4.2. Complex 3b
Yield: 90 mg (83%). Mp: >232°С (decomp.). 31Р{1H} NMR (161.98 MHz, (CD3)2SO,
1
3
δ/ppm): 38.88. Н NMR (400.13 MHz, (CD3)2SO, δ/ppm, J/Hz): 5.10 (d, 1Н, HС–С(O), JHH
=
6.6), 6.80 (d, 1Н, N–CH, 3JHH = 6.6), 6.96 (dd, 1Н, Н(С3), 3JHH = 7.6, 3JHP = 14.2), 7.27 (dt, 2Н,
m-H in P(S)Ph, 3JHH = 7.8, 4JHP = 3.6), 7.35–7.56 (m, 8Н, HAr), 7.64 (d, 2Н, o-H in C(O)Ph, 3JHH
= 7.7), 7.69–7.72 (m, 4Н, HAr), 7.77–7.86 (m, 2Н, HAr). 13С{1H} NMR (75.47 MHz, CDCl3,

ACCEPTED MANUSCRIPT
14
3
3
δ/ppm, J/Hz): 95.19 (s, HC–C(O)), 122.33 (d, С6, JС = 6.9), 124.84 (d, С4, JС = 12.5),
P
P
1
126.37 (d, ipso-С in P(S)Ph2, JС = 85.8), 127.11 (s, m-С in C(O)Ph), 127.98 (s, о-С in
P
C(O)Ph), 128.67 (d, С2, 1JСP = 86.5), 128.79 (d, m-С in P(S)Ph, 3JСP = 13.8), 129.00 (d, m-С in
3
2
P(S)Ph, JС = 12.5), 130.26 (s, p-С in C(O)Ph), 131.81 (d, С3, JС = 6.2), 131.93 (d, о-С in
P
P
P(S)Ph, 2JРС = 11.1), 132.16 (d, p-С in P(S)Ph, 4JCP = 3.0), 133.00 (d, p-С in P(S)Ph, 4JCP = 2.7),
2
133.23 (d, о-С in P(S)Ph, JС = 10.4), 134.73 (s, С5), 138.98 (s, ipso-С in C(O)Ph), 159.00 (d,
P
2
С1, JCP = 2.6), 159.98 (s, N–CH), 177.81 (s, С=О), 194.05 (s, СО), 194.35 (s, СО), 195.56 (s,
СО). IR (КBr, ν/cm–1): 485(w), 513(w), 525(w), 600(m) (ν(P=S)), 620(w), 651(w), 690(m),
707(m), 749(w), 768(w), 838(w), 998(w), 1024(w), 1070(w), 1100(w), 1107(w), 1125(w),
1158(w), 1185(w), 1254(w),1310(w), 1339(s), 1411(s), 1438(m), 1454(s), 1484(m), 1514(s)
(ν(С=С)), 1563(m), 1571(m), 1592(m) (ν(С=О)), 1891(vs) (ν(CO)), 1903(vs) (ν(CO)), 2011(vs)
(ν(СО)), 2922(vw), 3056(vw). Anal. Calcd for С30Н21NO4PReS·0.25 СН2Cl2: С, 49.77; Н, 2.97
N, 1.92. Found: С, 49.88; Н, 2.62; N, 1.80%.
4.4.3. Complex 4
Yield: 92 mg (88%). Mp: >248°С (decomp.). 31Р{1H} NMR (161.98 MHz, CDCl3, δ/ppm):
37.21. 1Н NMR (400.13 MHz, CDCl3, δ/ppm, J/Hz): 3.39 (dd, 1H, CH2, 2JHH = 15.4, 2JHP = 6.6),
2
2
3
3.80 (dd, 1H, СН2, JHH = 15.4, JHP = 20.1), 5.90 (d, 1Н, HС–С(O), JHH = 6.7), 7.04 (t, 1Н,
3
3
3
H(C4), JHH = 7.4), 7.11 (d, 1Н, H(C6), JHH = 7.6), 7.17 (d, 1Н, H(C3), JHH = 7.4), 7.30–7.34
(m, 3Н, HAr), 7.41–7.52 (m, 7Н, HAr), 7.54–7.64 (m, 3Н, HAr), 7.82 (dd, 2Н, o-Н in P(O)Ph, 3JHH
3
3
= 8.4, JHP = 11.9), 7.99 (d, 2Н, o-H in C(O)Ph, JHH = 7.7). 13С{1H} NMR (100.61 MHz,
1
4
CDCl3, δ/ppm, J/Hz): 35.80 (d, СН2, JС = 62.7), 93.92 (s, HC–C(O)), 123.74 (d, С6, JС
=
P
P
2
1
2.3), 124.35 (d, C2, JС = 8.3), 125.63 (s, С5), 126.13 (d, ipso-С in P(O)Ph, JС = 101.2),
P
P
127.05 (s, m-С in C(O)Ph), 128.08 (s, о-С in C(O)Ph), 128.73 (d, С4, 4JСP = 3.0), 128.88 (d, m-С
3
3
in P(O)Ph, JС = 12.1), 129.12 (d, m-С in P(O)Ph, JС = 12.1), 130.02 (d, ipso-С in P(O)Ph,
P
P
2
1JCP = 109.5), 130.03 (s, p-C in C(O)Ph), 130.32 (d, о-С in P(O)Ph, JСP = 10.6), 130.63 (d, С3,
3JСP = 7.6), 131.66 (d, о-С in P(O)Ph, 2JСP = 9.8), 132.67 (d, p-С in P(O)Ph, 4JCP = 2.3), 132.25
4
3
(d, p-С in P(O)Ph, JС = 3.0), 139.42 (s, ipso-С in C(O)Ph), 157.37 (d, С1, JС = 4.5), 158.16
P
P
(s, N–CH), 175.06 (s, С=О), 196.28 (s, СО), 199.02 (s, СО), 199.08 (s, СО). IR (КBr, ν/cm–1):
497(w), 536(w), 563(w), 692(m), 707(w), 715(w), 747(m), 759(w), 819(w), 997(w), 1025(w),
1073(w), 1098(w), 1121(m), 1142(m) and 1160(m) (both ν(Р=О)), 1248(w), 1361(m), 1401(m),
1415(m), 1439(m), 1456(m), 1481(s), 1518(s) (ν(С=С)), 1571(m), 1593(m) (ν(С=О)), 1862(vs)
(ν(СО)), 1875(vs) (ν(СО)), 1888(vs) (ν(CO)), 1900(s) (ν(СО)), 2007(vs) (ν(СО)), 2914(vw),
3060(vw). Anal. Calcd for С31Н23NO5PRe:·С, 52.69; Н, 3.28 N, 1.98. Found: С, 52.64; Н, 3.20;
N, 1.91%.
4.5. Synthesis of Pd(II) complex 5

ACCEPTED MANUSCRIPT
15
A solution of (PhCN)2PdCl2 (66 mg, 0.172 mmol) in 5 mL of dichloromethane was slowly
dropwise added to a solution of 1b (76 mg, 0.172 mmol) and triethylamine (24 ꢁL, 0.172 mmol)
in 5 mL of CH2Cl2. The resulting reaction mixture was left under ambient conditions for 12 h,
then the solvent was removed in vacuo, and the residue was purified by silica gel column
chromatography (eluent CH2Cl2) to give 52 mg of complex 5 as a red crystalline solid. Yield: 70
1
mg (70%). Mp: >178°С (decomp.). 31Р{1H} NMR (161.98 MHz, CDCl3, δ/ppm): 36.58. Н
3
NMR (400.13 MHz, CDCl3, δ/ppm, J/Hz): 5.76 (d, 1Н, HC–С(O), JHH = 7.2), 6.53 (d, 1Н, N–
3
3
3
3
CH, JHH = 7.2), 6.84 (dd, 1Н, Н(С3), JHH = 7.7, JHP = 15.1), 6.95 (dd, 1Н, Н(С6), JHH = 7.8,
4JHP = 6.1), 7.17 (m, 1Н, НAr), 7.31–7.34 and 7.39–7.43 (both m, 2Н + 1H, HAr), 7.52–7.59 (m,
3
5Н, HAr), 7.63–7.72 (m, 6Н, HAr), 7.89 (d, 2Н, o-HAr in C(O)Ph, JHH = 7.8). 13С{1H} NMR
(100.61 MHz, CDCl3, δ/ppm, J/Hz): 97.98 (s, HC–C(O)), 120.97 (d, С2, 1JСP = 83.8), 124.75 (d,
С4, 3JСP = 12.5), 125.56 (d, ipso-С in P(S)Ph2, 1JСP = 87.6), 126.42 (d, С6, 3JСP = 7.6), 127.80 (s,
3
m-С in C(O)Ph), 128.12 (s, о-С in C(O)Ph), 129.32 (d, m-С in P(S)Ph2, JСP = 13.2), 130.78 (d,
С3, 2JСP = 7.9), 131.14 (s, p-С in C(O)Ph), 132.70 (d, о-С in P(S)Ph2, 2JСP = 11.0), 133.40 (d, p-
С in P(S)Ph2, 4JСP = 3.0), 134.58 (d, C5, 4JСP = 2.3), 135.81 (s, ipso-С in C(O)Ph), 153.52 (d, С1,
2JС = 3.0), 154.94 (s, N–CH), 176.20 (s, С=О). IR (КBr, ν/cm–1): 502(m), 518(m), 541(w),
P
604(m) (ν(P=S)), 622(w), 690(m), 707(s), 748(m), 768(w), 844(w), 970(w), 998(w), 1025(w),
1072(w), 1104(m), 1134(w), 1163(w), 1183(w), 1231(m), 1261(m), 1274(w), 1332(s), 1403(s),
1437(s), 1450(s), 1461(s), 1483(m), 1513(s) (ν(С=С)), 1554(s), 1587(m) (ν(С=О)), 2852(vw),
2921(vw), 3055(w). Anal. Calcd for С27Н21ClNOPPdS: С, 55.88; Н, 3.65; N, 2.41. Found: С,
55.87; Н, 3.67; N, 2.30%.
4.6. General procedure for the synthesis of Cu(II) complexes 6,7
A solution of Cu(OAc)2·H2O (22 mg, 0.110 mmol), triethylamine (31 ꢁL, 0.220 mmol),
and the corresponding ligand (0.220 mmol) in 12 mL of methanol was refluxed for 1.5 h. After
cooling to room temperature, the solvent was removed under reduced pressure. The resulting
residue was washed with hot ethanol (10 mL) and diethyl ether (5 mL) and dried in vacuo to give
complexes 6,7 as green crystalline solids.
4.6.1. [κ3-O,N,O-(L–H)2Cu(II)] 6
Yield: 90 mg (88%). Mp: >255°С (decomp.). IR (КBr, ν/cm–1): 543(m), 554(m), 703(m),
710(m), 721(m), 748(w), 760(w), 773(w), 836(w), 998(w), 1025(w), 1072(w), 1100(w),
1118(w), 1126(m), 1157(w), 1174(m) and 1187(m) (ν(P=O)), 1235(w), 1274(w), 1309(w),
1350(m), 1419(s), 1436(m), 1457(s), 1485(m), 1517(s) (ν(С=С)), 1568(sh, m), 1571(m),
1592(m) (ν(С=О)), 2923(vw), 3054(w). Anal. Calcd for С54Н42СuN2O4P2·Н2О: С, 70.01; Н,
4.79; N, 3.02. Found: С, 69.50; Н, 4.89; N, 2.95%.
4.6.2. [κ3-O,N,O-(L–H)2Cu(II)] 7

ACCEPTED MANUSCRIPT
16
Yield: 104 mg (95%). Mp: >150°С (decomp.). IR (КBr, ν/cm–1): 499(w), 508(w), 537(w),
694(m), 714(m), 746(m), 824(w), 999(w), 1023(w), 1072(w), 1103(w), 1120(m), 1143(w),
1174(m) and 1183(m) (ν(Р=О)), 1240(w), 1279(w), 1308(w), 1358(m), 1420(m), 1437(m),
1457(m), 1480(s), 1520(s) (ν(С=C)), 1569(m), 1591(m) (ν(С=О)), 1630(w), 2943(vw),
3023(vw), 3056(w). Anal. Calcd for С56Н46СuN2O4P2·3Н2О: С, 67.90; Н, 5.29; N, 2.83. Found:
С, 67.92; Н, 5.30; N, 2.93%.
4.7. Synthesis of Ni(II) complex 8
A solution of Ni(OAc)2·4H2O (27 mg, 0.109 mmol) and 1a (92 mg, 0.218 mmol) in 12 mL
of EtOH was refluxed for 4.5 h. After cooling to room temperature, the resulting precipitate of
complex 8 was filtered off, washed with ethanol (2×3 mL) and diethyl ether (2×3 mL), and dried
in vacuo to give 74 mg of complex 8 as a yellow crystalline solid. Yield: 75%. Mp: >281°С
(decomp.). IR (nujol, ν/cm–1): 537(w), 561(m), 691(m), 703(m), 725(m), 741(w), 746(), 758(),
770(w), 830(w), 981(), 998(vw), 1023(w), 1071(w), 1098(w), 1117(w), 1128(m), 1152(m) and
1164(sh, m) (both ν(Р=О)), 1246(w), 1275(w), 1346(m), 1427(s), 1439(m), 1456(s), 1465(s),
1483(m), 1506(m) (ν(С=С)), 1561(m), 1571(m), 1595(m) (ν(С=О)), 3053(w). Anal. Calcd for
С54Н42N2NiO4P2: С, 71.78; Н, 4.69; N, 3.10. Found: С, 71.81; Н, 4.80; N, 3.04%.
4.8. X-ray crystallography
Single crystals suitable for X-ray experiments were obtained by recrystallization from
EtOAc/EtOH (1a) and MeOH (6) or slow diffusion of hexane (3a,b) or ether (5) into chloroform
solutions. X-ray diffraction experiments were carried out with an APEX2 DUO CCD
diffractometer for compounds 1a and 6 and with a SMART APEX2 CCD diffractometer for all
others, using graphite monochromated Mo-Kα radiation (λ = 0.71073 Å, ω-scans) at 100K. The
structures were solved by direct method and refined by full-matrix least-squares method against
F2 in anisotropic approximation for non-hydrogen atoms. Hydrogen atom of NH group in 1a and
that of OH group of a solvate methanol molecule in 6 were found in difference Fourier synthesis;
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 1a, 3a, 3b,
5, and 6 are given in Table 2. All calculations were performed using the SHELXTL software.17
Table 2. Crystal data and structure refinement parameters for 1a, 3a, 3b, 5, and 6.
1a
3a
3b
5
6
Empirical
formula
Formula
weight
C59H53Cl5N2O3P2 C56H50CuN2O6
C27H22NO2P C30H21NO5PRe C30H21NO4PReS
Pd2S2
P2
423.43
100
692.65
100
708.71
100
1354.14
972.46
T, K
100
100

ACCEPTED MANUSCRIPT
17
Crystal
system
Monoclinic
Monoclinic
Triclinic
Orthorhombic
Triclinic
Space group
P21/c
4
P21/c
4
P-1
Fdd2
8
P-1
Z
2
1
a, Å
10.3025(4)
8.3782(3)
24.5325(10)
90.00
11.1347(4)
17.9830(7)
13.0777(5)
90.00
9.6378(3)
10.0867(3)
14.8057(5)
74.7460(10)
82.5520(10)
71.1970(10)
1312.92(7)
1.793
31.998(5)
39.689(7)
9.1926(15)
90.00
8.2787(6)
10.9732(8)
13.1079(10)
79.643(2)
80.973(2)
83.683(2)
1152.75(15)
1.401
b, Å
c, Å
α, °
100.4940(10)
90.00
94.8740(10)
90.00
90.00
β, °
90.00
γ, °
V, Å3
Dcalc (g cm−1)
2082.14(14)
1.351
2609.15(17)
1.763
11674(3)
1.541
Linear
absorption,
µ
1.57
47.6
48.06
10.17
5.99
(cm−1)
F(000)
888
58
1352
58
692
58
5472
54
507
57
2θmax, °
Reflections
measured
Independent
reflections
Observed
20834
5528
28787
6931
15843
6971
29676
6372
14407
6127
reflections [I
4643
5817
6585
4605
5193
> 2σ(I)]
Parameters
R1
280
343
343
359
305
0.0395
0.1154
1.008
0.0281
0.0629
1.007
0.0191
0.0448
1.001
0.0511
0.0835
1.002
0.0350
0.0936
1.001
wR2
GOF
ꢀ
ρ
max/ ꢀρmin
0.615/-0.249
1.196/-0.991
1.164/-1.027
1.144/-0.914
0.545/-0.514
(e Å−3)
Acknowledgements
This work was supported by the Russian Foundation for Basic Research, project no. 12-03-
00793-a.
Appendix A. Supplementary material
CCDC 956539–956543 contain the supplementary crystallographic data for 1a, 3a, 3b, 5,
and
6.
These
data
can
be
obtained
free
of
charge
via
http://www.ccdc.cam.ac.uk/conts/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.

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18
Appendix B. Supplementary material
Supplementary material includes selected bond lengths and angles as well as hydrogen
bond parameters for the compounds obtained.
References
1
(a) A.-Z.A. Elassar, A.A. El-Khair, Tetrahedron 59 (2003) 8463–8480;
(b) G. Palmieri, C. Cimarelli, ARKIVOC (2006) vi 104–126;
(c) B. Govindh, B.S. Diwakar, Y.L.N. Murthy, Org. Commun. 5 (2012) 105–119.
2
(a) P. Lue, J.V. Greenhill, Adv. Heterocycl. Chem. 67 (1996) 207–343;
(b) G. Negri, C. Kascheres, A.J. Kascheres, J. Heterocycl. Chem. 41 (2004) 461–491;
(c) B. Stanovnik, J. Svete, Chem. Rev. 104 (2004) 2433–2480;
(d) S.M. Riyadh, I.A. Abdelhamid, H.M. Al-Matar, N.M. Hilmy, M.H. Elnagdi,
Heterocycles 75 (2008) 1849–1905;
(e) A.S. Shawali, ARKIVOC (2012) i 383–431.
3
(a) I.O. Edafiogho, M.S. Alexander, J.A. Moore, V.A. Farrar, K.R. Scott, Curr. Med.
Chem. 1 (1994) 159–175;
(b) N.D. Eddington, D.S. Cox, R.R. Roberts, J.P. Stables, C.B. Powell, K.R. Scott, Curr.
Med. Chem. 7 (2000) 417–436;
(c) N.N. Salama, N.D. Eddington, D. Payne, T.L. Wilson, K.R. Scott, Curr. Med. Chem. 11
(2004) 2093–2103;
(d) I.O. Edafiogho, S.B. Kombian, K.V.V. Ananthalakshmi, N.N. Salama, N.D. Eddington,
T.L. Wilson, M.S. Alexander, P.L. Jackson, C.D. Hanson, K.R. Scott, J. Pharm. Sci. 96
(2007) 2509–2531.
4
(a) R.H. Holm, G.W. Everett, Jr., A. Chakravorty, Metal complexes of Schiff bases and β-
ketoamines, in: F.A. Cotton (Ed.), Progress in Inorganic Chemistry, vol. 7, John Wiley &
Sons Inc., Hoboken, USA,1966, pp. 83–214;
(b) I.-M. Lee, Characteristics and applications of metal complexes with β-ketoiminate
ligands, in: M.A. Cato (Ed.), Focus on Organometallic Chemistry Research, Nova Science
Publishers Inc., New York, USA, 2005, pp. 133–142.
5
(a) D. Jones, K. Cavell, W. Keim, J. Mol. Catal. A Chem. 1999 (138) 37–52;
(b) J. Kim, J.-W. Hwang, Y. Kim, M.H. Lee, Y. Han, Y. Do, J. Organomet. Chem. 620
(2001) 1–7;
(c) X.-F. Li, K. Dai, W.-P. Ye, L. Pan, Y.-S. Li, Organometallics 23 (2004) 1223–1230;
(d) D. Zhang, G.-X. Jin, L.-H. Weng, F. Wang, Organometallics 23 (2004) 3270–3275;

ACCEPTED MANUSCRIPT
19
(e) L. Zhang, M. Brookhart, P.S. White, Organometallics 25 (2006) 1868–1874;
(f) X. He, Q. Wu, Appl. Organomet. Chem. 20 (2006) 264–271;
(g) W. Miao, S. Li, D. Cui, B. Huang, J. Organomet. Chem. 692 (2007) 3823–3834
(h) D.-H. Lee, A. Taher, W.-S. Ahn, M.-J. Jin, Chem. Commun. 46 (2010) 478–480;
(i) Z.-Z. Zhou, F.-S. Liu, D.-S. Shen, C. Tan, L.-Y. Luo, Inorg. Chem. Commun. 14 (2011)
659–662;
(j) C.C. Roberts, B.R. Barnett, D.B. Green, J.M. Fritsch, Organometallics 31 (2012) 4133–
4141;
(k) M. Weidauer, E. Irran, C.I. Someya, M. Haberberger, S. Enthaler, J. Organomet. Chem.
729 (2013) 53–59;
(l) N.M. Rezayee, K.A. Gerling, A.L. Rheingold, J.M. Fritsch, Dalton Trans. 42 (2013)
5573–5586.
6
7
D. Pugh, P. Marchand, I.P. Parkin, C.J. Carmalt, Inorg. Chem. 51 (2012) 6385–6395.
(a) E.M. Gussenhoven, M.M. Olmstead, J.C. Fettinger, A.L. Balch, Inorg. Chem. 47
(2008) 4570–4578;
(b) N. Chopin, M. Médebielle, G. Pilet, Eur. J. Inorg. Chem. (2012) 1093–1103;
(c) R. Yoshii, A. Nagai, K. Tanaka, Y. Chujo, Chem. Eur. J. 19 (2013) 4506–4512.
(a) S. Doherty, J.G. Knight, T.H. Scanlan, M.R.J. Elsegood, W. Clegg, J. Organomet.
Chem. 650 (2002) 231–248;
8
(b) A.I. Uraev, V.P. Kurbatov, A.L. Nivorozhkin, L.S. Tyl’chenko, V.G. Vlasenko, L.N.
Divaeva, K.A. Lyssenko, M.Yu. Antipin, A.D. Garnovskii, Russ. Chem. Bull., Int. Ed. 51
(2002) 1924–1927;
(c) A. Sachse, N.C. Mösch-Zanetti, G. Lyashenko, J.W. Wielandt, K. Most, J. Magull, F.
Dall’Antonia, A. Pal, R. Herbst-Irmer, Inorg. Chem. 46 (2007) 7129–7135;
(d) L.A. Lesikar, A.F. Gushwa, A.F. Richards, J. Organomet. Chem. 693 (2008) 3245–
3255;
(e) A.F. Lugo, A.F. Richards, Eur. J. Inorg. Chem. (2010) 2025–2035;
(f) A.F. Lugo, A.F. Richards, Inorg. Chim. Acta 363 (2010) 2104–2112;
(g) S. Basu, G. Gupta, B. Das, K.M. Rao, J. Organomet. Chem. 695 (2010) 2098–2104.
V.A. Kozlov, V.Yu. Aleksenko, D.V. Aleksanyan, E.V. Sharova, O.I. Artyushin, I.L.
Odinets, Phosphorus, Sulfur Silicon Relat. Elem. 188 (2013) 79–83.
V.Yu. Aleksenko, E.V. Sharova, O.I. Artyushin, D.V. Aleksanyan, Z.S. Klemenkova,
Yu.V. Nelyubina, P.V. Petrovskii, V.A. Kozlov, I.L. Odinets, Polyhedron 51 (2013) 168–
179.
9
10

ACCEPTED MANUSCRIPT
20
11
D.V. Aleksanyan, V.Yu. Aleksenko, Yu.V. Nelyubina, A.A. Vasil’ev, R.R. Aysin, Z.S.
Klemenkova, V.A. Kozlov, P.V. Petrovskii, I.L. Odinets, Inorg. Chim. Acta 404 (2013)
167–174.
12
13
A.A. Vasil’ev, V.Yu. Aleksenko, D.V. Aleksanyan, V.A. Kozlov, Mend. Commun., in
press.
D.V. Aleksanyan, V.A. Kozlov, B.I. Petrov, T.V. Balashova, A.P. Pushkarev, A.O.
Dmitrienko, G.K. Fukin, A.V. Cherkasov, M.N. Bochkarev, N.M. Lazarev, Yu.A.
Bessonova, G.A. Abakumov, RSC Advances, in press.
14
15
D.V. Aleksanyan, V.A. Kozlov, I.L. Odinets, I.V. Fedyanin, K.A. Lyssenko, M.P.
Pasechnik, P.V. Petrovsky, T.A. Mastryukova, Rus. Chem. Bull., Int. Ed. 56 (2007) 1891–
1899.
Y. Honma, Y. Sekine, T. Hashiyama, M. Takeda, Y. Ono, K. Tsuzurahara, Chem. Parm.
Bull. 30 (1982) 4314–4324.
16
17
L.J. Bellamy, The Infrared Spectra of Complex Molecules, Wiley, New York, 1975.
G.M. Sheldrick, Acta Cryst., Sect. A 64 (2008) 112–122.

ACCEPTED MANUSCRIPT
Condensation of (thio)phosphorylanilines with PhC(O)CH=CHONa afforded novel ligands.
P(X)-functionalized enaminoketones (X=O, S) show interesting structural behavior.
The ligands obtained readily form κ3-X,N,O-complexes (X=O, S) with transition metals.

ACCEPTED MANUSCRIPT
(Thio)phosphoryl-functionalized enaminoketones: Synthesis, structure, and complexing
properties towards transition metal ions
Diana V. Aleksanyan,* Valentina Yu. Aleksenko, Yulia V. Nelyubina, Zinaida S. Klemenkova,
Vladimir A. Kozlov
A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul.
Vavilova 28, Moscow, 119991 Russia
*Corresponding author. Tel.: +7 499 135 9356; e-mail address: aleksanyan.diana@ineos.ac.ru
Supplementary material
Table A. 1. Selected bond lengths (Å) and angles (°) for compounds 1a, 3a, 3b, 5, and 6.
1a
P(1)–O(1)
1.4995(10)
1.8069(13)
1.4020(17)
1.3491(17)
1.361(2)
N(1)–C(7)–C(8)
C(7)–N(1)–H(1N)
N(1)–C(7)–H(7C)
C(8)–C(7)–H(7C)
C(7)–C(8)–H(8C)
C(7)–C(8)–C(9)
C(9)–C(8)–H(8C)
O(2)–C(9)–C(8)
C(8)–C(9)–C(10)
O(2)–C(9)–C(10)
C(15)–C(10)–C(9)
124.90(13)
116.9
P(1)–C(2)
N(1)–C(1)
117.6
N(1)–C(7)
117.6
C(7)–C(8)
120.6
C(8)–C(9)
1.4544(19)
1.2408(18)
1.5003(19)
112.96(6)
119.24(12)
126.62(12)
116.5
118.82(13)
120.6
O(2)–C(9)
C(9)–C(10)
O(1)–P(1)–C(2)
N(1)–C(1)–C(2)
C(7)–N(1)–C(1)
C(1)–N(1)–H(1N)
121.90(13)
119.24(12)
118.85(13)
123.13(13)
3°
Re(1)–C(28)
Re(1)–C(29)
Re(1)–C(30)
Re(1)–O(1)
Re(1)–O(2)
Re(1)–N(1)
P(1)–O(1)
P(1)–C(2)
N(1)–C(1)
N(1)–C(7)
C(7)–C(8)
1.930(3)
1.889(4)
1.884(3)
2.173(2)
2.130(2)
2.151(3)
1.514(2)
1.799(3)
1.430(4)
1.313(4)
1.392(5)
N(1)–Re(1)–O(1)
O(2)–Re(1)–N(1)
C(28)–Re(1)–N(1)
C(29)–Re(1)–O(1)
C(30)–Re(1)–O(2)
O(1)–P(1)–C(2)
C(2)–C(1)–N(1)
C(7)–N(1)–C(1)
N(1)–C(7)–C(8)
N(1)–C(7)–H(7C)
C(8)–C(7)–H(7C)
82.33(9)
82.15(9)
173.73(13)
176.46(12)
177.90(12)
113.05(14)
117.6(3)
117.8(3)
125.8(3)
117.1
117.1

ACCEPTED MANUSCRIPT
C(8)–C(9)
1.386(5)
1.291(4)
1.494(5)
88.47(14)
85.31(15)
90.77(15)
85.45(8)
C(7)–C(8)–H(8C)
C(9)–C(8)–C(7)
C(9)–C(8)–H(8C)
O(2)–C(9)–C(8)
C(8)–C(9)–C(10)
O(2)–C(9)–C(10)
118.0
O(2)–C(9)
124.1(3)
118.0
C(9)–C(10)
C(30)–Re(1)–C(28)
C(30)–Re(1)–C(29)
C(29)–Re(1)–C(28)
O(2)–Re(1)–O(1)
124.6(3)
120.4(3)
114.9(3)
3b
Re(1)–C(28)
Re(1)–C(29)
Re(1)–C(30)
Re(1)–S(1)
1.925(2)
1.905(2)
1.901(2)
2.5396(6)
2.1269(15)
2.1584(18)
2.0075(8)
1.816(2)
1.421(3)
1.320(3)
1.397(3)
1.395(3)
1.280(3)
1.496(3)
87.14(9)
89.94(9)
88.88(9)
87.12(5)
N(1)–Re(1)–S(1)
O(2)–Re(1)–N(1)
C(28)–Re(1)–N(1)
C(29)–Re(1)–S(1)
C(30)–Re(1)–O(2)
C(2)–P(1)–S(1)
85.44(5)
84.33(6)
176.91(8)
176.38(7)
174.15(8)
116.45(8)
117.95(19)
118.30(18)
126.3(2)
116.9
Re(1)–O(2)
Re(1)–N(1)
P(1)–S(1)
C(2)–C(1)–N(1)
C(7)–N(1)–C(1)
N(1)–C(7)–C(8)
N(1)–C(7)–H(7C)
C(8)–C(7)–H(7C)
C(7)–C(8)–H(8C)
C(9)–C(8)–C(7)
C(9)–C(8)–H(8C)
O(2)–C(9)–C(8)
C(8)–C(9)–C(10)
O(2)–C(9)–C(10)
P(1)–C(2)
N(1)–C(1)
N(1)–C(7)
C(7)–C(8)
117.3
C(8)–C(9)
117.3
O(2)–C(9)
125.4(2)
117.3
C(9)–C(10)
C(30)–Re(1)–C(28)
C(30)–Re(1)–C(29)
C(29)–Re(1)–C(28)
O(2)–Re(1)–S(1)
125.3(2)
119.4(2)
115.25(19)
5
Pd(1)–O(2)
Pd(1)–N(1)
Pd(1)–S(1)
Pd(1)–Cl(1)
P(1)–S(1)
P(1)–C(2)
C(1)–N(1)
N(1)–C(7)
C(7)–C(8)
C(8)–C(9)
O(2)–C(9)
C(9)–C(10)
2.003(4)
2.042(5)
2.2921(16)
2.3093(16)
2.009(2)
1.787(6)
1.425(7)
1.318(7)
1.390(7)
1.392(8)
1.287(7)
1.490(8)
S(1)–Pd(1)–Cl(1)
O(2)–Pd(1)–Cl(1)
C(2)–P(1)–S(1)
C(2)–C(1)–N(1)
C(7)–N(1)–C(1)
N(1)–C(7)–C(8)
N(1)–C(7)–H(7C)
C(8)–C(7)–H(7C)
C(7)–C(8)–H(8C)
C(7)–C(8)–C(9)
C(9)–C(8)–H(8C)
O(2)–C(9)–C(8)
84.28(6)
85.85(12)
109.8(2)
121.3(5)
115.1(5)
129.4(6)
115.3
115.3
117.9
124.1(6)
117.9
123.0(5)

ACCEPTED MANUSCRIPT
N(1)–Pd(1)–O(2)
N(1)–Pd(1)–S(1)
N(1)–Pd(1)–Cl(1)
90.28(18)
99.60(14)
176.04(14)
C(8)–C(9)–C(10)
O(2)–C(9)–C(10)
121.5(5)
115.4(5)
6
Cu(1)–O(2)
Cu(1)–N(1)
Cu(1)–O(1)
P(1)–O(1)
1.9490(11)
1.9934(13)
2.4580(11)
1.4988(11)
1.8114(16)
1.4215(19)
1.319(2)
C(9)–O(2)–Cu(1)
O(1)–P(1)–C(2)
C(2)–C(1)–N(1)
C(7)–N(1)–C(1)
N(1)–C(7)–C(8)
N(1)–C(7)–H(7C)
C(8)–C(7)–H(7C)
C(7)-C(8)–H(8C)
C(9)–C(8)–C(7)
C(9)–C(8)–H(8C)
O(2)–C(9)–C(8)
C(8)–C(9)–C(10)
O(2)–C(9)–C(10)
125.23(10)
115.34(7)
118.21(13)
117.15(13)
125.72(15)
117.1
P(1)–C(2)
N(1)–C(1)
N(1)–C(7)
117.1
C(7)–C(8)
1.403(2)
118.4
C(8)–C(9)
1.395(2)
123.28(15)
118.4
O(2)–C(9)
1.2801(19)
1.503(2)
C(9)–C(10)
O(2)–Cu(1)–N(1)
C(7)–N(1)–Cu(1)
C(1)–N(1)–Cu(1)
125.04(14)
119.95(14)
115.01(13)
90.19(5)
121.79(11)
120.77(10)
Table A. 2. Hydrogen bond geometry for compounds 1a and 6 (Å, °).
D–H...A
d(D–H)
0.91
d(H...A)
1.94
d(D...A)
<(DHA)
147
1a
N(1)–H(1N)...O(1)
2.7525(16)
6
O(1S)–H(1SO)...O(1)
0.85
1.95
2.7796(17)
167
Symmetry transformations used to generate equivalent atoms: x,y,z