Coordination mode of the N-[bis(diethylamino)phosphoryl]benzenesulfonamide ligand in Lu(III) and Ag(I) complexes. Mass spectra, thermal properties and DFT calculations

Article abstract of DOI:10.1016/j.poly.2017.09.038

The sulfonylamidophosphate ligand C₆H₅SO₂NHPO(N(C₂H₅)₂)₂ (HL) has been used for the synthesis of two novel complexes: LuL₃ (1) and (AgL)_n (2). According to an X-ray diffraction study, in the structure of HL, the molecules are linked into polymeric chains by strong N–H?O = P hydrogen bonds. The three acido-ligands (L^?) in the structure of 1 are coordinated to the lutetium ion in a bidentate-chelate manner via two oxygen atoms of the phosphoryl and sulfonyl groups, forming six-membered metallocycles, which adopt a boat conformation. In the structure of 2, the ligand is coordinated in the bidentate-bridging mode via the oxygen atom of the phosphoryl group and the nitrogen atom of the imide group; the chelate adopts a twist-boat conformation. The thermal behavior of the complexes 1 and 2 was studied by means of TG analysis. Results of IR-spectroscopy and LDI, ESI MS are discussed and compared with those obtained from DFT calculations.

Full text of DOI:10.1016/j.poly.2017.09.038

Accepted Manuscript
Coordination mode of the N-[bis(diethylamino)phosphoryl]benzenesulfona-
mide ligand in Lu(III) and Ag(I) complexes. Mass spectra, thermal properties
and DFT calculations
Iuliia O. Shatrava, Vladimir A. Ovchynnikov, Kateryna E. Gubina, Tetyana Yu.
Sliva, Olga V. Severinovskaya, Anatoliy G. Grebenyuk, Svitlana V. Shishkina,
Vladimir M. Amirkhanov
PII:
S0277-5387(17)30615-0
https://doi.org/10.1016/j.poly.2017.09.038
POLY 12848
DOI:
Reference:
To appear in:
Polyhedron
Received Date:
Accepted Date:
18 July 2017
13 September 2017
Please cite this article as: I.O. Shatrava, V.A. Ovchynnikov, K.E. Gubina, T. Yu. Sliva, O.V. Severinovskaya, A.G.
Grebenyuk, S.V. Shishkina, V.M. Amirkhanov, Coordination mode of the N-
bis(diethylamino)phosphoryl]benzenesulfonamide ligand in Lu(III) and Ag(I) complexes. Mass spectra, thermal
properties and DFT calculations, Polyhedron (2017), doi: https://doi.org/10.1016/j.poly.2017.09.038
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Coordination mode of the N-[bis(diethylamino)phosphoryl]benzenesulfonamide
ligand in Lu(III) and Ag(I) complexes. Mass spectra, thermal properties and
DFT calculations
1
*
1
1
1
Iuliia O. Shatrava , Vladimir A. Ovchynnikov , Kateryna E. Gubina , Tetyana Yu. Sliva ,
2
2
3,4
Olga V. Severinovskaya , Anatoliy G. Grebenyuk , Svitlana V. Shishkina
1
and Vladimir M. Amirkhanov
1
2
3
4
Department of Chemistry, Taras Shevchenko National University of Kyiv, 64/13, Volodymyrska
Str., Kyiv 01601, Ukraine
Chuiko Institute of Surface Chemistry of National Academy of Sciences of Ukraine, 17 General
Naumov Str., Kyiv, 03164, Ukraine
SSI "Institute for Single Crystals", National Academy of Science of Ukraine, 60, Nauky Ave.,
Kharkiv 61001, Ukraine
Department of Inorganic Chemistry, V. N. Karazin Kharkiv National University, 4 Svobody sq.,
Kharkiv 61077, Ukraine
Keywords: Crystal structure; lutetium(III); silver(I); laser desorption/ionization (LDI MS); DFT
calculations.
Abstract
The sulfonylamidophosphate ligand C
synthesis of two novel complexes: LuL
6
H
5
SO
2
NHPO(N(C
2 5 2 2
H ) ) (HL) has been used for the
3
(1) and (AgL)
n
(2). According to an X-ray diffraction
study, in the structure of HL, the molecules are linked into polymeric chains by strong N-H···O=P
-
hydrogen bonds. The three acido-ligands (L ) in the structure of 1 are coordinated to the lutetium
ion in a bidentate-chelate manner via two oxygen atoms of the phosphoryl and sulfonyl groups,
forming six-membered metallocycles, which adopt a boat conformation. In the structure of 2, the
ligand is coordinated in the bidentate-bridging mode via the oxygen atom of the phosphoryl group
and the nitrogen atom of the imide group; the chelate adopts a twist-boat conformation. The thermal
behavior of the complexes 1 and 2 was studied by means of TG analysis. Results of IR-
spectroscopy and LDI, ESI MS are discussed and compared with those obtained from DFT
calculations.
1
. Introduction
Progress in coordination chemistry allows the development of novel compounds which may be used
as metallo-drugs, with directed and preset properties. Attention to coordination chemistry of
polyfunctional phosphorus compounds has recently grown due to the application of such
compounds as extractants [1], urease inhibitors, enzyme inhibitors, potential antiviral and anticancer
drugs [2]. Among them, CAPhs (carbacylamidophosphates) are interesting and promising
compounds to study: containing the structural fragment C(O)NHP(O), CAPhs can be considered as
P, N structural analogues of the well-known β-diketones. The presence of the phosphoryl group
allows the use of this ligand system in the coordination chemistry of lanthanides and actinides [3].
Recently, another type of structural analogue of β-diketones – sulfonylamidophosphates
(
SAPhs), with the S(O) NHP(O) functional core – has attracted the interest of researchers. This type
2
of phosphoramide was first synthesized by Kirsanov and co-workers [4] and has been utilized in
medicine as a bactericidal agent [5] and in agriculture as a pesticide [6]. In recent papers, we have
reported the preparation, structural investigation and coordination behavior of some representative
SAPh compounds. Moreover, the photophysical properties of a new series of NIR emitting
lanthanide complexes based on these compounds have been studied [7]. It is important to note that
–
tetrakis-complexes [LnL
4
] (where L is a SAPh ligand) usually contain eight coordinated lanthanide

3
ions [8], while the coordination sphere of the corresponding tris-complexes [LnL ] is not saturated
and therefore comprises additional solvent molecules. However, it is possible to obtain a six-
coordinated tris-lanthanide complex without any solvent molecules when using ions with small
radii. We report herein the structures of N′,N′′-tetraethyl-N ′′-(phenylsulfonyl)triamidophosphate
(
3 n
HL), LuL (1) and (AgL) (2) as part of our ongoing study on the coordination chemistry of
sulfonylamidophosphates. In the current work, mass spectrometric data obtained by two different
ionization techniques (ESI and MALDI) are presented. These methods are widely used for
characterization of novel transition metal complexes, along with screening their bioactivity and a
study of the interaction mechanism between metallo-drugs and biomolecules [9].
2
. Results and discussion
2
.1. Description of the structures
Crystallographic data for the compounds HL, 1 and 2 are summarized in Table 1.
Table 1. Selected crystallographic data for HL, LuL
3
(1) and (AgL) (2).
n
Compound
Formula
HL
O
1
2
C
14
H
26
N
3
3
PS
C
42
H
75LuN
9
O
9
P
S
3 3
C
14
H
3 3
25AgN O PS
Formula weight
Temperature (K)
Crystal system
Space group
a (Å)
b (Å)
c (Å)
α (°)
347.42
293(2)
1214.17
293(2)
hexagonal
R3
22.0475(7)
22.0475(7)
9.9007(3)
90.00
454.27
293(2)
monoclinic
1
P2 /c
9.2211(2)
17.9073(4)
11.4105(2)
90.00
monoclinic
P2 /c
10.1911(2)
1
33.7250(11)
10.8284(3)
90.00
β (°)
100.304(2)
90.00
100.598(2)
γ (°)
V (Å )
Z
90.00
3661.64(17)
8
0.279
1.260
120.00
4167.9(2)
3
2.032
1.451
90.00
1852.02(7)
4
1.303
1.629
3
–
1
µ (mm )
3
D
calc (g/cm )
2
Θmax (°)
50
60
60
Measured reflections
Independent reflections
17427
6122
12162
5251
15422
5335
R
int
0.022
0.020
0.018
Reflections with F>4σ(F) 5025
5200
3884
Parameters
496
206
212
R
wR
S
1
0.076
0.177
1.132
985455
0.019
0.043
0.908
985456
0.032
0.084
1.206
985457
2
CCDC number
Two molecules of HL (A and B) have been found in the asymmetric part of the unit cell. The
bond lengths in the sulfonyl groups, S1A–O2A, S1A–O3A and S1A–N1A (Table 2), are similar to
the corresponding values observed in C H SO NHP(O)(OMe) [10]. These values depend on the
6 5 2 2
substituent near the sulfur atom and are typical for sulfonylamide derivatives [11].
The P1A–O3A and P1A–N1A bond lengths for HL (Fig. 1, Table 2) have values which are
typical for CAPhs with amide-type substituents [12]. The length of the P=O bond is influenced by
the nature of the substituents attached to the phosphorus atom. The geometry around the phosphorus

atom in HL can be described as a distorted tetrahedron, with the N–P–N unequal angles centered at
the phosphorus atom (Table 2).
Fig. 1. The molecular structure of HL showing the atom numbering scheme (the disordering and the
hydrogen atoms are omitted for clarity, except for those involved in the intramolecular hydrogen
bond. The displacement ellipsoids are drawn at the 30% probability level.
Table 2. Selected bond lengths (Å) and bond angles (°) for HL.
Bond lengths (Å)
S1–O2
S1–O3
S1–N1
P1–N3
P1–N1
P1–N2
P1–O1
S1–C1
Mol. A
1.421(3)
1.426(3)
1.624(4)
1.629(4)
1.693(3)
1.622(4)
1.479(3)
1.756(5)
Mol. B
Bond angles (°)
Mol. A
119.2(2)
104.3(2)
112.2(2)
111.9(2)
113.9(2)
105.4(2)
103.2(2)
109.5(2)
Mol. B
119.2(2)
106.2(2)
114.3(2)
110.7(2)
114.4(2)
103.8(2)
107.0(2)
105.8(2)
1.433(3) O2–S1–O3
1.420(4) N1–S1–C1
1.620(3) O1–P1–N2
1.627(4) O1–P1–N1
1.686(4) O1–P1–N3
1.622(4) N3–P1–N1
1.470(3) N2–P1–N1
1.778(4) N2–P1–N3
Due to the steric effects, the values of the O–P–N angles in the derivatives of phosphoric acid
are usually larger than those in the ideal tetrahedron (Table 2).
In the structure of HL, pseudo-torsion angles between the P=O bond and the nearest S=O bonds
in the two independent molecules are –53.1 and –55.7º. A strong pπ-dπ conjugation between the
oxygen atom of the sulfonyl group and the phosphorus atom can be established by comparison of
the P…O(S) distances (3.06 Å in both molecules) with the sum of Van der Waals radii (3.12 Å)
[
13]. Strong hydrogen bonds, N–H···O=P (x, y, z) [d(H···O) = 1.98 Å, ∠N–H···O =166.5°] which
connect the molecules into polymeric (HL)
n
chains, also have significant influence on the ligand
conformation (Fig. 2, Table 3).

Fig. 2. The crystal packing of HL showing the N–H···O hydrogen bonds (dashed lines).
Table 3. Hydrogen bonding parameters (Å, °) for HL.
D–H···A
N1A–H1AA...O3B
D–H
0.86
0.86
H···A
1.98
1.97
D···A
2.819(4)
2.807(4)
∠D–H···A
166.5
163.9
(i)
N1B–H1BA...O3A
(
i)
Symmetry code: x–1, y, z
The compound 1 is located in a special position, where the Lu atom is situated at the triad axis.
The deprotonated ligands are coordinated to the Lu ion in the bidentate-chelate manner (Fig. 3). The
elongation of the S=O (coordinated) and P=O bonds and shortening of the S–N and P–N bonds
demonstrate the presence of strong π-conjugation within the S(O) NP(O) fragment. The S=O bond
2
length (for the non-coordinated fragments) remains practically the same as compared to the S=O
bond length in the structure of HL.
Fig. 3. The asymmetric part of the molecular structure of 1 showing the atom numbering scheme
(
A) and the whole complex with Lu (B). The displacement ellipsoids are drawn at the 30%
probability level. The hydrogen atoms are omitted for clarity.
The Lu–O bond lengths, formed by sulfonyl and phosphoryl groups (Table 4), are in accordance
to data for similar coordination compounds [8]. The shorter Lu–O(P) distance as compared to Lu–
O(S) can be explained by the higher affinity of the phosphoryl group to the lanthanide ion (Table
4
).

Table 4. Selected bond lengths (Å) and bond angles (°) for 1 and 2.
Bond lengths (Å)
1
Bond angles (°)
Lu1–O1
Lu1–O2
S1–O3
S1–O2
S1–N1
S1–C1
P1–O1
P1–N1
P1–N2
P1–N3
2
2.147(1)
2.252(2)
1.431(2)
1.482(2)
1.545(2)
1.772(2)
1.510(2)
1.611(2)
1.631(2)
1.632(2)
O1–Lu1–O2
O3–S1–O2
S1–N1–P1
O1–P1–N1
O1–P1–N3
O1–P1–N2
N1–P1–N2
N1–P1–N3
N2–P1–N3
80.75(5)
112.9(1)
124.9(1)
115.1(1)
112.1(1)
104.9(1)
112.6(1)
103.0(1)
109.3(1)
i
Ag1–O1
Ag1–O2
2.152(2)
2.555(2)
2.157(2)
1.436(2)
1.443(2)
1.592(2)
1.766(3)
1.647(2)
1.493(2)
1.632(2)
1.647(2)
O1–Ag1–N1
163.75(8)
78.12(6)
118.12(7)
116.2(1)
124.6(1)
114.0(1)
116.4(1)
107.2(1)
105.3(1)
111.8(1)
101.9(1)
O1–Ag1–O2i
N1–Ag1–O2
O3–S1–O2
S1–N1–P1
O1–P1–N1
O1–P1–N3
O1–P1–N2
N2–P1–N3
N2–P1–N1
N3–P1–N1
(i)
Ag1–N1
S1–O3
S1–O2
S1–N1
S1–C1
P1–N1
P1–O1
P1–N2
P1–N3
(
i)
Symmetry code: x, –y+1, z+0.5
The coordination environment of the Lu cation can be characterized as a distorted octahedron.
The P=O and S=O bonds are facial. A weak interaction between the neighboring molecules exists
through the non-coordinated oxygen atom of a sulfonyl group and one of the hydrogen atoms of the
benzene rings.
The classical bidentate coordination mode of the sulfonylamidophosphate ligand via the oxygen
atoms of the phosphoryl and sulfonyl groups was observed for 1. In the case of complex 2, the
ligand is coordinated to the Ag ion in the tridentate manner, since the Ag(I) ion has a high affinity
for N and O donors. As a result, one-dimensional polymeric chains along the c axis are formed in
n
the complex (AgL) : the ligand is coordinated to one Ag cation in the bidentate manner via the
oxygen atoms of the sulfonyl and phosphoryl groups, with an additional bridging coordination via
the nitrogen atom to the neighboring Ag ion (Fig. 4). A short contact has been observed between the
Ag ion and the oxygen atom of the sulfonyl group of the neighboring molecule (Ag1-O3 2.978Å).

A
B
Fig. 4. The molecular structure of 2 showing the atom numbering scheme (A). The displacement
ellipsoids are drawn at the 30 % probability level. The hydrogen atoms are omitted for clarity. A
view of the one-dimensional chain of 2 along the c axis (B).
The coordination environment of the Ag cation can be characterized as a distorted triangle. The
Ag1–N1 bond length is 2.157(2) Å. This value is smaller than the sum of ionic radii (2.26 Å) and
can be explained by a significant covalent contribution to the Ag–N bond. Ag–N bond lengths of
2
3 2 2 3
.169 and 2.135 Å were found for Na[Ag(CCl C(O)NP(O)(OMe) ) ]·CH CN [14] and
[
Ag(C10
H
8
N
2
)(NH )]NO [15], respectively. The Ag1–O1 (phosphoryl group) distance is notably
3
3
shorter than the Ag1–O2 (sulfonyl group) one (Table 4), with an O1–Ag1–N1 angle of 163.75(8)°.
The O2–Ag1–N1 angle is 118.12(7)° due to an additional weak coordination contact with the
sulfonyl oxygen atom O2.
For the analysis of the SAPh conformations, two parameters were chosen: a deviation of the six-
membered chelate cycle from a mean plane which contains the O, P, S and O atoms (both oxygen
atoms are coordinated to the metal ion), and the value of the pseudo-torsion angle between the P=O
and S=O (coordinated) groups. Thus, in the structure of 1, the value of the above-mentioned angle
is 0.50°. The metallocycle adopts a boat conformation with puckering parameters S = 0.48, Θ =
6
1.6°, Ψ = 58.6°. The deviations of the N1 and Lu atoms from the mean plane of the remaining
atoms of this cycle are 0.40 and 0.23 Å respectively. In the structure of 2, the pseudo-torsion angle
between the P=O and S=O (coordinated) bonds is equal to 26.1°, and the metallocycle adopts a
twist-boat conformation with the puckering parameters S = 0.76, Θ = 87.4°, Ψ = 21.6°. The
deviations of the N1 and Ag1 atoms from the O1–P1–O2–S1 mean plane are 0.393 and 0.688 Å,
respectively. The coordination environment of the Ag ion is planar; the sum of the angles at this
atom is equal to 360°. The deviation of the Ag1 atom from the O1–O2–N1 plane is 0.001 Å.
2
.2. Spectroscopic characterization

The literature data was used to tentatively assign the absorption bands of the valence vibrations
of the sulfonyl υas(SO ), υ (SO ) and phosphoryl υ(PO) groups [16]. The deprotonation of HL leads
to a significant delocalization of the π-electron density in the SO NPO fragment and to the
bathochromic shift of the valence vibrations in the spectra of the sodium salt NaL, 1 and 2 as
2
s
2
2
-
1
-1
2 s 2
compared to HL, by the values of ∆υas(SO ) = 60–120 cm , ∆υ (SO ) = 25–40 cm and ∆υ(P=O) =
-
1
3
5–60 cm .
The broad absorption band located at 2950–3100 cm in the IR spectrum of HL was tentatively
-1
assigned to the amide group υ(N–H). This band is missing in the spectra of the sodium salt and
complexes 1 and 2, which is evidence of ligand deprotonation.
2
.3. Laser desorption/ionization (LDI MS) and ESI MS of (AgL)
n
The mass spectrum fragmentation of the complex with the formula (AgL)
n
in the mass range of
3
20–850 Da is shown in Fig. S1, Supporting Information. The most intensive peak, with a m/z ratio
of 346.6, can be assigned to the deprotonated ligand. The peaks with m/z values of 453.9, 563.5,
and 802.1, which can be assigned to associates of silver and the ligand with various structures, are
summarized in the Table S1, Supporting Information.
The peaks with m/z values of 390.7 and 422.5, located in the negative part of the spectrum,
contain one silver atom and various fragments of the ligand molecule. The series of peaks with m/z
values of 490.6, 517.7, 532.7, 620.8 and 631.8 correspond to derivatives of an ion-molecular
–
associate with the formula [Ag
2
L] . All of these fragments contain two silver atoms. Further series
of peaks with m/z values over 650 (659.9, 715.9, 750.9) correspond to silver-containing fragments
–
2
of an ion-molecular associate with the formula [AgL ] . All of these fragments are formed by
–
acceptance of an electron, in contrast to the fragment with the formulae [L] , which is formed by
deprotonation of the starting compound. Thus, introducing the silver atom into the molecule
changes the ionization mechanism.
Peaks which correspond to ligand fragments participating in the association processes are
observed in the low-molecular area of the mass spectra.
It should be noted that the fragmentation of the complex studied in the negative mode is more
intensive in contrast to that in positive mode [17], where association processes due to acceptance of
protons and metal atoms play the main role.
Thus, we can suppose a two-step mechanism of the complex fragmentation, with the first step
including cleavage of the bonds between the basic units of the polymeric structure and participation
of different numbers of the silver atoms and the ligand residues (forming ion-molecular associates
with various structures). Another explanation of the fragmentation pathway includes formation of
the described unstable fragments already in the starting sample. The high ionization capability of
those fragments leads to high intensity of the corresponding peaks, in contrast to the less intensive
peaks related to the ion-molecular associates (more stable structures). The second step can be
explained by the interaction of ligand fragments with various complex associates in the gas phase
under the mass spectrometric conditions.
In the ESI mass spectrum of the studied complex, a small number of peaks is observed, the most
–
intensive one corresponding to [L] (Table S2, Supporting Information). This feature of the mass
spectrum can be explained by the “soft” ionization mechanism of the ESI MS method, which
reduces fragmentation. The series of peaks with m/z values about 238, 291 and 528, and at 538.1
correspond to fragments of the ligand and its associates which do not contain silver. The series of
peaks with m/z values about 498, 606 and 690 correspond to ion-molecular associates containing
two to four silver atoms and various fragments of the ligand molecule. The pesence of such
fragments in the negative mode mass spectrum confirms the high propensity of the complex studied
towards association in the gas phase.
We suppose that the studied complex (AgL)
n
is fragmented and ionized under the ESI
conditions due to association of the ligand mainly with the metal ions.

The possibility of the formation of different associates observed in the two mass-spectroscopic
studies was confirmed by quantum chemical calculations (see below).
2
.4. DFT calculations
Based on the values of the full energy of the neutral ligand and its anion (Fig. 5), the energy of
deprotonation was calculated (1.063 a.u. or 2792.6 kJ/mol). At 298.15 K, the Gibbs free energy of
this process is equal 2746.6 kJ/mol; therefore, HL can be considered as a weak acid. Nevertheless, it
forms sodium and silver salts relatively simply.
A
B
Е
full = –188.96140 а.u.
Е
full = –187.8980776 а.u.
–
Fig. 5. The calculated geometry of HL (A) and L (B)
In the silver salt crystals, a chain structure with the ligand anions and the silver cations
alternating each other can be outlined. We calculated the spatial structure and total energy of the
dimer and monomer associates of the silver salt (Figs. 6 and 7). Considering the total energy of the
silver cation (-145.996 а.u.), it is possible to determine the affinity for the anion (0.768 а.u. or
2
016.4 kJ/mol) and for the monomer salt (0.126 а.u. or 330.3 kJ/mol). The energy of dimerization
of the silver salt is –0.045 а.u. (–117.1 kJ/mol).
A
B
Е
full = –188.62530 а.u.
Еfull = –334.66150 а.u.
Fig. 6. The calculated geometries of NaL (A) and AgL (B)

B
A
Е
full = –480.78304 а.u.
Е
full = –669.36761 а.u.
+
Fig. 7. The calculated geometries of the dimer Ag
L
2 2
(A) and the Ag
2
L (B) associate
It is well-known that the HOMO energy describes the electron donor properties, whereas the
LUMO energy characterizes the electron acceptor properties [18]. The HOMO–LUMO orbital
schemes for the compounds studied are shown in Fig. 8. In HL, the electron density of the HOMO
is localized mainly at the P=O, both C–N bonds, C–C and C–N bonds (ethyl substituents). In the
case of the LUMO, the orbital is located at the S=O and C–S bonds and the C–C bonds of the
phenyl ring. The ∆HOMO–LUMO value is 232.466 nm. For NaL and AgL, the electron density of the
HOMO is localized similarly to that of HL. The LUMO orbital is located at the Na and Ag ions.
The ∆HOMO–LUMO gap is 271.3 nm for NaL and 792.4 nm – for AgL.
(
A)

(
B)
(
C)
Fig. 8. The theoretically calculated electronic transitions and HOMO–LUMO orbital schemes
for HL (A), NaL (B) and Ag (C)
2 2
L
The presence of conjugation in the chelate fragment O=S–N–P=O is confirmed by the
analysis of bond orders and effective charges on the atoms. The bond order of S=O decreases in the
–
series: HL, Ag
2
L
2
, AgL, NaL and anion L . The bond order of P=O decreases from the largest value
–
for HL to the smallest for L . On the contrary, the S–N and N–P bond orders increase in AgL and
NaL as compared to that of HL. Meanwhile, conjugation of the benzene ring and terminal NEt
2
group with this fragment decreases. As a result, the effective charges increase on the oxygen atoms
that are in contact with the metal ion (Tables 5 and 6).
Table 5. The calculated bond orders.
-
HL
0.638
L
NaL
0.615
AgL
0.63
Ag
0.599
2 2
L fragment
C–S(
0.287
i)
S=O
S–N(
N–P
P=O(
P–N
1.710, 1.718 1.212, 1.113 1.710, 1.369* 1.733, 1.434* 1.681, 1.461*
0.765
0.891
1.934
0.712
1.01
1.473
0.892
1.047
1.860
0.905
0.979
1.907
0.915
1.042
1.670
ii)
iii)
1.037, 1.060 0.658, 0.670 0.941, 0.996
0.998, 0.996
0.191
0.340
0.972, 1.110
0.224, 0.070
0.360
Na,Ag–O
Na,Ag–N
0.221
0.270
(
(
i)
The coordinated S=O group.
Between the SO and P=O groups.
ii)
2

(
iii)
The terminal NEt
2
group.
Table 6. The calculated Mulliken charges.
O(S)
O(S)
N
O(P)
HL
LA
NaL
AgL
AgLAgK
–0.334
–0.471
–0.349
–0.333
–0.364
–0.339
–0.494
–0.474
–0.405
–0.387
–0.389
–0.413
–0.474
–0.460
–0.479
–0.446
–0.453
–0.426
–0.562
–0.448
–0.438
–0.490
–0.446
(
(
(
(
i)
i)
i)
i)
Ag
2
L fragment –0.296
2
(
i)
The coordinated S=O group
3
. Conclusions
The conformation of the deprotonated form of the SAPh type ligand N-
[
(
bis(diethylamino)phosphoryl]benzenesulfonamide (HL) within the coordination compounds
AgL) and LuL depends significantly on the nature of the metal ion. In the case of the Lu
n
3
complex, the usual coordination mode via the oxygen atoms of the sulfonyl and phosphoryl groups
occurs, whereas in the Ag complex, the chelate coordination of the SAPh ligand is accompanied by
a bridging function of the imide nitrogen atom. Such a type of coordination mode is observed for d-
metal complexes for the first time. It could be noted that no water or other solvent molecules are
found in the structure. The compounds are thermally stable up to 310 °C (LuL
3
) and 220 °C
(
(AgL) ); the decomposition starts upon further heating. ESI and MALDI mass-spectroscopic
n
studies show rather complicated pathways for the fragmentation process, but the major peaks can be
assigned. DFT calculations show the possibility of dimer formation, which was observed in the
mass spectra.
4
. Experimental
4
.1. Materials and methods
All reagents were purchased from commercial sources and used without purification. IR samples
were prepared as KBr pellets (in the case of the complex 2, nujol was used), and the spectra were
–
1
1
recorded with a Perkin-Elmer Spectrum BX spectrometer in the range 4000-400 cm . H (400
3
1
MHz) and P NMR (162.1 MHz) spectra were recorded on a Varian Mercury 400 NMR
spectrometer. The thermal stabilities of 1 and 2 have been determined between 20 and 1000 °C in
–
1
air with a heating rate of 10 °C min by thermal gravimetric (TG) and differential thermal analyses
DTA).
The samples for the MALDI-TOF analysis were prepared as follows: 1 mg of the complex was
(
dissolved in acetonitrile (1 mL). Aliquots of the solution were applied to the steel tips and dried.
MS analysis was performed by the method of laser desorption/ionization on an Autoflex II (Bruker
Daltonics, Germany) mass spectrometer with a nitrogen laser (λ = 337 nm). Experiments were
carried out in the reflectron mode for negative ions in the m/z range from 50 to 2000 a.m.u. The
resulting mass spectra were obtained by acquiring the data of 150 laser shots and processing by the
software FlexAnalysis (Bruker Daltonics, Germany).
LC/MS analysis was performed with an Agilent 1200 HPLC equipped with a single-quadrupole
MSD Agilent G1956B and Multimode ion source Agilent G1978A (Agilent Technologies, USA).
Signals were detected in the SCAN mode 50–500 m/z, fragmentor variable – from 70 to 300 V.
Ionization - MM-ESI in the negative mode, drying gas flow 5.0 L/min, nebulizer pressure 60 psi,
drying gas temperature 300 °C, vaporizer temperature 200 °C.
Quantum-chemical calculations were carried out with Firefly v.8.1.1 software [19] using DFT
[
20] with the hybrid three-parameter Becke–Lee–Yang–Parr functional (B3LYP) [21] with SBKJC

[
22] basis sets to compare the molecular (experimental and calculated) structure and vibrational
wave numbers. The wave number values computed contain known systematic errors [23], and
therefore, we have used the scaling factor values of 0.967 for the B3LYP functional.
Energetic effects of the condensation reactions were calculated according to the formula
∆
Е = Σ Еfull (reaction products) – Σ Еfull (precursors)
and the results are given in kJ / mol, based on the relation 1 a.u. = 2625.5 kJ / mol.
–
5
The accuracy of the energy parameters calculations was 10 a.u. (26 J / mol).
Electronic absorption spectra were calculated using electron density functional theory TD–DFT.
All crystallographic measurements were performed at room temperature on an XCalibur-3
diffractometer (graphite monochromator MoK
α
radiation, λ(MoK ) = 0.71073 Å, CCD-detector, ω-
α
scans). The structures were solved by direct methods using the SHELXTL package [24]. Positions
of the hydrogen atoms were located from the electron density difference maps and refined by the
“
1
riding” model with Uiso = nUeq of the non-hydrogen atom bonded with given hydrogen atom (n =
.5 for methyl groups and n = 1.2 for other hydrogen atoms). The ethyl fragments at the nitrogen
atoms in the structure of HL were disordered, each one over two sites, with refined occupancy
factors 0.600(13) (for C10A) and 0.400(13) (for C10B); 0.745(48) (for C12A) and 0.26 (48) (for
C12B); 0.602(16) (for C13A, C14A) and 0.400(16) (for C13B, C14B); 0.559(10) (for C7C, C7D)
and 0.441(10) for C8C, C8D); 0.510(11) (for C11C, C12C, C13C, C14C) and 0.490(11) (for C11D,
C12D, C12D, C14D).
4
.1 Synthesis
HL was synthesized according to the Scheme 1.
Scheme 1.
Synthesis of HL. A solution of diethylamine (53.4 mL, 1.035 mol) in dioxane (100 mL) was placed
into a three-neck round-bottomed flask equipped with a thermometer and cooled down to 5 ºC. A
solution of (phenylsulfonyl)phosphoramidic dichloride (C
6
H
5
SO
2
NPOCl ) (63.5 g, 0.250 mol) [10]
2
in dioxane (100 mL) was added dropwise to the diethylamine solution under stirring. The
temperature was kept below 10 ºC. After the addition was complete, stirring was continued for 1 h,
and then the mixture was left for 3 h. The solvent was then evaporated and the residue was dried in
vacuum. The resulting mixture of HL and HN(C H ) ·HCl was dissolved in water and the solution
2 5 2
was acidified with HClconc to pH ≈ 2. The final product precipitated as a yellowish crystalline
powder which was recrystallized from ethanol to give a white crystalline powder (90 g, 80%), mp =
1
20 °C. HL is soluble in acetone, methanol, ethanol, 2-propanol, DMF and DMSO, and insoluble in
-
1
non-polar solvents and water. IR (KBr, ν cm ): 2980 (NH), 1222 (PO); 1323, 1177 (SO
2
) (Fig. S2,
, 400 MHz, 25 °C) δ, ppm: 2.92 (m, 8Н, СН ); 1.02
). P NMR (162.1 MHz,
1
Supporting Information). H NMR (DMSO-d
t, 12Н, СН , JР-H = 7.2 Hz); 7.95 (Н
DMSO-d ) δ, ppm: 6.66 (m, JP-H=6.5 Hz).
6
2
31
(
3
α
, JH-H = 8 Hz, С
6
Н
5
6 5
), 7.55 (Нβ,γ, С Н
3
6
The sodium salt NaL was prepared by the reaction of equimolar amounts of sodium methoxide
and HL in 2-propanol medium. The resulting solution was evaporated to dryness and the fine-
-
1
crystalline powder was collected. IR (KBr, ν cm ): 1130 (PO); 1210, 1040, 1075 (SO
2
) (Fig. S3,
); 0.88 (t,
). P NMR (162.1 MHz,
1
Supporting Information). H NMR (DMSO-d , 400 MHz, 25 °C) δ, ppm: 2.86 (8Н, СН
2
6
3
1
1
2Н, СН
3
, JP-H = 6.8 Hz);7.77 (Н
α
, JP-H = 8 Hz, С
6
Н
5
), 7.33 (Нβ,γ, С
6
Н
5
3
DMSO-d ) δ, ppm: 10.16 (m, JP-H=11.3 Hz).
6

Synthesis of 1. Lu(NO
solution was added to a NaL solution (0.35 g, 0.95 mmol) in a mixture of i-PrOH and CH
0 mL). After 20 min of stirring, the precipitate of NaNO was filtered and washed with small
amount of cold i-PrOH. The resulting mother liquor was left for crystallization in a vacuum
3
)
3
·4.78H
2
O (0.14 g, 0.31 mmol) was dissolved in i-PrOH (10 mL), and the
3
OH (1:1,
2
3
-
1
desiccator. Colorless crystals of LuL
PO); 1194, 1113 (SO ) (Fig. S4, Supporting Information). H NMR (DMSO-d
δ, ppm: 2.49 (8Н, СН ); 0.89 (m, 12Н, СН , JP-H= 6.8 Hz); 7.89 (Н , JP-H = 7.6 Hz, С
).
3
were collected after several days. IR (KBr, ν cm ): 1164
1
(
2
6
, 400 MHz, 25 °C)
); 7.37
2
3
α
6 5
Н
(
6 5
Нβ,γ, С Н
Synthesis of 2. AgNO
was added to a NaL solution (0.21 g, 0.56 mmol) in i-PrOH (10 mL). After 30 min, the precipitate
of NaNO was filtered and washed with small amount of acetonitrile. The resulting clear solution
was left for crystallization in a dark vacuum dessicator. Colorless crystals of (AgL) were collected
after several days. The complex 2 is light sensitive. IR (nujol mull, ν cm ): 1150 (PO); 1270, 1090,
3
(0.097 g, 0.56 mmol) was dissolved in acetonitrile (10 mL), and the solution
3
n
-1
1
1
060 (SO
2
) (Fig. S5, Supporting Information). H NMR (DMSO-d
6
, 400 MHz, 25 °C): δ 2.65 (8Н,
СН ); 0.64 (t, 12Н, СН
2
3
, JP-H= 6.8 Hz); 7.56 (Н , С Н ), 7.05 (Нβ,γ, С Н ).
α
6
5
6
5
4
.2. Thermal gravimetric analysis
TGA was carried out to evaluate the thermal stabilities of 1 and 2. As can be seen (Fig. S6,
Supporting Information), the TGA curve of 1 does not show any weight loss until heating to
3
10 °C, which suggests that this compound does not contain solvent or water molecules. The largest
weight loss (approximately 77% of the starting weight) occurs in the range 310–410 °C, which
might be attributed to the decomposition of LuL . The decomposition process is completed around
20 °C, resulting in lanthanide polyphosphate as the final product (approximately 15% of the
starting weight). The TGA curves indicate that 2 is stable up to 220 °С, which suggests that this
compound also does not contain solvent or water molecules. Further destruction of (AgL) occurs in
3
9
n
three steps. The temperature range and weight loss percentages (shown in brackets) for the first
decomposition step are 220-310 °С (19 %, decomposition of the organic ligand), for the second step
–
8
310-350 °С (38%, final oxidation decomposition of the organic ligand) and for the third – 350-
00 °С (14%, polyphosphate conversion). The calculated metal content (28.7%) for the residue as
well as analysis of its IR spectrum testify Ag
3
PO as the residue’s main component.
4
Appendix A. Supplementary data
Crystallographic data for the structures reported in this paper have been deposited with the
Cambridge Crystallographic Data Center. The CCDC numbers are 985455, 985456 and 985457.
Copies of the data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html or
from the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033; E-mail:
deposit@ccdc.cam.ac.uk.
Acknowledgments
We are grateful to Dr. A.M. Ostapchuk (Danylo Zabolotny Institute of microbiology and virology)
for his help with ESI mass spectroscopy.
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3 n
We report the synthesis of two novel complexes, LuL and (AgL) , based on a
sulfonylamidophosphate ligand. The X-ray single crystal structures of the ligand and the complexes
were determined, showing two different coordination modes in the complexes. ESI and MALDI
mass-spectroscopic studies of (AgL)
n
show rather complicated pathways for the fragmentation
process. The results were supported by DFT calculations.