Specific features of the structure of chelate complexes of N-thiocarbamoylamidophosphates with Zn(II) and Cd(II) cations

Article abstract of DOI:10.1007/s11176-006-0014-2

The reaction of potassium salts of N-thiocarbamoylamidophosphates RC(S)NHP(O)(OPr-i)₂X [X = PhNH, p-MeOPhNH, p-BrPhNH, i-PrNH, t-BuNH, Et₂N, C₅H10N, OC₄H₈N, C ₆H₁₁NH] with Zn(II) cation gives complexes of the composition Zn(L-O,S)₂. The Cd(II) complexes could not be isolated under analogous conditions because of their hydrolytic lability. The reaction of thioureas (X = PhNH, p-MeOPhNH) with Cd(II) acetate in DMF provides stable solvato complexes of the composition Cd(DMF)₂L₂. The structure of the resulting compounds was studied by means of IR, ¹H, and ³¹P NMR spectroscopy and EI and ESI mass spectrometry.

Full text of DOI:10.1007/s11176-006-0014-2

Russian Journal of General Chemistry, Vol. 75, No. 12, 2005, pp. 1919 1926. Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 12, 2005,
pp. 2009 2017.
Original Russian Text Copyright
2005 by Sokolov, Safin, Zabirov, Zotov, Cherkasov.
Specific Features of the Structure of Chelate Complexes
of N-Thiocarbamoylamidophosphates
with Zn(II) and Cd(II) Cations
F. D. Sokolov, D. A. Safin, N. G. Zabirov, P. V. Zotov, and R. A. Cherkasov
Kazan State University, Kazan, Tatarstan, Russia
Received December 16, 2004
Abstract The reaction of potassium salts of N-thiocarbamoylamidophosphates RC(S)NHP(O)(OPr-i)2X
[X = PhNH, p-MeOPhNH, p-BrPhNH, i-PrNH, t-BuNH, Et2N, C5H10N, OC4H8N, C6H11NH] with Zn(II)
cation gives complexes of the composition Zn(L O,S)2. The Cd(II) complexes could not be isolated under
analogous conditions because of their hydrolytic lability. The reaction of thioureas (X = PhNH, p-MeOPhNH)
with Cd(II) acetate in DMF provides stable solvato complexes of the composition Cd(DMF)2L2. The structure
1
of the resulting compounds was studied by means of IR, H, and 31P NMR spectroscopy and EI and ESI mass
spectrometry.
N-Thioacyl- and N-thiocarbamoylamidophosphates
of the general formula RC(S)NHP(Y)R2 (HL) (Y = O
or S, R = OAlk, OAr) I are organoelement analogs of
-dicarbonyl compounds [1]. They are weak NH acids
(pKa 6 9). The negative charge in their anions is
distributed between the S, Y, and phosphorylamido N
atoms that can be involved in complex formation
[2 6].
bisamidothiophosphate IIc with Cd(II) cation is a
macrocyclic dimer containing two Cd(II) cations a
distorted tetrahedral CdS4 surrounding.
By contract, coordination compounds of Zn(II) and
Cd(II) cations with RC(X)NHP(Y)R2 ligands
that simultaneously contain the donor atoms of sulfur
and oxygen (X
Y) remain practically unexplored.
The appearance of the hard donor carbonyl or phos-
phoryl oxygen atoms in the coordination sphere of the
central ion makes it coordinately unsaturated, which,
in its turn, can lead to formation of heteroligand and
polynuclear complexes with the central atom having
the coordination number 5 or 6. Hence, amidothio-
phosphates I containing different donor atoms X and
Y can have much different coordination properties
compared to their dithio analogs RC(S)NHP(S)R2.
Amidophosphates I have long attracted resear-
chers’s attention due to their ability to form stable
chelates with IB, IIB, and VIIIB subgroup transition
metal cations. These compounds and their complexes
exhibit antiviral activity [7]. They can be used as
stationary phases for GLC [8], as well as components
of ion-selective electrodes [9-12], extractants [13], and
masking reagents in analytical chemistry [2].
The interest in amidophosphates I is also as-
sociated with their use as structural blocks in the
synthesis of supramolecular coordination compounds.
The structures of N-thioacylamidophosphates contain-
ing crown ether substituents on the thiocarbonyl group
and their complexes with Ni(II) and Cu(II) complexes
has been studied [14 16]. The macroring cavities in
these structures remain free and can be further in-
volved in complex formation. Zabirov et al. [17, 18]
have studied polynuclear complexes MnLn [M =
Co(II), Ni(II), Pd(II), Ag(I), Zn(II), Cd(II), Hg(II)]
with bipodal amidothiophosphates of the general
formula [(i-PrO)2P(S)NHC(S)NH]2Z IIa IId [Z =
(CH2)2O(CH2)2 (IIa), (CH2)2O(CH2)2O(CH2)2 (IIb),
(CH2)2 (IIc), (CH2)7 (IId]. By means of X-ray diffrac-
tion it has been established [18] that the complex of
The aim of the present work was to assess the ef-
fect of the structure of amidophosphate ligands I
(Y = O) and synthesis conditions on the composition
and structure of chelate complexes of Zn(II) and
Cd(II) cations. Complexes Zn[RC(S)NP(O)(OPr-i)2
O,S]2 were synthesized by the standard procedure [19]
in the water ethanol medium. The reaction of the
potassium salts of amidophosphates Ia Ii of the
general formula RC(S)NHP(O)(OPr-i)2 (HL) with
Zn(II) cation gives complexes ZnL2 (IIIa IIIi).
Complexes IIIa IIIi are crystalline compounds
stable in air. Their IR spectra give evidence for the
involvement of the C=S and P=O groups of ligands
Ia Ii in complex formation. The IR spectra of com-
plexes IIIa IIIi contain strong broad bands at 1512
1070-3632/05/7512-1919 2005 Pleiades Publishing, Inc.

1920
SOKOLOV et al.
ESI data for the Zn(II) and Cd(II) complexes, m/z (Irel, %)
Comp. no.
[M + H]+
[M + Na]+
[M + K]+
[2M
L]+
[2M + Na]+
IIIa
IIIb
IIIc
IIId
IIIe
IIIf
717 (100)
777 (100)
877 (100)a
649 (100)
677 (100)
677 (100)
701 (100)
705 (100)
729 (100)
767 (100)
827 (21.5)
733 (6.2)
793 (5.8)
891 (5.6)a
665 (19.0)
693 (8.0)
693 (10.8)
716 (5.2)
721 (2.5)
745 (8.4)
783 (12.1)
842 (13.2)
1077 (14.9)a
1167 (16.0)
1313 (10.0)a
975 (9.5)a
1413 (0.4)a
627 (6.8)
655 (2.0)
655 (1.6)
1279 (0.6)a
1334 (1.5)a
1335 (0.8)a
1015 (21.5)a
1017(1.4)a
IIIg
IIIh
IIIi
1049 (0.1)
1056 (0.9)a
1093 (11.0)a
1171 (25.5)
1261 (5.0)
707 (11.2)
IVab
IVbb
1511 (2.5)
a
The strongest peaks in the molecular ion cluster are presented. Unless otherwise specified, the peaks of the ions containing the most
b
abundant isotopes are given.
For the marked compounds, M is the chelate nucleus of the general formula CdL .
2
with cleavage of the intramolecular hydrogen bond
between the secondary NH group of the R fragment
and the P=O oxygen atom in the ligands [6].
OPr-i
H
R
i-PrO
OPr-i
OPr-i
1) KOH;
2) ZnCl2
O
P
S
N
R
P
Zn
N
N
P
OPr-i
OPr-i
1
The H NMR spectra of complexes IIIa IIIe and
S O
O
S
IIIi show a signal of the NH group of the R fragment
as a doublet (4JHP 6.7 8.6 Hz). In the spectra of com-
plexes IIId and IIIi, the broadened doublet of doub-
lets of the NH group of the R fragment degenerates
R
Ia Ii
IIIa IIIi
into a triplet (4JHP 3JHH). Large long-range coupling
constants in Zn(II) and Cd(II) chelates with amido-
phosphates I were previously found in thiourea
PhNHC(S)NHP(S)(OPr-i)2 complexes [19]. The
reason of the increased constant is the stability of the
planar W-shaped conformation of the H1N2C1N1P1
fragment [19].
R = PhNH (a), p-MeOC6H4NH (b), p-BrC6H4NH (c),
i-PrNH (d), t-BuNH (e), Et2N (f), C5H10N (g), OC4H8N
(h), C6H11NH (i).
1
1532 and 1540 1560 cm related to vibrations of the
S
C
N fragment in the N-thioacylamidophosphate
anion [19]. The P=O absorption band shifts by 76
1
116 cm to low frequencies as compared to the free
ligand. The IR spectra of complexes IIIf, IIIg, and
IIIh lack bands characteristic of NH stretching vibra-
tions. The IR spectra of complexes IIIa IIIe and IIIi
contain a single band in the range 3296 3328 cm
assignable to vibrations of the NH group of the R
substituent on the thiocarbonyl carbon atom.
R
N2
1
N
OPr-i
OPr-i
1
H
1
C
1
P
1
S
O
M
The coupling constants in compounds IIIa IIIe
and IIIi depend on the nature of the R substituent and
Complex formation causes a significant (9.5
13.4 ppm) downfield shift of the phosphorus signal
of amidophosphates Ia Ii. The 31P NMR spectra of
complexes IIIa IIIi contain narrow singlet signals at
variy in the series PhNH < p-BrC6H4NH
p-
MeOC6H4NH < i-PrNH < t-BuNH. In our opinion,
the reason for such an order is additional stabilization
of the W-shaped conformation due to increased rota-
tion barrier about the C1 N2 bond. In its turn, the
barrier is increased by increasing steric hindrances and
simultaneously increasing donor effect of the R2
substituent, which increases the electron density on
the C1 N2 bond.
5.7 7.0 ppm.
P
1
The H NMR spectra of chelates IIIa IIIi contain
one set of signals of the isopropoxy groups and the R
substituents of the ligand anions and lack NHP(O)
proton signals.
The signal of the NH proton of fragment R in che-
lates IIIa IIIe and IIIi is shifted upfield by 3 ppm
against free ligands Ia Ie and Ii. This is connected
The electron impact (EI) mass spectra of com-
pounds IIIa IIIe and IIIi contain molecular ion peaks
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 12 2005

SPECIFIC FEATURES OF THE STRUCTURE OF CHELATE COMPLEXES
1921
[M]+. The relative intensities of the isotope peaks of
the [M]+ cluster agree with those calculated from the
empirical formulas of compounds of the composition
ZnL2. Complexes IIIa IIIc with arylamine substitu-
ents on the thiocarbonyl carbon atom have less stable
molecular ions. Hence, the [M]+ peak has a very low
intensity (0.44%) in the mass spectrum of complex
IIIb and absent in the mass spectra of complexes IIIc
and IIId.
thioureas Ia and Ib with Cd(OAc)2 in anhydrous
DMF excludes hydrolysis of the resulting chelates.
But here, too, the unsaturation of the coordination
surrounding of the Cd(II) cation reveals itself by the
formation of stable solvato complexes Cd(DMF)2L2
(IVa, IVb) which were isolated from the reaction
mixture and purified by repeated precipitation with
hexane from methylene chloride. Their structure was
1
studied by IR and H and 31P NMR spectroscopy. The
composition of the complexes was confirmed by
elemental analysis. Compounds Va and Vb are color-
less crystalline powders stable in air.
Investigation of complexes IIIa IIIi by means of
electrospray ionization technique (ESI) allowed to
detect molecular ion peaks for all the synthesized
Zn(II) complexes. The base peak in the spectrum
belongs to the [M + Na]+ cation (see table). The
characteristic ions [M +K]+ are also observed in all
the spectra. The [M + H]+ cations are always unstable
(Irel 1.6 11.2%), and for complexes IIIa IIIc, IIIg,
and IIIh they are not observed at all.
An interesting specific feature of the [Zn2L4 + Na]+
compounds under discussion is the presence of weak
dimer peaks and [Zn2L3]+ fragment peaks in their
ESI spectra. The complexes can dimerize by forming
bridge bonds involving the donor atoms of the ligand,
like in Cd(II) complexes with diphosphinylamines
R2P(X)NHP(Y) [20]. In our case, the formation of
dimeric structures containig tridentate bridging and
bidentate terminal ligands in solution would lead to
either doubling or exchange broadening of NMR
signals. We failed to detect dimers of the Zn(II) com-
plexes by spectral methods. Evidently, they are ex-
tremely unstable in solutions. However, the intensity
of the [Zn2L3]+ and [Zn2L4 + Na]+ peaks for com-
pounds IIIa IIIe and IIIi is sufficiently high (see
table), which does not completely exclude dimeriza-
tion in the crystal phase.
The EI mass spectra of adducts IVa and IVb
contain no molecular ion peaks. The ESI mass spectra
of these complexes fragment ions characteristic of the
complex nucleus CdL2, that is [CdL2 + Na]+, [CdL2 +
K]+, [Cd2L3]+, and [Cd2L4 + Na]+ (see table). Ho-
wever, the ESI spectra contain weak molecular ion
peaks [Cd(DMF)2L2+H]+ at 889(12.0) and 950(2.0)
for products IVa and IVb, respectively.
Comparative analysis of the IR spectra of thioureas
Ia and Ib and their Zn(II) complexes IIIa and IIIb
and adducts IVa and IVb provides evidence for the
presence of a CdL2 chelate nucleus in the latter com-
pounds. Hence, the shift of the P=O absorption bands
1
by 72 cm in complexes IVa and IVb compared with
free ligands Ia and Ib and the appearance of a strong
absorption band of the conjugated SCN fragment
confirms the 1,5-O,S coordination of the ligand anions.
Along with the absorption bands typical of the anionic
form of ligands I, the IR spectra display broad strong
1
C=O absorption bands at 1656 cm , related to DMF.
The phosphorus signals in the NMR spectra are
located in the range characteristic of chelate com-
plexes of ligands I, but they are shifted dowfield by
1 1.5 ppm aganst the signals of Zn(II) complexes of
the same ligands.
The properties of complexes of the soft, easily
polarizable Cd(II) cation differ considerably from
those of Zn(II) chelates with the same ligands. The
coordination surrounding of CdO2S2 occurs to be
considerably less stable than of CdS4 and ZnO2S2. As
a result, the chelates formed are hydrolytically un-
stable and tend to increase the coordination number of
the central atom.
1
The H NMR spectra contain signals of the NMe2
and C(O)H groups of coordinated DMF molecules.
The C(O)NMe2 protons appear as two signals of equal
intensity spaced by 20 Hz, what is connected with
the nonequivalence of the DMF methyl groups due to
hindered rotation about the C(O) N bond.
Hence, attempted synthesis of Cd(II) complexes of
thioureas I in the water ethanol medium failed. The
starting thioureas were isolated from the reaction
mixture, and their unchanged structure was confirmed
The spectra show no signals of the NHP(O) groups
of ligands Ia and Ib. The ratio of the integral inten-
sities of the DMF signals and the signals of the PhNH
1
and i-PrO groups of the ligands in the H NMR spec-
1
by EI mass spectrometry and H and 31P NMR spec-
tra of adducts Cd(DMF)2L2 (IVa and IVb) provide
further evidence for the proposed composition of the
complexes.
troscopy. We suggest that the reason for the failure of
the synthesis is hydrolysis of the complexes in the
water ethanol medium.
Based on the resulting data we can suggest that
Performing the reaction of the potassium salts of
complexes IVa and IVb have a tetragonal bipyramidal
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 12 2005

1922
SOKOLOV et al.
H
O
Me
Me
N
OPr-i
OPr-i
P O
S
R
S
i-PrO
i-PrO
1) KOH;
O
P
R
2Me2NC(O)H
2) Cd(OAc)2
S
Cd
N
N
P
OPr-i
OPr-i
Ia, Ib
N
N
R
Cd
S O
O
P
OPr-i
R
OPr-i
Me
O
N
Me
H
IVa, IVb
R = PhNH (a), p-MeOPhNH (b).
structure. The axial positions in the coordination sur-
rounding of the Cd(II) cation are occupied by the
carbonyl oxygen atoms of the two DMF molecules.
EXPERIMENTAL
The IR spectra IR spectra were recorded on a
Specord M-80 spectrometer for suspensions in mineral
oil between KBr plates in the range 400 3600 cm .
We previously demonstrated the possibility of the
realization of such a coordination surrounding for
amidophosphates I containing donor atoms of dif-
ferent nature X and Y on an example of the com-
plexes of the phosphorylated thiobenzamide PhC(S)
NHP(O)(OPr-i)2(HQ, V) with Co(II) [21], Ni(II) [22],
and Cd(II) [23]. According to X-ray diffraction data,
they have the composition M(HQ)2Q2 (IV). The M(II)
cations have a tetragonal bipyramidal surrounding
M(Oa)2(Oe)2(Se)2. The axial positions are occupied
by two neutral molecules of ligand V coordinated in
monodentate fashion through the P=O oxygen atoms.
1
1
2
The H (300 MHz, internal stabilization by the H
resonance line) and 31P NMR spectra (121.42 MHz,
external standard 85% phosphoric acid) of 0.02 M
CDCl3 solutions were registered on a Varian Unity
300 spectrometer (300 MHz). The EI mass spectra
were obtained on TRACE MS Finnigan MAT in-
strument, ionizing ]energy 70 eV, ion source tempera-
ture 200 C. The ampule in the direct inlet probe was
heated from 35 to 150 C at 35 C/min steps. The mass
spectra were treated using the Xcalibur program. The
ESI mass spectra were registered on a Thermo Fin-
6
Hence, our study showed that the structure and
properties of Cd(II) complexes of N-thioacylamido-
phosphates RC(S)NHP(O)R2 with significantly differ
from our previously studied Zn(II) complexes. The
Cd(II) cation in these compounds exhibits pronounced
coordination unsaturation. This results in enhanced
tendency of theses complexes for hydrolysis and the
ability to increase the coordination number of the
central atom due to coordination with neutral donor
ligands. This allows adducts of the composition
Cd(B)2L2 (B = DMF, HL) to be isolated. Solvent
molecules and, as we showed previously [23], neutral
N-thioacylamidophosphate (HL) molecules can act as
such ligands. Evidently, the mode of coordination of
the neutral ligands in such compounds and the stab-
ility of the resulting adducts should strongly depend
on the nature of the N-thioacylamidophosphate and
the structure of the extra ligand. Due to that the
ability of the CdL2 complexes to react with molecules
containing polar groups can further be used for design
of new types of stationary phases for GLC and agents
for molecular recognition and transport of organic
compounds.
nigan-LCQ instrument for 10
M solutions in
1
CHCl3 MeCN (1:1), sample flow rate 3 lmin ,
ionizing voltage 4.10 kW, capillary temperature
210 C.
Commercially available amines vere used after
repeated fractionation. Diisopropyl isothiocyanato-
phosphinate [24] was prepared and purified according
to the published procedures. The solvents were puri-
fied and dried by conventional procedures [25]. All
starting materials and solvents were freshly distilled
or crystallized.
N-Phosphorylated thioureas Ia Ii (general pro-
cedure). A solution of 0.045 mol of amine in 15 ml
of anhydrous CH2Cl2 was treated with vigorous stir-
ring with a solution of 0.05 mol of diisopropoxyphos-
phoryl isothiocyanate in 15 ml of anhydrous CH2Cl2.
The mixture was stirred for an additional 30 min to
complete the reaction. The solvent was removed in a
vacuum, and the product was purified by crystalliza-
tion from a 1:5 mixture of methylene chloride and
hexane.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 12 2005

SPECIFIC FEATURES OF THE STRUCTURE OF CHELATE COMPLEXES
1923
N-(Diisopropoxyphosphoryl)-N -phenylthiocar-
bamide (Ia). Colorless crystals. Yield 7.5 g (53%),
N-(Diisopropoxyphosphoryl)-N ,N -diethylthiocar-
bamide (If). Colorless crystals. Yield 6.40 g (48%),
mp 107 108 C. IR spectrum, , cm : 1240 (P=O);
1
mp 124 125 C (124 125 C [24]). IR spectrum,
,
1
cm : 1244 (P=O); 1012 (POC); 1508 (S C NH);
1000, 1030 (POC); 1500, 1520 (S=C NH); 3128
1
1
(NH). H NMR spectrum, , ppm (J, Hz): 1.24 t [6H,
3136, 3304 (NH). H NMR spectrum, , ppm (J, Hz):
3
Me(Et), JHH 7.0]; 3.58 3.82 m [4H, CH2(Et)]; 1.36 d
7.20 7.26 m [1H, p-H(Ph)]; 7.35 7.40 m [2H, m-
H(Ph)]; 7.60 7.62 m [2H, o-H(Ph)]; 1.39 d [6H,
3
[6H, Me(i-PrO), JHH 6.2]; 1.37 d [6H, Me(i-PrO),
3
3
3JHH 6.1]; 4.82 d.septet [2H, CH(i-PrO), JHH = JPH
3
3
Me(i-PrO), JHH 6.0]; 1.40 d [6H, Me(i-PrO), JHH
6.1]; 4.75 d.septet [2H, CH(i-PrO), 3JHH 6.2, 3JPH 7.3];
6.2]; 6.88 s [1H, P(O)NH]. 31P {1H} NMR spectrum:
2
6.94 d [1H, P(O)NH, JPH 6.1]; 10.78 s (1H, PhNH).
3.9 ppm.
P
{1H} NMR spectrum :
5.3 ppm.
31
P
N-(Diisopropoxyphosphoryl)piperidine-1-thio-
carboxamide (Ig). Colorless crystals. Yield 12.50 g
N-(Diisopropoxyphosphoryl)-N -( p-methoxy-
phenyl)thiocarbamide (Ib). Light blue crystals.
Yield 11.21 g (72%), mp 127 128 C. IR spectrum, ,
1
(90%), mp 67 69 C, IR spectrum, , cm : 1248
1
(P=O); 1000 (POC); 1506 (S=CNH); 3147 (NH). H
1
cm : 1244 (P=O); 1020 (POC); 1512 (S=C NH);
NMR spectrum, , ppm (J, Hz): 1.62 1.69 m (6H,
1
3120, 3272 (NH). H NMR spectrum, , ppm (J, Hz):
, -CH2, C5H10N); 3.83 3.92
m
(4H,
-CH2,
3
3.79 s (3H, MeO); 6.89 6.92, 7.43 7.45 m (4H, Ar);
C5H1)N); 1.36 d [12H, Me(i-PrO), JHH 6.2];
3
3
3
1.38 d [12H, Me (i-PrO), JHH 6.1]; 4.73 d.septet [2H,
4.77 d.septet [2H, CH(i-PrO), JHH 6.3, JPH 7.3];
3
3
7.65 s [1H, P(O)NH]. 31P {1H} NMR spectrum:
CH(i-PrO), JHH 6.3, JPH 7.3]; 6.67 s [1H, P(O)NH];
P
10.53 s (1H, p-MeOPhNH). 31P {1H} NMR spectrum:
3.4 ppm.
6.9 ppm.
P
N-(Diisopropoxyphosphoryl)morpholine-4-thio-
carboxamide (Ih). Colorless crystals. Yield 13.40 g
N-(Diisopropoxyphosphoryl)-N -( p-bromo-
phenyl)thiocarbamide (Ic). Pink crystals. Yield
1
(96%), mp 99 101 C. IR spectrum, , cm : 1236
1
1
11.38 g (64%), mp 133 134 C. IR spectrum, , cm :
(P=O); 1020 (POC); 1508 (S=C NH); 3128 (NH). H
1228 (P=O); 1012 (POC); 1508 (S=C NH); 3160,
NMR spectrum, , ppm (J, Hz): 3.69 3.72 m [4H,
1
3248 (NH). H NMR spectrum, , ppm (J, Hz): 7.46
(OC4H8N)]; 3.94 3.97 m [4H, (OC4H8N)]; 1.33 d
3
7.54 m (4H, Ar); 1.37 d [6H, Me(i-PrO), 3JHH 6.1],
[12H, Me(i-PrO), JHH 6.1]; 4.73 d.sept [2H, CH(i-
3
3
3
1.38 d [6H, Me(i-PrO), JHH 6.0]; 4.72 d.septet [2H,
PrO), JHH 6.3, JPH 7.2]; 8.26 s [1H, P(O)NH]. 31P
3
3
CH(i-PrO), JHH = JPH 6.3]; 6.99 s [1H, P(O)NH];
{1H} NMR spectrum:
3.8 ppm.
P
10.79 s (1H, p-BrPhNH). 31P {1H} NMR spectrum:
N-Cyclohexyl-N -(diisopropoxyphosphoryl)thio-
carbamide (If). Colorless crystals. Yield 15.78 g
(98%), mp 108 110 C (107.5 109 [26]). IR spectrum,
5.8 ppm.
P
N-(Diisopropoxyphosphoryl)-N -isopropylthio-
carbamide (Id). Colorless crystals. Yield 4.1 g
1
, cm : 1220 (P=O), 1016 (POC); 1500, 1552
1
1
(32%), mp 91 92 C. IR spectrum, , cm : 1216
(S=C NH); 3160, 3280 (NH). H NMR spectrum, ,
(P=O); 966, 1020 (POC); 1504, 1552 (S=C NH);
ppm (J, Hz): 1.08 1.48 m (5H, multiplet overlapping
with i-PrO methyl proton signals), 1.48 1.76 m (3H),
1.88 2.08 m (2H), [ , , -CH2 (C6H11N)], 4.08
4.22 m [1H, CHN (C6H11N)]; 1.33 d [6H, Me(i-PrO),
1
3144, 3272 (NH). H NMR spectrum, , ppm (J, Hz):
3
1.30 d [6H, Me(i-Pr), JHH 6.5]; 4.46 d.septet [1H,
3
3
CH(i-Pr), JHH 6.6. JHP 7.8]; 1.39 d [6H, Me(i-PrO),
3JHH 6.1]; 1.40 d [6H, Me(i-PrO), JHH 6.1];
4.69 d.septet [2H, CH(i-PrO), JHH 6.3, JPH 7.5];
3JHH 6.2]; 1.34 d [6H, Me(i-PrO), JHH 6.1)];
3
3
3
3
3
3
4.63 d.septet [2H, CH(i-PrO), JHH 6.3, JPH 7.4];
2
2
7.28 d [1H, P(O)NH, JPH 6.8]; 8.81 d (1H, i-PrNH,
6.84 d [1H, P(O)NH, JPNH 4.5]; 8.83 d (1H, C6H11
NH, JHCNH 7.4). 31P {1H} NMR spectrum:
3JHH 7.8). 31P {1H} NMR spectrum:
5.3 ppm.
3
P
P
4.8 ppm.
N-(Diisopropoxyphosphoryl)-N -tert-butylthio-
carbamide (Ie). Colorless crystals. Yield 12.39 g
(93%), mp 109 110 C (107 109 C [26]). IR spect-
Zn(II) complexes IIIa IIIi) (general procedure).
A solution of 0.005 mol of compound Ia Ii in 10 ml
of ethanol was treated with a solution of 0.0055 mol
(10%) of KOH in 20 ml of ethanol. The reaction mix-
ture was stirred for 30 min, and then a solution of
0.0075 mol (50% excess) of ZnCl2 in 20 ml of distil-
led water was added dropwise. After the addition was
complete, the reaction mixture was stirred for 3 4 h.
The product was extracted from the reaction mixture
1
rum, , cm : 1236 (P=O), 988, 1024 (POC); 1528
1
(S=C NH); 3128, 3288 (NH). H NMR spectrum, ,
ppm (J, Hz): 1.51 s (9H, t-Bu); 1.33 d [6H, Me(i-PrO),
2
3JHH 6.0); 1.34 d [1H, P(O)NH, JPH 6.0]; 4.64
3
3
d.septet [2H, CH(i-PrO), JHH 6.2, JPH 7.1], 6.34 d
P(O)NH, JPH 6.4], 8.87 s (1H, t-BuNH). 31P
2
[1H,
{1H} NMR spectrum:
6.4 ppm.
P
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 12 2005

1924
SOKOLOV et al.
1
with small portions of CH2Cl2, and the combined
solutions were dried over MgSO4. The solvent was
removed, and the product was crystallized from a 1:5
methylene chloride hexane mixture. The resulting
complexes all were colorless crystals.
(NH). H NMR spectrum, , ppm (J, Hz): 1.10 d
3
[12H, Me(i-Pr), JHH 6.5]; 4.07 d.septet [2H, CH(i-Pr),
3JHH 6.8, JHNNNH 7.1]; 1.27 d [12H, Me(i-PrO), JHH
6.1]; 1.28 d [12H, Me(i-PrO), JHH 6.1]; 4.57 d.septet
[4H, CH(i-PrO), JHH 6.5, JPN 7.0]; 5.70 t (2H,
i-PrNH, JHNCNP = JHH 8.0). 31P {1H} NMR spec-
[M]+ (1P8.4), 563 [M SH]+ (1.15), 584 [M C3H6]+
(1.54), 568 [M i-PrNH]+ (3.6), 536 (3.9), 510 (8.4),
468 (5.6), 402 (8.5), 346 (12.2), 282 [HL] (37.3), 265
(14.6), 261 (14.3), 240 (11.6), 197 (27.1), 165 (80.3),
123 (100.0), 98 (43.3), 83 (66.0), 58 (88.4), 43 [C3H7]+
(92.5). Found, %: C 38.27, H 7.03, N 8.89, P 9.90, S
10.23, Zn 10.22. C20H44N4O6P2S2Zn. Calculated, %:
C 38.25, H 7.06, N 8.92, P 9.86, S 10.21, Zn 10.41.
3
3
3
3
3
2
3
Bis[N-(diisopropoxyphosphoryl)-N -phenylthio-
carbamido-O,S]zinc(II) (IIIa). Yield 0.99 g (57%),
trum:
7.0 ppm. Mass spectrum, m/z (Irel, %): 626
1
mp 118 119 C. IR spectrum, , cm : 1096, 1140
(P=O); 1000 (POC); 1528, 1560 (S
C
N); 3312
(NH). 1H NMR spectrum, , ppm (J, Hz): 4.05
7.10 m [2H, p-H(Ph)]; 7.25 7.30 m [4H, m-H(Ph)];
7.48 7.50 m [4H, o-H(Ph)]; 1.31 d [24H, Me(i-PrO),
3JHH 6.3]; 4.63 d.septet [4H, CH(i-PrO), 3JHH 6.2, 3JPH
4
7.6]; 7.57 d (2H, PhNH, JHNCNP 6.7). 31P {1H}
NMR spectrum:
6.3 ppm. Mass spectrum, m/z (Irel,
%): 694.40 [M]+ P(0.4), 661 [M
SH]+ (0.6), 602
[M PhNH]+ (1.1), 316 [HL] (60.6), 282 (69.8), 274
(15.8), 240 (58.2), 198 (100), 181 (50.3), 152 (39.5),
135 (46.7), 118 (98.2), 93 (79.4), 77 (49.0), 65 (54.9),
Bis[N-tert-butyl-N -(diisopropoxyphosphoryl)-
thiocarbamido-O,S]zinc(II) ((IIIe). Yield 1.61 g
1
(95%), mp 166 167 C. IR spectrum, , cm : 1108,
43 [C3H7]+ (78.0). Found, %: C 44.83, H 5.74, N 8.07, 1144 (P=O); 1004, 1032 (POC); 1516, 1544 (S
C
1
P 8.93, S 9.19, Zn 9.37. C26H40N4O6P2S2Zn. Cal-
culated, %: C 44.86, H 5.79, N 8.05, P 8.90, S 9.21,
Zn 9.39.
N); 3328 (NH). H NMR spectrum, , ppm (J, Hz):
1.32 s (18H, t-Bu); 1.26 d [12H, Me(i-PrO), 3JHH 6.4];
3
1.29 d [12H, Me(i-PrO), JHH 6.5]; 4.57 d.septet [4H,
CH(i-PrO), JHH=3JPH 6.4]; 4.78 d (2H, t-BuNH,
3
Bis[N-(diisopropoxyphosphoryl)-N -(p-methoxy-
phenyl)thiocarbamido-O,S]zinc(II) (IIIb). Yield
4JHNCNP 8.6). 31P {1H} NMR spectrum:
5.7 ppm.
P
1
Mass spectrum, m/z (Irel, %): 654 [M]+ (14.0), 621
[M SH]+ (3.4), 598 [M C4H6]+ (19.0), 565 [M
C4H6 SH]+ (6.4), 542 [M 2C4H6]+ (30.0), 523 (8.3),
509 (6.8), 500 (11.6), 481(8.5), 467 (8.6), 458 (8.6),
425 (8.6), 341 (11.4), 306 (18.0), 295 [M ZnL]+
(49.1), 296 (45.9), 265 (25.1), 253 (41.6), 211 (58.0),
165 (76.5), 156 (68.3), 123 (100.0), 97 [ZnSH]+
(39.3), 83 (54.6), 57 [t-Bu]+ (55.2), 43 [C3H7] (56.6).
Found, %: C 40.31, H 7.34, N 8.55, P 9.41, S 9.81,
Zn 9.99. C22H48N4O6P2S2Zn. Calculated, %: C 40.28,
H 7.37, N 8.54, P 9.44, S 9.77, Zn 9.97.
1.39 g (74%), mp 116 117 C. IR spectrum, , cm :
1104, 1136 (P=O); 1020 (POC); 1512 (S
3296 (NH). H NMR spectrum, , ppm (J, Hz): 3.76 s
C
N);
1
(6H, MeO); 6.79 6.82, 7.35 7.39 m (8H, Ar); 1.26 d
3
[24H, Me(i-PrO), JHH 6.2]; 4.57 d.septet [4H,
3
CH(i-PrO), JHH
=
3JPH 6.1]; 7.47 d (2H, p-
4
MeOPhNH, JHNCNP 7.7). 31P {1H} NMR spectrum:
6.5 ppm. Mass spectrum, m/z (Irel, %) [M]+ absent.
FPound, %: C 44.46, H 5.88, N 7.44, P 8.22, S 8.50,
Zn 8.42. C28H44N4O8P2S2Zn. Calculated, %: C 44.48,
H 5.87, N 7.41, P 8.19, S 8.48, Zn 8.65.
Bis[N-(p-bromophenyl)-N -(diisopropoxyphos-
phoryl)thiocarbamido-O,S]zinc(II) (IIIc). Yield
2.04 g (96%), mp 178 179 C. IR spectrum, , cm :
Bis[N,N-diethyl-N -(diisopropoxyphosphoryl)-
thiocarbamido-O,S]zinc(II) (IIIf). Yield 1.50 g
1
1
(92%), mp 58 59 C. IR spectrum, , cm : 1104,
1
1100, 1128 (P=O); 1028 (POC); 1516, 1560 (S
1135 (P=O); 996 (POC); 1520 (S
C
N). H NMR
1
3
C
N); 3304 (NH). H NMR spectrum, , ppm (J,
spectrum, , ppm (J, Hz): 1.06 t [6H, Me(Et), JHH
7.0]; 1.17 t [6H, Me(Et), JHH 7.0]; 3.48 q [4H,
CH2(Et), JHH 6.9]; 3.71 q [4H, CH2(Et), JHH 6.6];
1.24 d [24H, Me(i-PrO), JHH 6.1]; 4.54 d.septet [4H,
CH(i-PrO), JHH = JPH 6.3]. 31P {1H} NMR spec-
3
3
Hz): 7.37 s (8H, Ar); 1.29 d [24H, Me(i-PrO), JHH
6.0]; 4.59 d.sept [4H, CH(i-PrO), JHH 6.2, JPH 7.0];
7.53 d (2H, p-BrPhNH, JHNCNP 7.7). 31P {1H} NMR
3
3
3
3
4
3
3
3
spectrum:
6.2 ppm. Mass spectrum, m/z (Irel, %):
[M]+ absentP. Found, %: C 36.60, H 4.46, Br 18.70,
N 6.55, P 7.28, S 7.53, Zn 7.70. C26H38Br2M4O6
P2S2Zn. Calculated, %: C 36.57, H 4.49, Br 18.72,
N 6.56, P 7.25, S 7.51, Zn 7.66.
trum:
5.6 ppm. Mass spectrum, m/z (Irel, %): 654
P
[M]+ (40.8), 625 [M Et]+ (5.0), 582 [M Et2N]+
(32.1), 556 (4.8), 540 (10.7), 524 (12.2), 498 (16.8),
482 (12.4), 456 (18.4), 414 (36.7), 380 (20.1), 360
(25.5), 355 (20.9), 275 (40.8), 227 (21.3), 179 (100.0),
151 (30.0), 123 (18.4), 99 (40.0), 72 [Et2N]+ (77.8),
43 [C3H7]+ (59.3). Found, %: C 20.31, H 7.40, N
8.52, P 9.41, S 9.81, Zn 9.95. C22N48N4O6P2S2Zn.
Bis[N-(diisopropoxyphosphoryl)-N -isopropyl-
thiocarbamido-O,S]zinc(II) (IIId). Yield 1.57 g
1
(68%), mp 124 125 C. IR spectrum, , cm : 1104,
1140 (P=O); 1008 (POC); 1532 (S
C
N); 3312
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 12 2005

SPECIFIC FEATURES OF THE STRUCTURE OF CHELATE COMPLEXES
1925
Calculated, %: C 40.28, H 7.37, N 8.54, P 9.44, S
9.77, Zn 9.97.
237 (41.6), 205 (79.0), 165 (22.5), 157 (76.5),
123 (100.0), 98 (94.9), 81 (63.4), 55 (71.3), 43 [C3H7]+
(92.5). Found, %: C 44.07, H 7,38, N 7.93, P 8.74, S
9.08, Zn 9.26. C26H52N4O6P2S2Zn. Calculated, %:
C 44.07, H 7.38, N 7.93, P 8.74, S 9.08, Zn 9.26.
C26H52N4O6P2S2Zn. Calculated, %: C 44.10. H 7.40,
N 7.91, P 8.75, S 9.05, Zn 9.23.
Bis[N-(diisopropoxyphosphoryl)piperidine-1-
thiocarboxamido-O,S]zinc(II) (IIIg). Yield 1.41 g
1
(83%), mp 74 75 C. IR spectrum, , cm : 1104,
1
1144 (P=O); 996 (POC); 1504 (S
C
N). H NMR
spectrum, , ppm (J, Hz): 1.46 br.s [4H, -CH2,
(C5H10N)]; 1.57 br.s [8H, -CH2, (C5H10N)];
Cd(DMF)2L2 complexes IVa and IVb (general
procedure). A solution of 0.0045 mol of compound
Ia or Ib in 20 ml of acetone was treated with a
solution of 0.009 mol (100% excess) of KOH, and
0.1 g of 18-crown-6 was added. The reaction mixture
was stirred for 1 h, and a solution of 0.0023 mol of
Cd(AcO)2 2H2O in 5 ml of DMF was added drop-
wise with stirring. After the addition was complete
the reaction mixture was stirred for an additional 1 h.
The resulting solution was filtered off, the solvent was
removed, and the residue was crystallized from a 1:5
mixture of methylene chloride and hexane. The com-
plexes were obtained as fine crystalline colorless
powders.
3.74 br.s [4H, -CH2, (C5H1)N)], 3.96 br.s [4H,
3
-CH2, (C5H10N)]; 1.25 d [24H, Me(i-PrO), JHH
3
3
6.4]; 4.54 d.septet [4H, CH(i-PrO), JHH = JPH 6.4].
31P {1H} NMR spectrum: P 6.1 ppm. Mass spectrum,
m/z (Irel, %): 678 [M]+ (19.4), 594 [M C5H10N]+
(10.43), 568 (4.58), 552 (3.98), 536 (8.52), 510 (6.2),
468 (6.9), 454 (9.3), 426 (17.1), 372 (17.2), 333
(11.2), 287 (22.0), 269 (8.5), 239 (11.9), 207 (14.8),
191 (36.1), 166 (8.4), 140 (20.7), 123 (16.5), 111
(28.6), 84 [C5H10N]+ (100.0), 43 [C3H7]+ (40.5).
Found, %: C 42.35, H 7.13, N 8.22, P 9.13, S 9.44,
Zn 9.62. C24H48N4O6P2S2Zn. Calculated, %: C 42.38,
H 7.11, N 8.24, P 9.11, S 9.43, Zn 9.61.
Bis[N-(diisopropoxyphosphoryl)morpholine-4-
thiocarboxamido-O,S]zinc(II) (IIIh). Yield 1.35 g
(79%), mp 70 71 C. IR spectrum, cm (J, Hz):
3.62 br.s [4H, OCH2 (OC4H8N)]; 3.66 br.s [4H,
OCH2(OC4H8N)]; 3.81 br.s [4H, NCH2 (OC4H8N)];
4.03 br.s [4H, NCH2(OC4H8N)]; 1.27 d [24H, Me(i-
Bis[N-(diisopropoxyphosphoryl)-N -phenylthio-
carbamido-O,S]bis(dimethylformamide-O)-
cadmium(II) (IVa). Yield 0.46 g (27%), mp 126
1
1
127 C. IR spectrum, , cm : 1172 (P=O); 1012
(POC); 1536 (S
C
N); 3232 (NH), 1656 (C=O).
1H NMR spectrum, , ppm (J, Hz): 6.92 6.96 m [2H,
3
3
PrO), JHH 6.2]; 4.55 d.septet [4H, CH(i-PrO), JHH
Hp (Ph)]; 7.14 7.19 m [4H, Hm (Ph)]; 7.52 7.54 m
6.4, JPH 7.5]. 31P {1H} NMR spectrum:
6.4 ppm.
3
3
Mass spectrum, m/z (Irel, %): 6.82 [M]+ (P33.8), 619
(7.9), 596 [M C4H8NO]+ (27.5), 570 (2.9), 554 (9.8),
538 (9.9), 512 (14.0), 470 (22.4), 428 (57.3), 369
(30.4), 335 (22.7), 321 (16.5), 289 (50.1), 209 (28.4),
193 (67.3), 166 (18.5), 140 (43.4), 123 920.8), 113
(61.2), 86 (70.2), 57 (54.8), 43 [C3H7]+ (100). Found,
%: C 38.65, H 6.51, N 8.17, P 9.09, S 9.34, Zn 9.53.
C22H44N4O8P2S2Zn. Calculated, %: C 38.63, H 6.48,
N 8.19, P 9.06, S 9.37, Zn 9.56.
[4H, Ho (Ph)]; 1.21 d [12H, Me(i-PrO), JHH 6.1];
3
1.24 d [12H, Me(i-PrO), JHH 6.2]; 4.52 d.septet [4H,
3
CH(i-PrO), JHH = 3JPH 6.4]; 8.21 s (2H, PhNH), 2.87 s
[6H, Me(DMF)]; 2.94 s [6H, Me(DMF)]; 8.00 s [2H,
C(O)H(DMF)]. 31P {1H}: 7.5 ppm. Mass spectrum,
m/z (Irel, %): [M]+ absent. Found, %: C 43.25, H 6.14,
Cd 12.61, N 9.48, P 6.99, S 7.22. C32H54CdN6O8P2S2.
Calculated, %: C 43.22, H 6.12, Cd 12.64, N 9.45,
P 6.97, S 7.21.
Bis[N-(diisopropoxyphosphoryl)-N -(p-methoxy-
phenyl)thiocarbamido-O,S]bis(dimethylform-
amide-O)cadmium(II) (IVb). Yield 0.89 g (48%),
Bis[N-cyclohexyl-N -(diisopropoxyphosphoryl)-
thiocarbamido-O,S]zinc(II) (IIIi). Yield 1.11 g
1
(63%), mp 110 111 C. IR spectrum, , cm : 1104,
1
mp 122 124 C. IR spectrum, , cm : 1172 (P=O);
1132 (P=O); 1016 (POC); 1532 (S
C
N); 3312
1010 (POC); 1538 (S
(C=O). H NMR spectrum, , ppm (J, Hz): 3.73 s
C
N); 3235 (NH), 1660
1
(NM). H NMR spectrum, , ppm (J, Hz): 1.05 1.17
m (6H, multiplete overlapping with i-PrO methyl
proton signals), 1.50 1.66 m (6H), 1.84 2.01 m (8H),
[ , , -CH2(C6H11N)]; 3.66 3.82 m (2H, CHN(C6
1
[6H, Me(MeO)]; 6.72 6.75, 7.37 7.40 m (8H, Ar);
3
1.18 d [12H, Me(i-PrO), JHH 5.8]; 1.24 d [12H,
3
Me(i-PrO), JHH 5.9]; 4.47 d.septet [4H, CH(i-PrO),
3
H11N)]; 1.25 d [12H, Me(i-PrO), JHH 6.1]; 1.26 d
3
3JHH = JPH 6.1]; 7.86 s (2H, p-MeOPhNH); 2.85 s
3
[12H, Me(i-PrO), JHH 6.0]; 4.53 m [4H, CH(i-PrO),
[6H, Me(DMF)]; 2.92 s [6H, Me(DMF)]; 7.99 s [2H,
3
4
3JHH 6.4, JPH 6.3]; 5.74 t (2H, C6H11NH, JHNCNP
=
C(O)H(DMF)]. 31P {1H} NMR spectrum:
P
3JHH 7.3). 31P {1H} NMR spectrum:
Mass spectrum, m/z (Irel, %): 706 [M]+ (2,5), 673 [M
CH]+ (0.4), 6.24 [M C6H10]+ (0.9), 608 [M
C6H11NH]+ (0.6), 322 (44.0), 279 (18.3), 247 (14.5),
7.1 ppm.
7.9 ppm. Mass spectrum, m/z (Irel, %): [M]+ absent.
Found, %: C 42.99, H 6.13, Cd 11.85, N 8.87, P 6.56,
S 6.73. C34H58CdN6O10P2S2. Calculated, %: C 43.02,
H 6.16, Cd 11.84, N 8.85, P 6.53, S 6.75.
P
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 12 2005

1926
SOKOLOV et al.
13. Navratil, O., Herrmann, E., Chau, N.T.T., Tea, Ch.,
ACKNOWLEDGMENTS
and Smola, J., Collect. Czech. Chem. Commun., 1993,
The work was financially supported by the Russian
Foundation for Basic Research (project nos. 03-03-
32372-a, 03-03-96225-r2003, Tatarstan), Program for
Support of Scientific and Research work of Post-
Graduate Students of State Institutions of Higher
Professional Education Subordinate to the Federal
Agency for Education (project no. A04-2,11-778), and
Basic Research and Higher Education Bilateral
Program of CRDF and the Ministry of Education of
the Russian Federation (project no. REC-007), and
Basic Research and Higher Education 2004 Program
for Support of Young Scientists (project no. Y2-C-07-
02).
vol. 58, no. 4, p. 798.
14. Zabirov, N.G., Sokolov, F.D., Brusko, V.V., Tash-
mukhamedova, A.K., Saifullina, N.I., and Cherka-
sov, R.A., Mendeleev Commun., 2002, vol. 12, no. 4,
p. 154.
15. Zabirov, N.G., Verat, A.Yu., Sokolov, F.D., Badash-
kina, M.G., Krivolapov, D.V., and Brusko, V.V.,
Mendeleev Commun., 2003, vol. 13, no. 4, p. 163.
16. Sokolov, F.D., Zabirov, N.G., Brusko, V.V., Krivola-
pov, D.V., and Litvinov, I.A., Mendeleev Commun.,
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