Copper(I) complexes of N-thioacylamido(thio)phosphates and triphenylphosphine

Article abstract of DOI:10.1016/j.ica.2005.09.061

Heteroligand copper(I) complexes of bi- or bis-bidentate acylamidophosphates PhC(S)NHP(S)(OPr-i)₂, PhC(S)NHP(O)(OPr-i) ₂, Et₂NC(S)NHP(S)(OPr-i)₂, PhNHC(S)NHP(S)(OPr- i)₂, N-(4-aminobenzo-15-crown-5)-C

Full text of DOI:10.1016/j.ica.2005.09.061

Inorganica Chimica Acta 359 (2006) 475–483
www.elsevier.com/locate/ica
Copper(I) complexes of N-thioacylamido(thio)phosphates and
triphenylphosphine
a,
a,
a
a
Alexander Y. Verat *, Felix D. Sokolov *, Nail G. Zabirov , Maria G. Babashkina ,
b
a
b
Dmitry B. Krivolapov , Vasiliy V. Brusko , Igor A. Litvinov
a
A.M. Butlerov Chemical Institute, Kazan State University, 18 Kremlevskaya street, Kazan 420008, Russian Federation
A.E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Centre of the Russian Academy of Sciences,
8 Arbuzov street, Kazan 420088, Russian Federation
b
Received 21 May 2005; received in revised form 21 September 2005; accepted 22 September 2005
Available online 28 November 2005
Abstract
Heteroligand copper(I) complexes of bi- or bis-bidentate acylamidophosphates PhC(S)NHP(S)(OPr-i)2, PhC(S)NHP(O)(OPr-i)2,
Et2NC(S)NHP(S)(OPr-i)2, PhNHC(S)NHP(S)(OPr-i)2, N-(4-aminobenzo-15-crown-5)-C(S)NHP(S)(OPr-i)2, N,N-(1,10-diaza-18-
crown-6)-[C(S)NHP(S)(OPr-i)2]2, and triphenylphosphine were prepared and characterised. Copper is bound by two PPh3 and one
SCNPX (X = O, S) fragment of chelating ligand in all cases. Triphenylphosphine molecules reversibly dissociate in solution. Details
of the X-ray structures of (Ph3P)2Cu[PhC(S)NP(S)(OPr-i)2] and (Ph3P)2Cu[Et2NC(S)NP(S)(OPr-i)2] are reported.
ꢀ 2005 Elsevier B.V. All rights reserved.
Keywords: Copper complexes; N-phosphorylated thioureas; N-phosphorylated amides; Triphenylphosphine; Crystal structures
1. Introduction
ophosphorylated thiourea 2a (both R = Et; R0 = OPh)
[11]. The copper atoms of 5 adopt a trigonal configuration
as well. The alteration in the ring size for 4 and 5 in com-
parison with each other can be explained both by the differ-
ence in ligand structure and in ionic radii of Cu(I) and
Ag(I) cations.
N-(thio)phosphorylated (thio)amides (1) and N-
(thio)phosphorylated (thio)ureas (2) are known to form
complexes with a variety of metals both soft and hard.
Many complexes of transition [1–5] and alkaline [5–9] met-
als with N-acylamidophosphinates (the general name of
compounds containing XCNPY backbone) have been
reported (see Scheme 1). Among them, transition metal
complexes with C(S)NHP(S) ligands have been investigated
most extensively.
Cu(I) and Ag(I) complexes with 1 and 2 are polynuclear
in solid state. Thus, Ag(I) cations with thiobenzamide
PhC(S)NHP(S)(OPr-i)2 (3) form a tetrameric cyclic com-
plex (4) [10]. The silver atom in 4 has trigonal configura-
tion. A similar cyclic structure has been found in the
trimeric complex of Cu(I) (5), obtained with the N-thi-
Ph
N
OPh
P OPh
N
NEt2
(i-PrO)2
P
C
S
N
S
C
S
S
S
C
S
PhO
PhO
S
P(OPr-i)2
N
Ag
Ag
P
S
Cu
Ph
N
Cu
C
C
S
S
S
Cu
NEt2
Ph
Ag
Ag
Et2N
C
S
S
C
(i-PrO)
2 P
S
N
P
OPh
(OPr-i)
P
2
N
Ph
OPh
4
5
Complexes of monovalent copper are of interest as cat-
alysts of numerous processes including homolytic C–Hal
(Hal = Cl, Br) bond cleavage in polyhaloalkanes [12]. N-
thiophosphorylated bis-thioureas containing a crown ether
*
Corresponding authors. Tel.: +7 8432 315310; fax: +7 8435 543754.
E-mail addresses: averat@mail.ru (A.Y. Verat), felix.sokolov@ksu.ru
(F.D. Sokolov).
0020-1693/$ - see front matter ꢀ 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2005.09.061

476
A.Y. Verat et al. / Inorganica Chimica Acta 359 (2006) 475–483
R'
R'
ther purification. Infrared spectra (Nujol) were recorded on
R'
R'
H
N
H
N
R
R
a Specord M-80 spectrometer in the 400–3600 cmꢀ1 range.
NMR spectra of CDCl3 solutions were obtained on a Var-
R
N
C
X
P
Y
C
X
P
Y
1
ian Unity-300 NMR spectrometer at 25 ꢁC. H, 31P, and
1
2
13C chemical shifts, in ppm, were recorded at 299.948,
121.420, and 75.429 MHz, respectively. Chemical shifts
are reported with reference to SiMe4 (1H and 13C) and
H3PO4 (31P). Electron ionization mass spectra were
recorded on a MKh-1310 instrument. Electron ionization
energy was 70 eV and collector current was 30 lA. The
substance was injected directly into the ion source at
100 ꢁC. The exact values of molecular masses were deter-
mined automatically from the reference peaks of perfluoro-
kerosene with the accuracy of no less than 5 · 10ꢀ6 amu.
ESI mass spectra were recorded on a Thermo Finnigan
LCQ device. Concentrations were about 10ꢀ6 M (1:3
CHCl3/CH3CN), capillary temperature 210 ꢁC. For com-
plexes characterised by ESI in ionic clusters of particles
containing three and more copper atoms the most abun-
dant peaks in theory are mainly not the most intensive.
This is due to overlapping of several closely located peaks.
Here, we report masses of the most theoretically abundant
peaks.
Scheme 1. General formula of N-(thio)phosphoryl(thio)amides (1) and N-
(thio)phosphoryl(thio)ureas (2); X, Y = S, O; R0 = Ar, OAlk, OAr;
R = H, Alk, Ar.
ring as a spacer are of special interest. The latter can par-
ticipate in complexation by binding alkaline metal cations.
Such complexes are interesting as potential binuclear com-
plex catalysts, as models for studying redox processes
within complexes, and as reagents for supramolecular syn-
thesis [13].
Heteroligand copper(I) complexes of triphenylphos-
phine and XCNPY or XPNPX (X, Y = O, S, Se) backbone
ligands (6–9) [5,14–16] have been earlier reported. (The
style of representing the negative charge distribution
through the XPNPX backbone in 6 and 7 was adopted
from the papers cited.)
N
N
N
Ph2P
O
Ph2P
X
PPh2
X
PPh2
O
PhC
O
PPh2
S
2.2. PhC(S)NHP(O)(OPr-i)2 (10)
Cu
Cu
Cu
Synthesis of this compound was published for the first
time in [18]. NaH (2.4 g, 0.1 mol) was added to a solution
of thiobenzamide (6.85 g, 0.05 mol) in THF (100 ml). To
the obtained suspension diisopropylchlorophosphate
(10.02 g, 0.05 mol) was added dropwise. After it the precip-
itate of NaCl was filtered out, and the solvent was removed
in vacuum. The residue was extracted with 1 N KOH solu-
tion. Water phase was separated and treated with H2SO4
(1 N solution) till reaching pH 1. Formed product was
extracted with benzene, dried over MgSO4, solvent was
removed and residue was crystallized from benzene–hexane
mixture (1:3). Yield: 3.0 g (20%). M.p. 134–135 ꢁC. Calc.
for C13H20NO3PS (301.09): C, 51.81; H, 6.69; P, 10.28;
Found: C, 51.70; H, 6.82; P, 10.19%. 31P{1H} NMR
(CD3CN): d = ꢀ7.00. 1H NMR (CD3CN): d = 1.27 (d,
3JHH = 6.0 Hz, 12H, CH3), 4.74 (m, 2H, OCH), 7.34–7.80
PPh3
PPh3
Ph3P
PPh3
X = S 6
X = Se 7
9
8
Haiduc et al. [14] aimed to prepare the non-cluster com-
plex of Cu(I), where the copper atom is bound only to one
molecule of chelating SPNPS ligand. In this case, the filling
of coordination sites of copper(I) is necessary to prevent
cluster formation. The triphenylphosphine was used for
this purpose. We conceived to employ an analogous
method for synthesis of the complexes of crown containing
thiophosphorylated thioureas.
Published data reveal that structure and properties of
triphenylphosphine containing complexes 6–9 are strongly
dependent on the nature of chelating ligand. That is why
we at first prepared copper(I) complexes with thioacylami-
dothiophosphates and triphenylphosphine similar to 6–9.
Recently, we reported some synthetic results presented here
as a preliminary communication [17]. Here we report the
synthesis, characterization, and structure of complexes of
triphenylphosphine and thiophosphorylated amides and
ureas with copper(I). Structures of the obtained complexes
are also discussed.
2
(m, 5H, Ph), 9.50 (d, JPNH = 10.0 Hz, 1H, NH). IR
m
m
NH = 3125s, mNCS = 1500m, mCS = 1346w, mPO = 1274m,
P–O–C = 1012s br cmꢀ1
.
2.3. Potassium salts of 3 and 10
Synthesis of these compounds was published for the first
time in [7]. General procedure: To the solution of 0.1 mol of
3 or 10 in 50–70 ml of methanol in three-necked flask,
0.1 mol of KOH in methanol was added dropwise whilst
stirring. After completion of addition, the solution was stir-
red for 2 h, then methanol was removed at residual pres-
sure 0.1 torr and at temperature 100–110 ꢁC. The
products were isolated as light-yellow powders.
[PhC(S)NP(S)(OPr-i)2]K: Yield 89%. M.p. 165–166 ꢁC.
2. Experimental
2.1. General procedures
All solvents (except EtOH) were dried and distilled prior
to use. Ethanol was of 95.6% grade and used without fur-

A.Y. Verat et al. / Inorganica Chimica Acta 359 (2006) 475–483
477
Calc. for C13H19KNO2PS2 (355.50): C, 43.92; H, 5.39; K,
11.00; P, 8.71; Found: C, 43.84; H, 5.53; K, 10.96; P,
6.12; N, 3.45; P, 10.39; S, 6.45%. 1H NMR (C6D6):
3
d = 1.26 (t, JHH = 7.2 Hz, 3H, CH2CH3), 1.37 (t,
3
8.78%. 31P{1H} NMR (acetone): d = 67.00. IR mPNC
=
.
3JHH = 7.2 Hz, 3H, CH2CH3), 1.53 (d, JHH = 6.3 Hz, 6
1435s, mCS = 1210m, mKꢁ ꢁ ꢁO(P)–C = 960s, mPS = 625w cmꢀ1
H, CHCH3), 1.55 (d, JHH = 6.9 Hz, 6H, CHCH3), 3.67
3
3
3
[PhC(S)NP(O)(OPr-i)2]K: Yield 95%. M.p. 177 ꢁC. Calc.
for C13H19KNO3PS (339.05): C, 46.00; H, 5.54; K, 11.52;
P, 9.13; Found: C, 45.77; H, 5.40; K, 11.56; P, 9.37%.
31P{1H} NMR (acetone): d = 5.00.
(q, JHH = 7.0 Hz, 2H, CH2), 4.04 (q, JHH = 7.1 Hz, 2H,
CH2), 5.19 (d sept, JHH + 3JPH = 10.3 Hz, 2H, OCH),
3
7.20–7.30 (m, 12H, Ph), 7.70–7.80 (m, 18H, Ph). 31P{1H}
NMR (C6D6): d = ꢀ0.70 (PPh3), 54.96 (NPS). IR mNCS
=
.
1580m, mP–O–C = 970–1030s, mPC = 690m, mPS = 564w cmꢀ1
2.7. (Ph3P)2Cu[PhNHC(S)NP(S)(OPr-i)2-S,S0] (14)
2.4. Et2NC(S)NHP(S)(OPr-i)2 (11)
A solution of diethylamine (0.365 g, 5 mmol) in benzene
(25 ml) was added dropwise whilst stirring to a solution of
SCNP(S)(OPr-i)2 (1.2 g, 5 mmol) in benzene (15 ml). After
an hour, benzene was partially removed in vacuum and
reaction mixture became viscous. Then, n-hexane was
added and after several days, colourless crystals began to
form. Yield: 0.99 g (63%). 31P NMR (CCl4 + C6H6):
d = 59.98. 1H NMR (CDCl3): d = 1.30 (br s, 6H, CH2CH3),
This was prepared similarly to compound 13 by using
PhNHC(S)NHP(S)(OPr-i)2 (15). Yield 42%. M.p. 146 ꢁC.
Calc. for C49H50CuN2O2P3S2 (919.53): C, 64.00; H, 5.48;
N, 3.05; P, 10.11; S, 6.97; Found: C, 63.15; H, 6.02; N,
1
3.14; P, 10.77, S, 6.16%. H NMR (CDCl3): d = 1.33 (d,
3
3JHH = 6.3 Hz, 6H, CH3), 1.36 (d, JHH = 6.2 Hz, 6H,
3
3
CH3), 4.79 (d sept, JHH = 6.2 Hz, JPH = 10.6 Hz, 2H,
3
3
3
1.46 (d, JHH = 6.0 Hz, 6H, CH(CH3)2), 1.47 (d, JHH
=
OCH), 7.08 (t, JHH = 7.1 Hz, 1H, p-Ph), 7.24–7.50 (m,
4
6.1 Hz, 6H, CH(CH3)2), 3.66 (br s, 4H, CH2), 4.98 (d sept,
32H, P–C6H5 and o-Ph), 7.57 (d, JPNCNH = 7.9 Hz, 1H,
3JHH = 6.2 Hz, 3JPH = 10.6 Hz, 2H, OCH). IR mNH = 3400,
NH), 7.73 (t, JHH = 8.4 Hz, 2 H, m-Ph). 31P NMR
3
3
m
NCS = 1504s, mP–O–C = 992br, s, mPS = 648m, cmꢀ1
.
(CDCl3): d = ꢀ0.70 (PPh3), 54.96 (d t, JPOCH + 4JPNCNH
= 9.3 Hz, NPS A2MX,). IR mNH = 3260s, mNCS = 1538m,
2.5. (Ph3P)2Cu[PhC(S)NP(S)(OPr-i)2-S,S0] (12)
m .
P–O–C = 984br, mPC = 696m, mPS = 560w cmꢀ1
A solution of (PPh3)2CuNO3 (0.34 g, 0.523 mmol) in
CH2Cl2 (25 ml) was added dropwise whilst stirring to a
solution of [PhC(S)NP(S)(OPr-i)2]K (0.186 g, 0.523 mmol)
in ethanol (25 ml). The mixture was stirred for an hour
and precipitate was filtered off. The filtrate was concen-
trated until crystallization began. Isolated crystals were
precipitated from a dichloromethane/n-hexane mixture
1:5 (v/v). Yield 0.32 g (70%). M.p. 143 ꢁC. Calc. for
C49H49CuNO2P3S2 (904.52): C, 65.06; H, 5.46; Found: C,
65.57; H, 5.59%. 1H NMR (CDCl3): d = 1.30 (d,
2.8. (Ph3P)2Cu[4-(1,2-benzo-15-crown-5)NHC(S)NP(S)
(OPr-i)2-S,S0] (16)
This was prepared similarly to compound 13 by using 4-
(1,2-benzo-15-crown-5)NHC(S)NHP(S)(OPr-i)2 (17). Yield
45%. M.p. 115–117 ꢁC. 1H NMR (CDCl3): d = 1.29 (d,
3
3JHH = 8.4 Hz, 6H, CH3), 1.32 (d, JHH = 6.6 Hz, 6H,
CH3), 3.78 (s, 8H, PhOCH2CH2OCH2CH2), 3.91 (m, 4H,
PhOCH2CH2), 4.12 (m, 4H, PhOCH2), 7.2–7.8 (m, 34H,
C6H5 + C6H3 + NH). 31P{1H} NMR (CDCl3): d = ꢀ0.30
(PPh3), 54.5 (NPS). IR mNCS = 1480m, mP–O–C = 980–
3
3JHH = 6.4 Hz, 6H, CH3), 1.35 (d, JHH = 6.2 Hz, 6H,
3
3
CH3), 4.90 (d sept, JHH = 6.2 Hz, JPH = 10.1 Hz, 2H,
OCH), 7.03–7.76 (m, 35H, Ph). 31P{1H} NMR (CH2Cl2):
d = ꢀ0.62 (2P, PPh3), 54.76 (1P, NPS). IR mNCS = 1508m,
1020s, mPS = 600m, 620m cmꢀ1
.
2.9. (Ph3P)2Cu[PhC(S)NP(O)(OPr-i)2-O,S] (18)
m
P–O–C = 968s, 990s, 1016s, mPS = 586w cmꢀ1
.
This was prepared similarly to compound 12 by using
potassium salt of 10. Yield 86%. M.p. 161 ꢁC. Calc. for
C49H49CuNO3P3S (888.45): C, 66.24; H, 5.56; N, 1.58; S,
3.61; Found: C, 66.76; H, 5.31; N, 1.68; S, 3.92%. 1H
2.6. (Ph3P)2Cu[Et2NC(S)NP(S)(OPr-i)2-S,S0] (13)
To a suspension of Et2NC(S)NHP(S)(OPr-i)2 (11)
(0.156 g, 0.5 mmol) in ethanol (25 ml) a KOH (0.5 mmol)
solution in ethanol (15 ml) was added and the mixture
was stirred until the ligand dissolved completely. To the
resulting potassium salt, a solution of (PPh3)2CuNO3
(0.325 g, 0.5 mmol) in CH2Cl2 (25 ml) was added dropwise.
The mixture was stirred for an hour and a precipitate was
filtered off. The filtrate was concentrated until crystalliza-
tion began. Isolated crystals were precipitated from a
dichloromethane/n-hexane mixture 1:5 (v/v) and used for
a subsequent X-ray analysis. Yield 0.27 g (60%). M.p.
104 ꢁC. Calc. for C47H54CuN2O2P3S2 (899.54): C, 62.76;
H, 6.05; N, 3.11; P, 10.33; S, 7.13; Found: C, 62.25; H,
3
NMR (CDCl3): d = 1.39 (d, JHH = 6.3 Hz, 6 H, CH3),
1.43 (d, 3JHH = 6.3 Hz, 6H, CH3), 4,83 (d sept, 3JHH + 3JPH
= 6.7 Hz, 2H, OCH), 7.24–7.86 (m, 35H, C6H5). 31P{1H}
NMR (CDCl3): d = 4.70 (1P, PO), ꢀ3.62 (2P, PPh3). IR
m
NCS = 1500m, mPO = 1176m, mP–O–C = 1020s br cmꢀ1
.
2.10. (Ph3P)4Cu2{1,10-diaza-18-crown-6[C(S)NP(S)
(OPr-i)2]2-S,S0,S00,S000} (19)
This was prepared similarly to compound 13 using 1,10-
(diaza-18-crown-6)-[C(S)NHP(S)(OPr-i)2]2 (20), a double
amount of KOH, and (PPh3)2CuNO3. Yield 76%. M.p.

478
A.Y. Verat et al. / Inorganica Chimica Acta 359 (2006) 475–483
144–145 ꢁC. Calc. for C98H112Cu2N4O8P6S4 (1915.16): C,
[20]. All non-hydrogen atoms were refined anisotropically.
The hydrogen atoms were included in calculated position
with thermal parameters 30% larger than atom to which
they attached. All calculations were performed on PC using
WINGX [21] program. Cell parameters, data collection and
data reduction were performed on Alpha Station 200 com-
puter using MOLEN [22] program. All figures were made using
the program ORTEP [23].
61.46; H, 5.89; N, 2.93; P, 9.70; S, 6.70; Found: C, 61.22;
1
H, 5.82; N, 2.77; P, 10.15; S, 6.34%. H NMR (CDCl3):
3
d = 1.28 (d, JHH = 6.3 Hz, 12H, CH3), 1.36 (d,
3JHH = 6.0 Hz, 12H, CH3), 3.59–3.65 (m, 8H, NCH2),
3
3.75 (t, JHH = 6.3 Hz, 4H, NCH2CH2O), 3.85 (t,
3
3JHH = 5.4 Hz, 4H, NCH2CH2O), 3.96 (t, JHH = 5.8 Hz,
3
4H, OCH2CH2O), 4.21 (t, JHH = 5.4 Hz, 4H, OCH2-
3
CH2O), 4.73 (d sept, JHH + 3JPH = 8.7 Hz, 4H, OCH
(Pr-i)), 7.32–7.76 (m, 60H, P–C6H5). 31P{1H} NMR
3. Results and discussion
(CDCl3): d = ꢀ0.60 (PPh3), 51.51 (s, NPS). IR mNCS
=
.
1480m, mP-O-C = 1000br, s, mPC = 696m, mPS = 575w cmꢀ1
3.1. Synthesis
N-diisopropoxyphosphorylthiobenzamide 10 has been
obtained by the reaction of thiobenzamide with diisopro-
pylchlorophosphate in the presence of NaH. N-dii-
sopropoxythiophosphorylthiobenzamide 3 was prepared
according to the previously described method [24]. Thi-
ophosphorylated thioureas 11, 15, 17, 20, and 21 (Scheme
2) were prepared by addition of the corresponding amine
to diisopropylthiophosphoryl isothiocyanate [1,25,26].
Heteroligand copper(I) complexes were prepared by the
metathesis reaction between the potassium salts of ligands
and Cu(PPh3)2NO3 (Scheme 3).
2.11. X-ray crystallography
The X-ray diffraction data for the crystals of 12 and 13
were collected on a Enraf-Nonius CAD4 automatic diffrac-
tometer using graphite monochromated Mo Ka (0.71073 A)
˚
radiation. The details of crystal data, data collection, and
the refinement are given in Table 1. The stability of crystals
and experimental conditions was checked every 2 h using
three control reflections, while the orientation was moni-
tored every 200 reflections by centering two standards. No
significant decay was observed. The structure was solved
by direct method using the SIR [19] program and refined by
the full matrix least-squares using the program SHELXL-97
Obtained complexes have been crystallized from
CH2Cl2–hexane solutions. They are readily soluble in
CH2Cl2, CHCl3, acetone, and benzene, poorly soluble in
C2H5OH, i-C3H7OH and insoluble in hexane. The com-
1
pounds have been characterized by IR, NMR H and 31P
Table 1
spectroscopy, two of them have been studied by X-ray crys-
tallography. We also tried to use (PPh3)3CuBr as a starting
material, but in this case it is necessary to separate free tri-
phenylphosphine emerges and so we decided to utilize
Cu(PPh3)2NO3.
Crystallographic data for complexes 12 and 13
12
13
Chemical formula
Crystal habit
C
49H49CuNO2P3S2
C47H54CuN2O2P3S2
colorless prism
0.4 · 0.35 · 0.35
899.49
monoclinic
P21/n
13.058(2)
20.931(2)
17.560(6)
90.00
109(2)
90.00
4538(1)
4
1.32
1888
Mo Ka (0.71073)
293
x/2h
yellow prism
0.4 · 0.4 · 0.4
904.46
Crystal size (mm)
Formula weight
Crystal system
Space group
Reaction of (PPh3)2CuNO3 with the potassium salt of
bis-thiourea 21 along with the target complex affords by-
products. 31P NMR spectrum of the isolated mixture con-
tains resonances at 54.82 (84.0%), 60.15 (5.0%), 51.95
(7.5%) and 43.87 ppm (3.5%). The most intensive signal
was ascribed to the thiophosphoryl group of the expected
complex (22) (Scheme 4) by comparison with the stable
complexes 12–14, 16; the resonance at 60.15 ppm corre-
sponds to the imidothiophosphate (R2N)2C@N–
P(S)(OPr-i)2 (23a and 23b) environment of phosphorus
atom [27]; the resonance at 51.95 ppm corresponds to the
amidothiophosphate environment of phosphorus (24) and
the resonance at 43.87 ppm is due to the thiophosphorylis-
triclinic
ꢀ
P1
˚
a (A)
12.092(2)
12.053(2)
18.899(4)
98.25(2)
104.12(2)
114.65(2)
2332.26
2
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
3
˚
V (A )
Z
Dcalc (g cmꢀ3
)
1.29
F(000)
Radiation (A)
Temperature (K)
Scan mode
944
˚
Mo Ka (0.71073)
293
x/2h
1
othiocyanate SCNP(S)(OPr-i)2 (25). The H NMR spec-
Recording range hmax (ꢁ)
Absorption correction
22.76
Not applied
7.0
23.87
trum also contains signals of low intensity, which
correspond to the products of ligand decomposition. In
the IR spectrum of the mixture there is a strong broad
band in the range 1600–1650 cmꢀ1, which has been
ascribed to the stretching vibration of C@N group. Such
decomposition processes which proceed via N-thiophos-
phoryl-N0-phenylcarbodiimide (RO)2P(S)N@C@NPh (26)
have been previously observed for a number of complexes
of phosphorylated thioureas [1,28–30]. Scheme 4 illustrates
wꢀscans
l (cmꢀ1
)
7.2
Scan speed (deg minꢀ1
Reflections measured
No. of independent
reflections with
F2 P 4r(F0)
R (%)
)
Variable, 1–16.4
5761
5556
Variable, 1–16.4
3298
2241
0.039
0.099
1.03
0.040
0.066
1.02
Rw (%)
S

A.Y. Verat et al. / Inorganica Chimica Acta 359 (2006) 475–483
479
H
N
H
N
H
N
H
N
Ph
R
Z
C
S
P(OPr-i)2
O
C
S
P(OPr-i)2
S
(i-PrO)2P
S
P(OPr-i)2
S
C
S
C
S
10
3, 11, 15, 17
20, 21
Scheme 2. Parent N-acylamido(thio)phosphates. R = Ph (3), NEt2 (11), NHPh (15), 4-aminobenzo-15-crown-5 (17), Z = 1,10-diaza-18-crown-6 (20),
HN(CH2)2O(CH2)2NH (21).
N
R
N
K
R
C
S
P(OPr-i)2
Y
C
S
P(OPr-i)2
Y
(PPh3)2CuNO3
KNO3
+
+
Cu
Ph3P
PPh3
12, 13, 14, 16, 18
O
12 R = Ph, Y = S
13 R = NEt2, Y = S
14 R = NHPh, Y = S
18 R = Ph, Y = O
O
O
16 R =
H
N
O
O
Y = S
O
O
O
O
N
K
N
(i-PrO)2P
S
C
N
N
C
S
P(OPr-i)2
S
(PPh3)2CuNO3
+
S
K
O
O
O
N
N
(i-PrO)2P
C
S
N
N
C
P(OPr-i)2
S
KNO3
+
S
S
O
Cu
Cu
Ph3P
PPh3
Ph3P
PPh3
19
Scheme 3. Synthesis of complexes.
in generalized fashion the decomposition process of the
complex.
molecular ion. In the mass spectrum of 13, there are peaks
of the monomeric complex [CuL]+ cation (m/z 374.2, 21%)
and of dimeric one [Cu2L2]+ (m/z 750.5, 25%). (Here, HL
and H2L are neutral ligands and L is its deprotonated form.)
The spectrum also shows peaks of HL+ (m/z 312.2 8%) and
L+ (m/z 311.3, 11%) cations. In the spectrum of 14, along
with the peak of complex cation [CuL]+ (m/z 394, 5%), the
peaks of carbodiimide [PhN@C@NP(S)(OPr-i)2]+ (m/z
298.2, 100%) and of HL+ (m/z 332.2, 45%) are present.
The carbodiimide peak is even more intense than PPh3
one, again stressing the trend of complexes (and ligands)
containing the RNH– group at carbamide carbon to form
carbodiimides.
Electrospray ionization mass spectra of the complexes
12, 14 and 19 also do not contain molecular ion peaks. This
fact is an evidence for dissociation of labile Cu–PPh3 bond
at high dilution and high temperature conditions. The spec-
tra of the complexes 12, 14 and 19, however, show the pres-
ence of peaks due to species formed in a PPh3 dissociation
process. These are: [CuLPPh3 + H]+ for 12 and 14 (m/z
NMR and IR spectra of the complex 16 contain signals
or bands of small intensity, which correspond to the
decomposition products shown in the Scheme 4. Because
16 is not pure, according to the spectral data, the elemental
analysis has not been performed. It was also observed that
after several days in CHCl3 at 25 ꢁC the solution of 16 is
mainly decomposed. This results in an increase in the sig-
nals of the starting ligand 17 and O@PPh3 resonances in
31P NMR spectra (at 53.2 and 29.5 ppm, respectively).
Overall, complex 16 has greater stability than the complex
formed by bis-urea 21. Decomposition of complex 14,
which also contains the NHCS fragment, was not
observed.
3.2. Mass-spectroscopy
Electron ionization mass spectra of the complexes 12–14
and 18 do not demonstrate peaks corresponding to the

480
A.Y. Verat et al. / Inorganica Chimica Acta 359 (2006) 475–483
H
N
N
C
S
P(OPr-i)2
S
N
C
N
P(OPr-i)2
S
Cu2S
H2S
PPh3
+
+
+
Cu
26
Ph3P
PPh3
22
S
NHC(S)NHP(OPr-i)2
H2O
EtOH
H
N
S
S
H
N
NH C
N
P(OPr-i)2
NH C
O
P(OPr-i)2
S
C
N
P(OPr-i)2
N
C
OEt
H
S
N
P(OPr-i)2
23a
24
S
H
S
N
C
N
P(OPr-i)2
SCNP(OPr-i)2
S
+
N
H
23b
25
Scheme 4. Decomposition processes in the complexes of the phosphorylated thioureas containing RNHCS moiety.
642.0, 4.4% and m/z 657.0, 7.8%, respectively) and
[Cu2LPPh3]+ (m/z 1126.6, 1.2%) for 19. Spectra of 12 and
14 contain peaks of [Cun + 1Ln]+ ions. For the 12:
[Cu3L2]+ (m/z 822.7, 25.6%), [Cu4L3]+ (m/z 1201.7,
100%), [Cu5L4]+ (m/z 1581.0, 0.44%) and for the 14:
[Cu3L2]+ (m/z 852.8, 31.7%), [Cu4L3]+ (m/z 1246.8,
100%), [Cu5L4]+ (m/z 1640.2, 4.7%). Such a high intensity
of the [Cu4L3]+ ions is caused by their stability. We suggest
these ions have cluster structure like the cation
[Cu4{(SPPh2)2N}3]+ [31]. The [Cu3L2]+ and [Cu5L4]+ ions
probably also have a cluster structure, for example the
[Cu5L4]+ ions may originate from tetramers like 4. Diaza-
crown containing complex 19 shows a peak assignable to
[Cu2L + H]+ (m/z 866.9, 70.7%) and peaks where metal
cations are trapped by the crown ether ring: [Cu2L + Na]+
(m/z 889.0, 100%) and [Cu3L] (m/z 928.9, 5.7%). Further-
more, the spectrum of 19 shows peaks of [Cu4L2]+ (m/z
1730.8, 1.9%) and of [Cu5L2]+ (m/z 1793.0, 2.6%). In this
case the extra Cu(I) ions are probably bound by crown
rings and are likely to form cluster centers.
comparison with the free ligand 10 (1252 cmꢀ1). Absorp-
tion band of phosphorylamide NH group disappears
under complexation.
The 1H NMR spectra of the complexes contain the
only signals which corresponds to the proposed structure.
Signals of Et2N group in 13 are doubled due to hindered
rotation. The spectrum of 19 shows more signals in the
region of crown ether ring than the expected number of
nonequal protons, this is evidence for the crown ether
ring having different conformers in solution. Methyl pro-
tons in isopropyl groups are diastereotopic and show two
4
signals in spectra. A rather high JPNCNH coupling con-
stant (7.9 Hz) in 14 was already observed for Cd, Zn,
Pd and Ni, complexes of the ligand 15 [4]. It was
explained by the fact that the PNCNH chain in these
complexes meets the so-called W-criterion [32]. The reso-
nance at 51.4–55.0 ppm in 31P NMR spectra of 12–14, 16,
and 19 corresponds to the phosphorus of thiophosphoryl
group. The resonance of the phosphoryl phosphorus in 18
appears at 4.70 ppm and is shifted to low field in compar-
ison with the free ligand 10 (ꢀ7 ppm). The signals of tri-
phenylphosphine are observed from ꢀ0.3 to ꢀ3.62 ppm,
and occur downfield of free PPh3. Triphenylphosphine
signals in the complexes 12–14, 16, and 19, which contain
thiophosphoryl groups have a chemical shift found to be
very close to that in the trigonal complex 6 (ꢀ0.7 ppm)
[14].
3.3. IR and NMR spectroscopy
The IR spectra of copper complexes exhibit absorption
bands at the ranges 1490–1580, 970–1030 and 690–
696 cmꢀ1, which were assigned to the group and stretch-
ing vibrations of SCN, POC and P–C (P–Ph) groups,
respectively. The P@S absorption band shifts to lower fre-
quency from 620–648 in parent ligands to 560–600 cmꢀ1
in the complexes. In complex 18, the P@O vibration is
observed at 1176 cmꢀ1 and shifts to lower frequencies in
Fast exchange between free and bound triphenylphos-
phine in solutions of studied complexes results in phos-
phine signal broadening in 31P NMR spectra, as was
observed for the Cu(I) thioether complexes (see [33] and

A.Y. Verat et al. / Inorganica Chimica Acta 359 (2006) 475–483
481
references therein). An exchange equation can be written as
follows:
example of stronger hindrance is a (PPh3)3CuI molecule:
Cu–P bond length is 2.362 A [34].
˚
P–S and C–S bonds are longer while P–N and C–N are
shorter in comparison to those for the free ligand 3 [35],
and have intermediate bond order values between the dou-
ble and the single. The six-membered CuSPNCS metallocy-
cle in 12 has the conformation of a distorted boat with the
Cu[RC(S)NP(S)(OPr-i)2] (PPh3)2
¢ Cu[RC(S)NP(S)(OPr-i)2]PPh3 + PPh3
Peak widths of signals at half height maximum are in the
range 30–50 Hz. This broadening affords the infringement
of the ratio of integral intensity of the signals of triphenyl-
phosphine and thiophosphoryl groups. For instance, in the
compound 14 the integral intensity of the PPh3 phosphorus
is 1.47 times higher than it is for the thiophosphoryl phos-
phorus. At the same time, the ratio of intensity of the phos-
phine phosphorus to the phosphoryl one is exactly 2:1 in
the 13, 16 and 18. A similar drawback is absent in the pro-
ton spectra. The ratio of integral intensity of phenyl pro-
1
tons to the alkyl protons in the H NMR spectra reveals
the composition of phosphorylthiourea: PPh3 = 1:2 for
complexes 12–14, 16, 18, and 1:4 for the 19.
3.4. Crystal structure of complexes 12 and 13
The molecular structures of 12 and 13 are shown in Figs.
1 and 2, respectively. Selected bond lengths, bond and tor-
sion angles are given in Table 2. The geometry around the
Cu atom is tetrahedral in both complexes formed by two
sulfurs and two PPh3. The values of bond angles around
Cu are in the range from 103.14(4)ꢁ to 119.58(5)ꢁ and from
105(2)ꢁ to 116(2)ꢁ for 12 and 13, respectively. P–Cu bonds
are longer than they are in the trigonal complexes 6, 7, 9
˚
(2.216, 2.222, 2.190 A, respectively) and tetrahedral 8
Fig. 2. ORTEP view of (Ph3P)2Cu[Et2NC(S)NP(S)(OPr-i)2] 13.
˚
(2.255 and 2.245 A). The difference in P–Cu bond lengths
in comparison with trigonal complexes testifies for some
sterical hindering of triphenylphosphine molecules. An
Table 2
˚
Selected bond distances (A), bond and torsion angles (ꢁ) for compounds 12
and 13
12
13
Cu(1)–S(1)
Cu(1)–S(2)
Cu(1)–P(1a)
Cu(1)–P(1b)
S(1)–P(1)
S(2)–C(1)
P(1)–N(1)
N(1)–C(1)
2.356(1)
2.299(1)
2.311(1)
2.280(1)
1.965(1)
1.715(4)
1.593(3)
1.290(5)
2.337(2)
2.304(2)
2.302(2)
2.335(2)
1.980(3)
1.727(9)
1.575(7)
1.32(1)
S(1)–Cu(1)–S(2)
S(1)–Cu(1)–P(1a)
S(1)–Cu(1)–P(1b)
S(2)–Cu(1)–P(1a)
S(2)–Cu(1)–P(1b)
P(1a)–Cu(1)–P(1b)
Cu(1)–S(1)–P(1)
Cu(1)–S(2)–C(1)
S(1)–P(1)–N(1)
107.09(4)
103.74(5)
107.65(4)
103.14(4)
114.58(4)
119.58(4)
103.30(5)
109.0(1)
120.8(1)
134.3(3)
129.4(3)
108(2)
116(2)
105(2)
111(2)
108(2)
109(2)
98(2)
111(2)
123(2)
130(2)
128(2)
P(1)–N(1)–C(1)
S(2)–C(1)–N(1)
S(1)–P(1)–N(1)–C(1)
P(1)–N(1)–C(1)–S(2)
P(1)–N(1)–C(1)–C(2)
P(1)–N(1)–C(1)–N(2)
ꢀ41.0(5)
0.2(6)
ꢀ176.4(3)
55(2)
ꢀ8(2)
173(2)
Fig. 1. ORTEP view of (Ph3P)2Cu[PhC(S)NP(S)(OPr-i)2] 12.

482
A.Y. Verat et al. / Inorganica Chimica Acta 359 (2006) 475–483
Table 3
Y2-C-07-02) and the Russian Foundation for Basic Re-
search (Grants # 03-03-32372-a, 03-03-96225-r2003tatar-
stan_a) for financial support.
Deviations of atoms from the least square plane of the CuSPNCS cycle in
12 and 13
12
13
0.027(2)
0.275(3)
ꢀ0.362(3)
0.148(7)
0.154(9)
ꢀ0.242(3)
Cu
ꢀ0.139(1)
ꢀ0.158(2)
0.295(2)
ꢀ0.137(4)
ꢀ0.159(4)
0.297(2)
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S(1)
P(1)
N(1)
C(1)
S(2)
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Acknowledgements
We thank the joint programme of CRDF and Russian
Ministry of Education (Grants # REC-007, BRHE 2004 #

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