Studies on cobalt(II) complexes with N-thioacylamido(thio)phosphates: X-ray crystal structure of the Co[PhC(S)NP(S)(OPri)2]2

Article abstract of DOI:10.1016/j.poly.2006.06.005

Reaction of the potassium salts of N-thioacylamidophosphates RC(S)NHP(O)(OPri)₂ (R = Ph, PhNH, p-MeOPhNH, p-BrPhNH, iPrNH, tBuNH, Et₂N, c-C₅H₁₀N, c-OC₄H₈N, c-C₅H₁₁NH)

Full text of DOI:10.1016/j.poly.2006.06.005

Polyhedron 25 (2006) 3330–3336
www.elsevier.com/locate/poly
Studies on cobalt(II) complexes with
N-thioacylamido(thio)phosphates: X-ray crystal structure
of the Co[PhC(S)NP(S)(OPri)2]2
a,
a
a
a
Damir A. Safin *, Felix D. Sokolov , Nail G. Zabirov , Vasiliy V. Brusko ,
b
b
c
a
Dmitry B. Krivolapov , Igor A. Litvinov , Robert C. Luckay , Rafael A. Cherkasov
a
Department of Chemistry, Kazan State University, Kremlevskaya Street 18, 420008, Kazan, Tatarstan, Russia
b
Arbusov Institute of Organic and Physical Chemistry, Arbuzov Street 8, 420088, Kazan, Russia
Department of Chemistry, University of Stellenbosch, Private Bag X1, MATIELAND 7602, Stellenbosch, South Africa
c
Received 17 January 2006; accepted 7 June 2006
Available online 13 June 2006
Abstract
Reaction of the potassium salts of N-thioacylamidophosphates RC(S)NHP(O)(OPri)2 (R = Ph, PhNH, p-MeOPhNH, p-BrPhNH,
iPrNH, tBuNH, Et2N, c-C5H10N, c-OC4H8N, c-C5H11NH) with Co(II) cation in aqueous EtOH leads to the complexes of Co(L-
O,S)2 type structure. Complexes Co(B)L2 were obtained by the reaction of chelate complexes CoL2 (R = Ph, PhNH) with 2,20-bipyridine
and 1,10-phenanthroline. Structures of the compounds obtained were investigated by EIMS, IR, UV–Vis spectroscopy and microanal-
ysis. Complex Co[PhC(S)NP(S)(OPri)]2 was investigated by single crystal X-ray diffraction.
ꢀ 2006 Elsevier Ltd. All rights reserved.
Keywords: Organoelement analogues of b-dicarbonyl ligands; N-Thioacylamido(thio)phosphates; Cobalt(II) chelates; Crystal structure; UV–Vis spectra
1. Introduction
have been extensively investigated. Formation of chelate
complexes of the ML2 structure is characteristic for them.
Ligands are coordinated bidentately in these compounds,
through the atoms of sulfur of the thiocarbonic and
thio(seleno)phosphoric groups. Cobalt(II) chelates with
oxygen-containing ligands RCðOÞNHPðOÞR02 (2) show
the expressed propensity to oligomerization in the solid
phase and to the formation of complexes with the solvent
molecules. Dimeric structures of complexes have been stud-
ied, e.g. complexes Co2[L]4D2, where [L] = [CCl3C(O)NP-
(O)(OMe)2]ꢀ or [CCl3C(O)NP(O)(NHBz)2]ꢀ; D = iPrOH
[11,12]. An attempt to synthesise the heteroligand Co(II)
complexes by reaction of Co(PPh3)2Cl2 or Co(PPh3)2NO2
with Ph2P(Se)NHP(Se)Ph2 was unsuccessful [13]. Only
the [Co(Ph2P(Se)NHP(Se)Ph2)2] complex was obtained.
The structure of the Co(II) cation coordination com-
pounds with RCðSÞNHPðOÞR02 (3) (HL) ligands, contain-
ing donor atoms of sulfur and oxygen simultaneously is
practically not studied. On the one hand, prevalence of
N-(Thio)acylamido(thio)phosphates RCðXÞNHPðYÞR20
(X, Y = O or S; R = Alk, Ar, ArNH, AlkNH, Alk2N;
R0 = OAlk, OAr, Ar) are important because of the variety
of ways of interaction with d8- and d10-metal cations [1].
These compounds and their complexes can be used as
extractants, analytical reagents [2] and structural fragments
for construction of metal-containing macrocycles [3] and
polycrown-compounds [4].
Dithioderivatives of these compounds, N-thioacylami-
dothiophosphates RCðSÞNHPðSÞR02 (1) [5–8] or their
diphosphorus analogues R2PðXÞNHPðXÞR02 (X = S, Se)
[9,10] and their complexes with divalent d-metal cations
*
Corresponding author. Tel./fax: +7 843 2543734.
E-mail addresses: damir.safin@ksu.ru (D.A. Safin), felix.sokolov@
ksu.ru (F.D. Sokolov).
0277-5387/$ - see front matter ꢀ 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2006.06.005

D.A. Safin et al. / Polyhedron 25 (2006) 3330–3336
3331
2.2.1. Co[PhC(S)NP(O)(OPri)2]2 (4a)
This complex was prepared according to the previously
R`
R`
R`
R
N
N
R
N
R
P
P
P
R`
R`
R`
described technique [14]. UV–Vis spectra (CH2Cl2) [kmax
,
X
Y
Y
X
Y
X
nm (e, 1 molꢀ1 cmꢀ1)]: 569 (394), 614 (386), 666 (173).
M
M
M
B
A
2.2.2. Co[PhNHC(S)NP(O)(OPri)2]2 (4b)
Scheme 1.
This complex was prepared according to the previ-
ously described technique [19]. UV–Vis spectra (CH2Cl2)
[kmax, nm (e, 1 molꢀ1 cmꢀ1)]: 560 (342), 610 (360), 657
(187). EIMS, m/z (rel. int. %): 690 (0.1) [M]+, 316 (32)
[HL]+.
the X-enolic form (A) (Scheme 1) with the negative charge
delocalization in N-thioacylamidophosphate-anions [6]
pulls them together with ligands 1.
On the other hand, the presence in coordination sphere
of the central ion ‘‘hard’’ donor atom of oxygen of the
phosphoric group makes it coordinatively unsaturated.
Because of this, it can lead to complex formation, in which
the central ion has a coordination number of 6. A similar
coordination environment for N-thioacylamidophosphates
3 has been shown by us previously as an example of phos-
phorylated thiobenzamide PhC(S)NHP(O)(OPri)2 (HQ)
complexes with Co(II) [14], Ni(II) [15] and Cd(II) [16] cat-
ions. The X-ray data confirms that they have the
M(HQ)2Q2 type structure. Central atoms having a tetrago-
nal-bipyramidal environment (Oax)2(Oeq)2(Seq)2 is obtained
in these compounds. Axial positions are occupied by two
neutral molecules HQ. They are coordinated through the
oxygen atoms of P@O-groups. Thus, N-thioacylamido-
phosphates 3 can undergo significant changes of coordina-
tion properties both in comparison with oxygen-containing
2 and with dithioanalogues 1.
2.2.3. Co[p-MeOPhNHC(S)NP(O)(OPri)2]2 (4c)
Yield: ꢁ68%, m.p. 156 ꢁC. Anal. Calc. for C28H44Co-
N4O8P2S2: C, 44.86; H, 5.92; N, 7.47; S, 8.55. Found: C,
44.96; H, 6.01; N, 7.39; S, 8.58%. IR (cmꢀ1): 1508(s)
(SCN), 1008(b, vs) (POC), 1128(s) (P@O), 3296(b) (NH).
UV–Vis spectra (CH2Cl2) [kmax, nm (e, 1 molꢀ1 cmꢀ1)]:
560 (326), 611 (340), 662 (173). EIMS, m/z (rel. int. %):
750 (0.1) [M]+, 346 (19) [HL]+.
2.2.4. Co[p-BrPhNHC(S)NP(O)(OPri)2]2 (4d)
Yield: ꢁ79%, m.p. 170 ꢁC. Anal. Calc. for
C26H38Br2CoN4O6P2S2: C, 36.85; H, 4.52; Br, 18.86; N,
6.61; S, 7.57. Found: C, 36.81; H, 4.57; Br, 18.94; N,
6.63; S, 7.62%. IR (cmꢀ1): 1512(s) (SCN), 1008(b, vs)
(POC), 1116(s) (P@O), 3288(b) (NH). UV–Vis spectra
(CH2Cl2) [kmax, nm (e, 1 molꢀ1 cmꢀ1)]: 559 (332), 610
(340), 662 (166). EIMS, m/z (rel. int. %): 848 (0.2) [M]+,
395 (5) [HL]+.
In the present study, new data about the structure and
properties of N-thioacylamidophosphate chelate complexes
3 with the Co(II) cation are reported.
2.2.5. Co[iPrNHC(S)NP(O)(OPri)2]2 (4e)
Yield: ꢁ48%, m.p. 166 ꢁC. Anal. Calc. for C20H44Co-
N4O6P2S2: C, 38.64; H, 7.13; N, 9.01; S, 10.32. Found: C,
38.93; H, 7.11; N, 9.09; S, 10.34%. IR (cmꢀ1): 1512(s)
(SCN), 1000(b, vs) (POC), 1128(s) (P@O), 3312(b) (NH).
UV–Vis spectra (CH2Cl2), [kmax, nm (e, 1 molꢀ1 cmꢀ1)]:
561 (251), 611 (289), 660 (161). EIMS, m/z (rel. int. %):
622 (74) [M]+, 282 (89) [HL]+.
2. Experimental
2.1. Synthesis of [RC(S)NHP(O)(OPri)2] (3a–j)
N-Diisopropoxyphosphorylthiobenzamide (3a) (R = Ph)
and N-phosphorylated thioureas (3b–j) (R = PhNH, p-
MeOPhNH, p-BrPhNH, iPrNH, tBuNH, Et2N, c-C5H10N,
c-OC4H8N, c-C6H11NH), were prepared according to the
previously described techniques [17] and [18].
2.2.6. Co[tBuNHC(S)NP(O)(OPri)2]2 (4f)
Yield: ꢁ74%, m.p. 164 ꢁC. Anal. Calc. for C22H48Co-
N4O6P2S2: C, 40.67; H, 7.45; N, 8.62; S, 9.87. Found: C,
40.63; H, 7.42; N, 8.74; S, 9.91%. IR (cmꢀ1): 1522(s)
(SCN), 1000(b, vs) (POC), 1120(s) (P@O), 3320(b) (NH).
UV–Vis spectra (CH2Cl2), [kmax, nm (e, 1 molꢀ1 cmꢀ1)]:
561 (246), 611 (279), 661 (154). EIMS, m/z (rel. int. %):
650 (4) [M]+, 296 (10) [HL]+.
2.2. Synthesis of [CoL2] (4a–j and 5a)
A suspension of 3a–j (5 mmol) in aqueous ethanol
(20 ml) was mixed with an ethanol solution of potassium
hydroxide (6 mmol). To the resulting potassium salt, a
water (20 ml) solution of Co(NO3)2 Æ 6H2O (2.8 mmol)
was added dropwise whilst stirring. The mixture was stirred
at room temperature for a further 3 h and left overnight.
The resulting complexes 4a–j were extracted with methy-
lene chloride, washed with water and dried over anhydrous
MgSO4. The solvent was then removed under vacuum.
Dark blue precipitates were obtained from a methylene
chloride–n-hexane mixture, 1:5 v/v.
2.2.7. Co[Et2NC(S)NP(O)(OPri)2]2 (4g)
Yield: ꢁ80%, m.p. 64 ꢁC. Anal. Calc. for C22H48Co-
N4O6P2S2: C, 40.67; H, 7.45; N, 8.62; S, 9.87. Found: C,
39.93; H, 7.51; N, 8.94; S, 9.77%. IR (cmꢀ1): 1512(s)
(SCN), 1000(b, vs) (POC), 1135(s) (P@O). UV–Vis spectra
(CH2Cl2) [kmax, nm (e, 1 molꢀ1 cmꢀ1)]: 558 (275), 610 (302),
663 (169). EIMS, m/z (rel. int. %): 650 (51) [M]+, 296 (5)
[HL]+.

3332
D.A. Safin et al. / Polyhedron 25 (2006) 3330–3336
2.2.8. Co[C5H10NC(S)NP(O)(OPri)2]2 (4h)
Yield: ꢁ71%, m.p. 62 ꢁC. Anal. Calc. for C24H48Co-
N4O6P2S2: C, 42.79; H, 7.18; N, 8.32; S, 9.52. Found: C,
42.66; H, 7.23; N, 8.54; S, 9.61%. IR (cmꢀ1): 1510(s)
(SCN), 1010(b, vs) (POC), 1140(s) (P@O). UV–Vis spectra
(CH2Cl2) [kmax, nm (e, 1 molꢀ1 cmꢀ1)]: 559 (263), 610 (281),
662 (167). EIMS, m/z (rel. int. %): 674 (15) [M]+, 308 (3)
[HL]+.
m/z (rel. int. %): 659 (94) [M]+, 301 (54) [HL]+, 180 (20)
[phen]+.
2.3.3. Co[PhNHC(S)NP(O)(OPri)2]2(bpy) (6c)
Yield: ꢁ91%, m.p. 142 ꢁC. Anal. Calc. for C36H48Co-
N6O6P2S2: C, 51.12; H, 5.72; N, 9.94; S, 7.58. Found: C,
51.16; H, 5.69; N, 9.98; S, 7.53%. IR (cmꢀ1): 1522(s)
(SCN), 1000(b, vs) (POC), 1172(s) (P@O), 3272(b) (NH).
UV–Vis spectra (CH2Cl2), [kmax, nm (e, 1 molꢀ1 cmꢀ1)]:
551 (56). EIMS, m/z (rel. int. %): 690 (0.8) [M]+, 316 (27)
[HL]+, 156 (15) [bpy]+.
2.2.9. Co[OC4H8NC(S)NP(O)(OPri)2]2 (4i)
Yield: ꢁ67%, m.p. 58 ꢁC. Anal. Calc. for C22H44Co-
N4O8P2S2: C, 38.99; H, 6.54; N, 8.27; S, 9.46. Found: C,
39.05; H, 6.49; N, 8.22; S, 9.50%. IR (cmꢀ1): 1504(s)
(SCN), 1010(b, vs) (POC), 1120(s) (P@O). UV–Vis spectra
(CH2Cl2) [kmax, nm (e, 1 molꢀ1 cmꢀ1)]: 560 (257), 612 (287),
659 (163). EIMS, m/z (rel. int. %): 678 (12) [M]+, 310 (9)
[HL]+.
2.3.4. Co[PhNhC(S)NP(O)(OPri)2]2(phen) (6d)
Yield: ꢁ97%, m.p. 156 ꢁC. Anal. Calc. for C38H48Co-
N6O6P2S2: C, 52.47; H, 5.56; N, 9.66; S, 7.37. Found: C,
52.51; H, 5.60; N, 9.61; S, 7.42%. IR (cmꢀ1): 1538(s)
(SCN), 992(b, vs) (POC), 1172(s) (P@O), 3240(b) (NH).
UV–Vis spectra (CH2Cl2), [kmax, nm (e, 1 molꢀ1 cmꢀ1)]:
560 (60). EIMS, m/z (rel. int. %): 690 (0.5) [M]+, 316 (22)
[HL]+, 180 (23) [phen]+.
2.2.10. Co[C6H11NHC(S)NP(O)(OPri)2]2 (4j)
Yield: ꢁ77%, m.p. 144 ꢁC. Anal. Calc. for C26H52Co-
N4O6P2S2: C, 44.50; H, 7.47; N, 7.98; S, 9.34. Found: C,
44.26; H, 7.34; N, 7.63; S, 8.97%. IR (cmꢀ1): 1524(s)
(SCN), 1010(b, vs) (POC), 1130(s) (P@O), 3312(b) (NH).
UV–Vis spectra (CH2Cl2), [kmax, nm (e, 1 molꢀ1 cmꢀ1)]:
562 (259), 611 (294), 663 (160). EIMS, m/z (rel. int. %):
702 (1) [M]+, 322 (35) [HL]+.
2.4. Physical measurements
Infrared spectra (Nujol) were recorded on a Specord
M-80 spectrometer in the range 400–3600 cmꢀ1. Electron
ionization mass-spectra were measured on the TRACE
MS Finnigan MAT instrument. Ionization energy was
70 eV. The substance was injected directly into the ion
source at 150 ꢁC. Heating was carried out in a programmed
mode from 35 to 200 ꢁC at a rate of 35 ꢁC/min. Electronic
spectra of absorption in 0.001 M solution of CH2Cl2 were
measured on a Lambda-35 spectrometer in the range 200–
1000 nm.
2.2.11. Co[PhC(S)NP(S)(OPri)2]2 (5a)
This complex was prepared according to the previously
described technique [20].
2.3. Synthesis of [Co(B)L2] (6a–d)
A solution of complexes 4a or 4b (0.45 mmol) in benzene
(10 ml) was added dropwise whilst stirring to a solution of
2,20-bipyridine (bpy) or 1,10-phenanthroline (phen) in ben-
zene (10 ml). After complete addition, the solution was stir-
red for an hour. The solvent was then removed under
vacuum. The residue was recrystallized from a methylene
chloride–n-hexane mixture and the complexes 6a–d have
been isolated as red powders.
2.5. Crystal structure determination and refinement
The crystals of 5a were obtained from the mixture of
dichloromethane and n-hexane by the method of slow
evaporation. The X-ray diffraction data for the crystal
of 5a were collected on a CAD4 Enraf-Nonius automatic
diffractometer using graphite monochromated Cu Ka
˚
(1.54158 A) radiation. The molecule of 5a in the crystals
2.3.1. Co[PhC(S)NP(O)(OPri)2]2(bpy) (6a)
Yield: ꢁ86%, m.p. 133 ꢁC. Anal. Calc. for C36H46Co-
N4O6P2S2: C, 53.00; H, 5.68; N, 6.87; S, 7.86. Found: C,
52.96; H, 5.74; N, 7.17; S, 7.62%. IR (cmꢀ1): 1488(s)
(SCN), 1016(b, vs) (POC), 1172(s) (P@O). UV–Vis spectra
(CH2Cl2) [kmax, nm (e, 1 molꢀ1 cmꢀ1)]: 546 (62). EIMS, m/z
(rel. int. %): 659 (100) [M]+, 301 (49) [HL]+, 156 (18)
[bpy]+.
occur in a special position. The details of the crystal data,
data collection and the refinement are given in Table 1.
The stability of the crystal and experimental conditions
were checked every 2 h using three control reflections,
while the orientation was monitored every 200 reflections
by centralising two standards. The decay of three control
reflections was not observed. An empirical absorption
correction based on w-scans was applied. Cell parameters,
data collection and data reduction were performed on an
Alpha Station 200 computer using the MOLEN [21] pro-
gram. The structures were solved by direct methods using
the SIR 92 [22] program, and refined using the SHELXL-97
program [23]. The positions of the hydrogen atoms were
idealised. All figures were made using the program
PLATON [24].
2.3.2. Co[PhC(S)NP(O)(OPri)2]2(phen) (6b)
Yield: ꢁ94%, m.p. 148 ꢁC. Anal. Calc. for C38H46Co-
N4O6P2S2: C, 54.35; H, 5.52; N, 6.67; S, 7.64. Found: C,
54.29; H, 5.57; N, 6.72; S, 7.68%. IR (cmꢀ1): 1490(s)
(SCN), 996(b, vs) (POC), 1172(s) (P@O). UV–Vis spectra
(CH2Cl2) [kmax, nm (e, 1 molꢀ1 cmꢀ1)]: 549 (58). EIMS,

D.A. Safin et al. / Polyhedron 25 (2006) 3330–3336
3333
Table 1
R
N
OPr-i
H
O
1) KOH
2) Co(NO3)2
Crystal data, data collection and refinement details for 5a
N
R
S
i-PrO
N
P
O
P
5a
Co
i-PrO
S
OPr-i
3a-j
S
O
P
OPr-i
OPr-i
Chemical formula
Crystal type
C26H38N2O4P2S4Co
R
green prism
0.8 · 0.6 · 0.4
691.73
monoclinic
P21/c
10.016(9)
17.960(8)
19.15(2)
90.00
100.88(7)
90.00
Crystal size (mm3)
Formula weight
Crystal system
Space group
4a-j
i-PrO
OPr-i
N
P
N
˚
a (A)
N
R
O
Co
N
˚
b (A)
S
˚
R
c (A)
S
6a-d
R = Ph, PhNH
N
a (ꢁ)
b (ꢁ)
c (ꢁ)
N
O
P
OPr-i
OPr-i
3
˚
V (A )
3383(5)
4
1.36
Z
Dcalc (mg mꢀ3
)
N
F(000)
Radiation (A)
Temperature (K)
Scan mode
1444
Cu Ka (1.54158)
293
˚
or
N
N
N
N
N
x
Recording range hmax (ꢁ)
Absorption correction
57.20
w-scans
74.45
variable, 1–16.4
4002
3098
Scheme 2.
l (cmꢀ1
)
Scan speed (deg minꢀ1
Reflections measured
)
The research has shown that all listed complexes 4a–j
have the same coordination environment at the Co(II)
atom. The UV–Vis spectroscopic data confirm that in a
CH2Cl2 solution only ML2 chelates with a tetrahedral
MO2S2 core exist. In the case of complexes 6a–d the coor-
dination environment of the central atom differs from com-
plexes 4a–j. According to UV–Vis spectroscopy data
obtained in a CH2Cl2 solution, complexes 6a–d have an
octahedral MO2S2N2 core.
Number of independent
reflections with F2 P 2r(F2)
R (%)
Rw (%)
S
0.053
0.134
1.031
3. Results and discussion
3.2. IR and UV–Vis spectroscopy
3.1. Synthesis
According to the IR spectroscopy, the absorption bands
of the P@O group of anionic forms 3a–j in complexes 4a–j
are shifted by approximately 76–116 cmꢀ1 at low frequen-
cies with respect to the parent ligand bands. It confirms
their participation in chelate formation. In the spectra of
the suspension of complexes 4a–j in Nujol, there are intense
absorption bands at 1504–1524 cmꢀ1, these are assigned to
vibrations of the SCN fragment in the N-thioacylamido-
phosphate-anion [7]. The signal of the NH proton is absent
in the IR spectra of the complexes 4a,g–i and in the spectra
of 4b–f and sj, there is only a signal in the 3288–3320 cmꢀ1
interval, corresponding to the NH-group vibrations of the
R substituent.
The comparative analysis of IR spectra of 3a and 3b thi-
oureas, their complexes with Co(II) cation formulas 4a and
4b, and adducts 6a–d confirms the preservation of the CoL2
core in compounds 6a–d. The absorption band of the P@O
group in complexes 6a–d is shifted by approximately 72–
80 cmꢀ1 at low frequencies with respect to the free ligand
bands 3a and 3b, and there is also an intense absorption
band of the SCN fragment. All this confirms 1,5-S,O-coor-
dination of the ligand anions. However, the shift of the
P@O groups absorption bands in adducts 6a–d is less than
The ligand 3a was prepared by reaction of thiobenza-
mide PhC(S)NH2 with diisopropoxychlorphosphate
(iPrO)2P(O)Cl. Ligands 3b–j were prepared by reaction of
the corresponding amine with (iPrO)2P(O)NCS.
Complexes of 3a–j with Co(II) 4a–j were prepared by the
following procedure: the ligand was converted to the potas-
sium salt, followed by interaction with Co(NO3)2 Æ 6H2O.
The compounds obtained are crystalline solids soluble in
most polar solvents.
Unsaturation of the CoO2S2 coordination environment
opens up possibilities of a wide number of heteroligand
complex syntheses. This can be obtained by interaction of
such complexes with various donor agents [25]. As donors,
both monodentate ligands and chelating agents might be
used. A variety of donor structures opens up prospects
for supramolecular units within the realm of advanced syn-
thesis. We used bpy and phen in our work as donor ligands
(Scheme 2).
Complexes 6a–d were prepared by the following proce-
dure: a benzene solution of bpy or phen was added drop-
wise to a benzene solution of the complex 4a or 4b. The
compounds obtained 6a–d are crystalline solids which are
soluble in most polar solvents.

3334
D.A. Safin et al. / Polyhedron 25 (2006) 3330–3336
32–36 cmꢀ1, compared to the initial Co(II) complexes 4a
and 4b.
the red color of complexes 6a–d. The observable absorp-
4
4
tion band is caused by a T1g(F) ! T1g(P) transition. It
4
4
The structure of the chelate unit in Co(II) complexes in
the CH2Cl2 solution is established by UV-spectroscopy.
In complexes 4a–j there is an absorption band with peaks
in the ranges 558–562, 610–614 and 657–666 nm and with
molar extinction coefficient (e) 246–394, 279–386 and
154–187, respectively. Values of e for complexes 4a–d, con-
taining arylamine substituents at thiocarbonic groups, are
greater than 80–119 nm, compared to complexes 4e–j.
Absorption is observed in the red region of the spectrum,
which explains the dark blue color of the complexes of
Co(II) 4a–j. The specified absorption band corresponds
is easy to establish that the T1g(F) ! T2g transition
should correspond to the value of energy which is slightly
4
lower in comparison with the energy of the T1g(F) !
4
4T1g(P) transition. But as the state A2g arises from a con-
figuration t23geg4 and a state 4T1g(F) mainly from t52ge2g, tran-
4
4
sition T1g(F) ! A2g is in essence a two-electron transfer,
and for this reason the band should be less intense (approx-
imately by two orders), than the bands of other transitions.
4
4
The specified two circumstances for T1g(F) ! A2g transi-
tion: small intensity and affinity to the band
4
4T1g(F) ! T1g(P) lead to fact that this transition is not
4
4
to a transition from the basic state A2 to a T1(P) state.
The thin structure is caused by spin–orbital interaction as
a result of which, first, there is a splitting of the state
4T1(P) and, secondly, there are resolved transitions in the
next doublet states with the same intensity. Other possible
observed in a spectrum. Data from UV-spectroscopy con-
firm a change of a Co(II) cation geometrical environment
in compounds 4a and 4b after reaction with bpy and phen
with the formation of adducts 6a–d.
4
4
4
4
transitions: A2 ! T2 and A2 ! T1(F) – are outside of
the visible area. Data of UV-spectroscopy unequivocally
confirm the tetrahedral environment of the Co(II) cation
in complexes 4a–j.
3.3. EI mass spectrometry
The electron impact (EIMS) mass spectra of 4b–j con-
tains the [CoL2]+ structure molecular ion peaks. The iso-
tope bearing peaks of a molecular ion cluster correspond
to the data calculated on the basis of gross-formulas of
the CoL2 structure. Stability of [M]+ falls at complexes
4b and 4c, containing arylamine substituents at the carbon
atom of the thiocarbonic groups. So, the peak of a molec-
ular ion in the mass-spectrum of the complex 4b has a very
In the UV-spectra of complexes 6a–d there is a shoulder
with a peak of absorption in the region of 546–560 nm.
Values of e for 6a–d are less, compered to the initial com-
plexes 4a and 4b, which are in the 56–62 nm range. It is
important to note that the absorption is weak enough
and shifted to the violet part of a spectrum that causes
Table 2
˚
Selected bond distances (A), bond and torsion angles (ꢁ) for six-membered cycles M–S–C–N–P–Y in the complexes ML2-S,Y [Y = O, S; M = Co(II),
Ni(II), Pd(II)]
Co[L-S,O]2 (4a) [19]
Co[L-S,O]2 (4b) [14]
Co[L-S,S0]2 (5a)
Ni[L-S,S0]2 [26]
Ni[L-S,S0]2 [27]
Pd[L-S,S0]2 [28]
L
PhNHC(S)-
NP(O)(OPr-i)2
PhC(S)NP(O)-
(OPr-i)2
PhC(S)NP(S)-
(OPr-i)2
n-Pr2NC(S)-
NP(S)(OPh)2
MeNHC(S)-
NP(S)Ph2
PhC(S)NP(S)-
(OPr-i)2
M–S(C)
M–Y
2.306
2.319
2.289
1.940
1.731
1.297
2.301
2.292
2.2050
2.226
1.745
1.321
1.337
1.574
1.978
97.62
11.56
27.43
2.214
2.217
1.760
1.294
1.347
1.610
2.016
98.17
0.00
2.310
2.341
1.712
1.299
1.974
1.959
2.311
2.320
C–S
1.789
1.779
1.735
1.733
C–N
1.305
1.305
1.283
1.300
C–N (exocyclic)
P–N
1.358
1.370
1.614
1.625
1.610
1.488
101.27
ꢀ3.11
15.72
1.612
1.613
1.613
1.994
96.76
2.15
P–Y
1.513
1.526
1.987
1.983
S–M–Y (endocyclic)
S–C–N–P
C–N–P–Y
99.6
100.0
108.26
106.67
0.9
0.5
ꢀ7.10
ꢀ1.12
61.78
60.14
12.0
12.7
41.30
40.92

D.A. Safin et al. / Polyhedron 25 (2006) 3330–3336
3335
small intensity equal to 0.1%, and in mass-spectrum of the
complex 4c – 0.2%. In EI mass-spectra of the 6a–d adducts
there are no peaks of molecular ions. Molecular ions of
complexes 6a–d are unstable under the conditions of mea-
surement, and the heaviest molecular ion, observed in the
spectra of 6a–d, corresponds to the neutral CoL2 complex
core. In the EI-spectra there are also peaks of ligands 3a,
3b, bpy and phen, respectively.
deviation of atoms S1A and Co1 ꢀ1.527(1) and
ꢀ0.8364(7), respectively; similarly, the fragment S2B–
˚
C1B–N1B–P1B is flat within the limits of 0.029(4) A, with
a deviation of atoms Co1 and S1B of 1.1306(7) and
˚
1.473(1) A, respectively (Fig. 1)). Six-membered chelate
cycles in molecules 4a and 4b, on the contrary, are appre-
ciably flattened (Table 2).
4. Conclusion
3.4. The comparative analysis of molecular structure of CoL2
complexes
This research has shown that the structure and proper-
ties of N-thioacylamidophosphate complexes with the
CoO2S2 core essentially differ from that investigated by
us previously with the same cation. The Co(II) cation in
such complexes shows coordination unsaturation. A conse-
quence of this is the ability to increase the coordination
number of the central atom with neutral donor ligands,
with the formation of Cd(B)L2 adducts. Ligands like the
N-thioacylamidophosphate, as has been shown by us ear-
lier [12], and also molecules of bpy and phen can act in this
manner. Thus, complexes with CoO2S2 core can be used as
electrophilic binding centers in organometallic receptor
molecules, e.g. in polynuclear macrocyclic chelates of
bifunctional N-thioacylamidophosphates [3].
The structure of complexes 4a [14] and 4b [19] have been
investigated earlier by X-ray studies. It is of interest to
compare their structure with the dithioanalogue 5a.
According to the X-ray data complexes 4a, 4b and 5a
are spirocycling chelates in the crystal with a distorted-
tetrahedral CoO2S2 core for 4a and 4b or CoS4 for 5a.
The selected bond lengths and torsion angles are given in
Table 2.
Distribution of bond lengths in a fragment S–C–N–P–Y
for all compounds considered confirms the existence of two
tautomeric forms: S-enolic (A) and Y-enolic (B) (Scheme 1).
Bond lengths C–N and P–N in complexes of phosphory-
lated (Y = O) and thiophosphorylated (Y = S) derivatives
differ slightly (Table 2). In order to make sense of this,
one sees that the character of the negative charge delocal-
ization in the coordinated N-thioacylamido(thio)phos-
phate-anion and the resonant forms (A) and (B) (Scheme
1) practically does not change at the transition from thio-
phosphoric derivatives to phosphoric derivatives.
Acknowledgements
This work was supported by the Russian Foundation
for Basic Research (# 03-03-32372-a, 03-03-96225-
r2003tatarstan_a) and the joint program of CRDF and
the Russian Ministry of Education (BRHE 2004 Y2-C-
07-02).
In N-thioacylamidophospate complexes 1 the six-mem-
bered M–S1–P–N–C–S2 cycle, usually, has the conforma-
tion of a distorted boat. So, for example, in the complex
5a, the cycles conformation is an asymmetrical boat with
a planar PNCS fragment and with a deviation of metal
and thiophosphoryl sulfur atoms (the fragment S2A–
Appendix A. Supplementary data
Atomic coordinates, bond lengths, bond angles and
thermal parameters have been deposited at the Cambridge
Crystallographic Data Centre (CCDC). Data can be
obtained free of charge via www.ccdc.cam.uk/conts/
retrieving.html (or from the CCDC, 12 Union Road, Cam-
bridge CB2 1EZ, UK; fax: +44 1223 336 033; or depos-
it@ccdc.cam.ac.uk). Any requests to the CCDC for data
should quote the full literature citation and CCDC refer-
ence number 291905. Supplementary data associated with
this article can be found, in the online version, at
doi:10.1016/j.poly.2006.06.005.
˚
C1A–N1A–P1A is flat within the limits of 0.003(4) A, a
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