Synthesis and structure of monoribbed-functionalized disulfide iron(II) clathrochelates and their coordination as the ligands toward platinum(II) and platinum(IV) ions

Article abstract of DOI:10.1016/j.ica.2008.03.055

Disulfide monoribbed-functionalized clathrochelates (i.e., fuctionalization of one of the three α-dioximate fragments) with ribbed thioalkyl, S₃-thioalkyl and hydroxythioalkyl substituents have been synthesized starting from the FeBd₂

Full text of DOI:10.1016/j.ica.2008.03.055

Inorganica Chimica Acta 362 (2009) 149–158
Contents lists available at ScienceDirect
Inorganica Chimica Acta
journal homepage: www.elsevier.com/locate/ica
Synthesis and structure of monoribbed-functionalized disulfide iron(II)
clathrochelates and their coordination as the ligands toward platinum(II)
and platinum(IV) ions
a,*
b
c
a
a
Yan Z. Voloshin , Oleg A. Varzatskii , Dmitry I. Kochubey , Ivan I. Vorontsov , Yurii N. Bubnov
a
Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, 119991 Moscow, Russia
Vernadskii Institute of General and Inorganic Chemistry, Kiev-142 03680, Ukraine
Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, 630090 Novosibirsk, Russia
b
c
a r t i c l e i n f o
a b s t r a c t
Article history:
Disulfide monoribbed-functionalized clathrochelates (i.e., fuctionalization of one of the three a-dioximate
fragments) with ribbed thioalkyl, S -thioalkyl and hydroxythioalkyl substituents have been synthesized
starting from the FeBd (Cl Gm)(BF)
hloroglyoxime dianions) using the corresponding thiol/triethylamine system in dichloromethane solu-
tion. Clathrochelate S -dithiol in basic media underwent the intramolecular dealkylation to yield the
-thiocrown etheric clathrochelate. Clathrochelates obtained have been studied as the ligands toward
Received 26 November 2007
Accepted 12 March 2008
Available online 16 March 2008
3
2ꢀ
2ꢀ
2
2
2 2
precursor (where Bd and Cl Gm are a-benzyldioxime and dic-
6
Keywords:
Iron complexes
Clathrochelates
Macrocyclic compounds
X-ray crystallography
S
3
2+
4+
2ꢀ
Pt and Pt ions. The S-demethylation reaction of the methylsulfide complex with [PtCl
4
]
dianion pro-
duced the polynuclear complexes of the dianionic clathrochelate dithiolate ligand. The reaction of n-
IV
4 6 5 2 2
butylsulfide clathrochelate with the trans-Pt Cl (C H CH CN) afforded the binuclear compound with
the disulfide iron(II) clathrochelate as a monodentate ligand. The obtained macrobicycles, their clathr-
ochelate derivatives, and polynuclear complexes have been characterized using elemental analysis,
MALDI-TOF and PD mass, IR, UV–Vis, and NMR spectra, and X-ray crystallography. The encapsulated iro-
n(II) ion coordination polyhedra distortion angle u values and the main distances in the molecules of
5
7
polynuclear complexes have been deduced (obtained) using Fe Mössbauer parameters and EXAFS data,
respectively.
Ó 2008 Elsevier B.V. All rights reserved.
1
. Introduction
Thiolate anions of different types have proved to be the most
this allowed us to synthesize monoribbed-functionalized clathr-
ochelates (i.e., complexes with the functionalizing substituents in
one of the three dioximate fragments).
efficient nucleophilic agents in the substitution reactions of the
reactive chlorine atoms of halogenide clathrochelate precursors
2
. Experimental
[
1–11]. These reactions allow a number of ribbed-functionalized
di- and polysulfide clathrochelates to be obtained with different
pendant substituents [2–5,8,9,11]. The disulfide a-dioximate frag-
ments of these clathrochelates with donor sulfur atoms are able
to coordinate as cis-ligands to the metal ions. Such sulfur atoms
are soft Pearson bases (in accordance with the hard-soft acid-base
2
.1. General information
The reagents used, FeCl
2
ꢁ 4H
2
O, a-benzyldioxime (H
2
Bd), Cs
2
CO
3
,
K
2
CO
O(C
tained commercially (Fluka). ((n-C
tained by the reduction of the commercial K
with aqueous N followed by precipitation with an excess of
(n-C N)Cl. trans-PtCl
3 4 9 3
, n-C H SH, CH SH, 2-mercaptoethanol, (HSCH
2
CH S, BF
)
2 2
3
ꢁ
2
5
H )
2
, sorbents, organic bases and organic solvents, were ob-
N) PtCl complex was ob-
PtCl (Reakhim)
[
HSAB] principle [12]) that should form the most stable complexes
4
9
H )
4
2
4
with metal ions that are soft Pearson acids (in particular, with plat-
inum group metal ions).
2
6
2 4
H
We thought it was important to obtain clathrochelates with
various ribbed sulfur-containing substituents and to study their
(
H
4 9
)
4
4
6
(C H
5
CH
2
CN)
2
complex [13] was do-
Gm)(BF) complex was
complexation with Pt2 and Pt ions. We used the dichloride
+
4+
nated by Prof. V.Y. Kukushkin. FeBd
prepared as described in Ref. [9].
2
(Cl
2
2
2 2 2
FeBd (Cl Gm)(BF) complex as a reactive clathrochelate precursor:
Analytical data (C, H, N content) were obtained with a
Carlo Erba model 1106 microanalyzer. Iron content was deter-
mined spectrophotometrically. Chlorine content was obtained by
*
Corresponding author.
E-mail address: voloshin@ineos.ac.ru (Y.Z. Voloshin).
0
020-1693/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2008.03.055

1
50
Y.Z. Voloshin et al. / Inorganica Chimica Acta 362 (2009) 149–158
mercurymetric titration. Platinum content was determined by
X-ray fluorescence with a VRA-30 Carl Zeiss spectrofluorimeter.
Plasma desorption (PD) mass spectra were recorded in the posi-
tive spectral region with a BC MS SELMI time-of-flight mass spec-
trometer and an accelerating voltage of 20 kV. Ionization was
2H, OH), 3.48 (m, 4H, CH
2
), 3.78 (m, 4H, CH
7.34 (m, 8H, Ph). C{ H} NMR (CDCl ): d (ppm) 37.4 (s, CH
61.7 (s, CH ), 127.9 (s, Ph), 128.8 (s, Ph), 130.2 (s, Ph), 130.7 (s,
2
), 7.30 (m, 12H, Ph),
1
3
1
3
2
),
2
ꢀ1
Ph), 148.7 (s, SC@N), 157.1 (s, PhC@N). IR (cm , KBr): 1563
m(SC@N), 1592 m(PhC@N), 946m, 1068 m(N–O), 1217m m(B–
2
52
ꢀ3
ꢀ1
ꢀ1
induced by
Cf spontaneous decay fragments, and typically
2 2
O) + m(B–F). UV–Vis (CH Cl ): kmax (10 e/mol l cm ) 247(34),
2
0000 decay events were registered. Samples (ꢂ1–2 mg) were ap-
282(12), 264(5.8), 296(12), 318(3.6), 425(4.8), 483(29) nm.
plied to a gilded disk.
MALDI-TOF mass spectra were recorded in both the positive
and negative spectral regions with a MALDI-TOF-MS Bruker Auto-
flex mass spectrometer in reflecto-mol mode. Ionization was in-
duced by UV-laser with wavelength 336 nm. Samples were
applied to a nickel plate and 2,5-dihydroxybenzoic acid was used
as a matrix. The accuracy of measurements was 0.1%.
IR spectra of solid samples (KBr tablets) in the range of 400–
3
2 3 2 2
.2. FeBd ((CH S) Gm)(BF) (2)
2 2 2
Complex FeBd (Cl Gm)(BF) , (0.71 g, 1 mmol), 5-fold excess of
methanethiol (0.5 ml, 9 mmol) and 1.5-fold excess of triethylamine
(
(
0.42 ml, 3 mmol) were dissolved/suspended in dichloromethane
25 ml). The reaction mixture was left overnight and then washed
2
with 3% HCl aqueous solution, dried with CaCl , and filtered. The
ꢀ1
4
000 cm
were recorded with a Specord M-80 Carl Zeiss
filtrate was rotary evaporated to 1/5 volume and precipitated with
hexane. The precipitate was washed with methanol, hexane, and
dried in vacuo. Yield: 0.67 g (93%). Elemental analysis, IR, UV–Vis
and MS(PD) spectral data are identical to earlier obtained in Ref.
spectrophotometer.
UV–Vis spectra of solutions in chloroform were recorded in the
range of 230–800 nm with a Lambda 9 Perkin Elmer spectropho-
tometer. Individual Gauss components of these spectra were calcu-
lated using the SPECTRA program [14].
[
9].
1
13
H and C NMR spectra were recorded from the CDCl
solutions with a Bruker AC-200 FT-spectrometer.
Fe Mössbauer spectra were obtained with a YGRS-4M spec-
3
and
2 4 9 2 2
3.3. FeBd ((n-C H S) Gm)(BF) (3)
CD
2
Cl
5
2
7
This complex was synthesized like the previous one except that
.5-fold excess of n-butylmercaptan (0.32 ml, 3 mmol) was used
trometer with a constant acceleration mode. The spectra were col-
lected with a 256-multichannel amplitude analyzer. Isomer shift
1
instead of methanethiol. Yield: 0.73 g (85%). Anal. Calc. for
FeS : C, 53.42; H, 4.45; N, 9.84; Fe, 6.54. Found:
C, 53.48; H, 4.37; N, 9.75; Fe, 6.45%. MS(PD): m/z 854 [M] .
NMR (CD Cl ): d (ppm) 0.81 (t, 6H, CH ), 1.35 (m, 4H, CH ), 1.53
m, 4H, CH ), 3.28 (t, 4H, SCH ), 7.27 (m, 20H, Ph). C{ H} NMR
CD Cl ): d (ppm) 13.7 (s, CH ), 21.9 (s, CH ), 32.5 (s, CH ), 34.7
s, SCH ), 128.4 (s, Ph), 129.6 (s, Ph), 130.5 (s, Ph), 130.9 (s, Ph),
was measured relative to sodium nitroprusside, and a-Fe foil was
used for velocity scale calibration. 57Co in a Cr matrix was used
C
H
38 38
N
6
O
B
6 2
F
2
2
+
Å 1
H
as the source, which was always kept at room temperature. The
minimal absorption line width in the spectrum of a standard sam-
ple of sodium nitroferricyanide was 0.24 mm/s.
2
2
3
2
1
3
1
(
(
(
1
1
2
2
2
2
3
2
2
EXAFS spectra of iron K- and platinum LIII-edges for the three
complexes studied were obtained with an EXAFS Station at the
Siberian Synchrotron Radiation Center. The storage ring VEPP-3
with an electron beam energy of 2 GeV and an average stored cur-
rent of 80 mA was used as the source of radiation. X-ray energy
was monitored with a channel cut Si(111) monochromator. EXAFS
spectra were recorded in transmission mode with 1.4 eV steps and
treated using standard procedures with the VIPER program [15]. The
background was removed by extrapolating the pre-edge region
into the EXAFS region using Victoreen polynomials. Three cubic
splines were used to construct the smooth part of the adsorption
coefficient. The inflection point of the edge of the X-ray absorption
spectrum was used as the initial point (k = 0) of the EXAFS spec-
trum. Radial distribution functions of the atoms were calculated
2
ꢀ
1
50.1 (s, SC@N), 157.2 (s, PhC@N). IR (cm , KBr): 1550 m(SC@N),
584 m(PhC@N), 935m, 1065 m(N–O), 1213m m(B–O) + m(B–F). UV–
ꢀ
3
ꢀ1
ꢀ1
Vis (CH
2
2
Cl
2
):
k
max (10 e/mol l cm
)
262(11), 278(13),
97(9.4), 329(2.8), 400(3.0), 483(24) nm.
.4. FeBd ((HS(CH CH S) Gm)(BF) (4)
2 2
CH ) S (1.3 ml, 10 mmol) and triethyl-
3
2
2
2
)
2 2
2
Fivefold excess of (HSCH
amine (1.4 ml, 10 mmol) were dissolved in dichloromethane
20 ml). The solution of complex FeBd (Cl Gm)(BF) (0.75 g,
mmol) in dichloromethane (50 ml) was added dropwise to the
2
(
1
2
2
2
stirring reaction mixture for 5 h. The reaction mixture was stirred
for 5 h and left overnight. Then, the resulting red-brown solution
was washed with Na
two portions) and with water (100 ml, in two portions). The dichlo-
romethane extract was dried with MgSO and rotary evaporated to
2
from the EXAFS spectra in k v(k) as the modulus of the Fourier
ꢀ1
2 3
CO saturated aqueous solution (100 ml, in
transform at the wave number interval 2.5–12.0 Å . Curve-fitting
procedures from the VIPER and FEFF-7 programs were employed to
calculate the distances and coordination numbers precisely.
4
dryness. The oily residue was washed with methanol, and repre-
cipitated from dichloromethane with hexane. The precipitate was
separated chromatographically (sorbent: Silasorb SPH-300; eluent:
dichloromethane–hexane 2:1). The first major elute, which con-
tained the target product, was rotary evaporated to dryness. The
solid residue was reprecipitated from dichloromethane with hex-
ane, washed with hexane, and dried in vacuo. Yield: 0.32 g (33%)
3
. Syntheses
3.1. FeBd ((HOCH
2
2
CH
2
S)
2 2
Gm)(BF) (1)
Complex FeBd
suspended in dichloromethane (30 ml) and an 3.5-fold excess of
-mercaptoethanol (0.1 ml, 1.4 mmol) and triethylamine (0.19
ml, 1.4 mmol) was added. The reaction mixture was stirred for
h and rotary evaporated to dryness. The oily residue was washed
2
(Cl
2
Gm)(BF) (0.15 g, 0.2 mmol) was dissolved/
2
Anal. Calc. for C38
38 6 6 6 2 2
H N O S B F Fe: C, 46.44; H, 3.87; N, 8.55; Fe,
2
5.68. Found: C, 46.28; H, 3.83; N, 8.51; Fe, 5.62%. MS(PD): m/z
+
Å 1
982 [M] . H NMR (CD
(m, 12H, SCH CH SCH ), 3.40 (m, 4H, CltSCH
C{ H} NMR (CD Cl ): d (ppm) 23.00 (s, CH
(s, CH ), 33.3 (s, CH ), 34.3 (s, CH ), 126.3 (s, Ph), 127.3 (s, Ph),
128.6 (s, Ph), 128.8 (s, Ph), 146.7 (s, SC@N), 155.3 (s, PhC@N). IR
2
Cl
2
): d (ppm) 1.53 (t, 2H, SH), 2.49–2.80
), 7.24 (m, 20H, Ph).
), 30.6 (s, CH ), 32.7
1
2
2
2
2
1
3
1
with diluted acetic acid, and then with methanol, and dried in va-
cuo. The dark-red solid was reprecipitated from dichloromethane
with hexane, washed with hexane, and dried in vacuo. Yield:
2
2
2
2
2
2
2
ꢀ
1
0
3
6
.11 g (87%). Anal. Calc. for C34
H
30
N
6
O
8
2
B F
2
FeS
2
: C, 49.19; H,
(cm , KBr): 1538sh m(SC@N), 1582 m(PhC@N), 930–940m, 1064
m(N–O), 1208m m(B–O) + m(B–F). UV–Vis (CH
mol l cm ) 246(33), 291(17), 399(3.8), 485(27) nm.
ꢀ
3
.62; N, 10.13; Fe, 6.73. Found: C, 49.11; H, 3.61; N, 10.11; Fe,
.75%. MS(PD): m/z 830 [M] . H NMR (CDCl ): d (ppm) 2.67 (m,
3
2
Cl
2
): kmax (10 e/
+Å
1
ꢀ1
ꢀ1

Y.Z. Voloshin et al. / Inorganica Chimica Acta 362 (2009) 149–158
151
3.5. FeBd (((H C
2 5 2
2 2
)S(CH CH S)
2 2
) Gm)(BF)
2
(5)
2 4 9 2 4 n
3.8. [FeBd ((n-C H S) Gm)PtCl ] (8)
Complex 4 (0.16 g, 0.16 mmol), 40-fold excess of ethyl iodide
1 ml, 12.5 mmol) and 20-fold excess of triethylamine (1 ml,
.2 mmol) were dissolved in dry DMF (5 ml). The reaction mixture
was stirred for 10 h under argon, and then precipitated with
water. The solid residue was extracted with dichloromethane
and the extract was dried with K CO . The dichloromethane
2 3
solution was evaporated to dryness, and the solid residue was
washed with methanol, hexane, and dried in vacuo. Yield: 0.15 g
Complex 3 (0.15 g, 0.19 mmol) and trans-PtCl (C H CH CN)
4 6 5 2 2
(
7
(0.11 g, 0.19 mmol) were dissolved/suspended in nitromethane
(6 ml) and refluxed for 2 min. Then, the reaction mixture was evap-
orated to dryness in vacuo. The oily residue was dissolved/sus-
pended in toluene (10 ml) and evaporated to dryness. This
procedure was repeated two times, and then the solid residue
was dissolved in hot benzene. The hot benzene extract was filtered
and precipitated with hexane. The precipitate was washed with
hexane and dried in vacuo. Yield: 0.12 g (76%). Anal. Calc. for
(
92%). Anal. Calc. for C42
46 6 6 2 2 6
H N O B F FeS : C, 48.55; H, 4.43; N,
8
.09; Fe, 5.38. Found: C, 48.69; H, 4.31; N, 8.09; Fe, 5.31%. MS(PD):
38 38 6 6 2 2 2 4
C H N O S B F FePtCl : C, 38.31; H, 3.22; N, 7.06; Fe, 4.69; Pt,
16.37; Cl, 11.90. Found: C, 38.22; H, 3.05; N, 7.00; Fe, 4.51; Pt,
16.09; Cl, 11.78. MS(MALDI-TOF): m/z (I, %) (positive region):
+Å 1
m/z 1038 [M] . H NMR(CDCl
3
): d (ppm) 1.17 (t, 6H, CH
), 2.84 (m, 4H, SCH ), 3.58 (m,
): d (ppm)
), 32.1 (s, SCH ), 32.5
(Et)), 127.8 (s, Ph), 128.9 (s, Ph), 130.1
s, Ph), 130.7 (s, Ph), 147.9 (s, SC@N), 156.8 (s, PhC@N). IR
3
), 2.48
(
4
1
(
m, 4H, SCH ), 2.66 (m, 8H, SCH
2
2
2
13
1
ꢀ +
Åꢀ
H, SCH
4.7 (s, CH
), 34.3 (s, SCH
2
(Et)), 7.35 (m, 20H, Ph). C{ H} NMR(CDCl
3
1156 [MꢀCl ] , (negative region): ꢀ1191(10) [M] ; ꢀ1134(20)
ꢀ ꢀ ꢀ
3
), 25.8 (s, SCH ), 31.6 (s, SCH
2
2
2
[MꢀBu] ; ꢀ1099(25) [MꢀBuꢀCl] ; ꢀ1063(100) [MꢀBuꢀ2Cl] ;
ꢀ ꢀ
s, SCH
2
2
ꢀ1006(45) [Mꢀ2Buꢀ2Cl] ; ꢀ971(50) [Mꢀ2Buꢀ3Cl] ; ꢀ935(15)
ꢀ
1
(
[Mꢀ2Buꢀ4Cl]
1.46 (m, 4H, CH
(m, 2H, SCH
(ppm) 13.4, 13.6 (both s, CH
.
H NMR (CD
2
Cl
2
): d (ppm) 0.86 (m, 6H, CH
(Pt)), 3.52 (m, 2H, SCH ), 3.90
Cl ): d
(Pt)), 21.8, 21.9 (both s,
+ CH (Pt)), 43.8, 44.7 (both
(Pt)), 128.3, 128.4 (both s, Ph), 128.9, 129.1 (both s,
3
),
ꢀ1
(
cm , KBr): 1546 m(SC@N), 1595 m(PhC@N), 941m, 1067 m(N–O),
2
), 2.04 (m, 4H, CH
2
2
ꢀ
3
13
1
1
210m m(B–O) + m(B–F). UV–Vis (CH
2
Cl
2
):
k
max
(10 e/
2
(Pt)), 7.29 (m, 20H, Ph). C{ H} NMR (CD
+ CH
(Pt)), 29.4, 30.1 (both s, CH
2
2
ꢀ1
ꢀ1
mol l cm
85(32) nm.
)
261(16), 280(18), 300(11), 328(3.0), 396(3.8),
2
2
4
CH
2
+ CH
2
2
2
s, SCH
2
+ SCH
2
2
3.6. FeBd (S
3
-cwGm)(BF)
2
(6)
Ph), 130.7, 130.9 (both s, Ph), 131.4, 131.5 (both s, Ph), 140.6,
Complex 4 (0.16 g, 0.16 mmol) and 10-fold excess of Cs
2 3
CO
(
0.6 g, 1.8 mmol) were dissolved/suspended in dry DMF (12 ml).
Table 1
The reaction mixture was stirred under argon for 12 h, and then
precipitated with water. The precipitate was extracted with dichlo-
romethane and the extract was filtered through Silasorb SPH-300
layer (10 mm). The filtrate was evaporated to 1/2 volume and
precipitated with hexane. The solid was washed with hexane and
2 4 9 2 2
Crystallographic data and experimental details for FeBd ((n-C H S) Gm)(BF) (3) and
FeBd
2
(((H
5
C
2
)S(CH
2
CH
2
S)
2
)
2
Gm)(BF)
2
(5) ꢁ C
6
H
6
complexes
Data
3
5
Empirical formula
Fw
Temperature (K)
Color, habit
Crystal
dimensions
(mm)
a (Å)
C
38
H
38
B
2
F
2
FeN
6
O
S
6 2
48 52 2 2 6 6 6
C H B F FeN O S
1116.79
110(2)
red, plate
0.07 ꢄ 0.18 ꢄ 0.55
854.33
110(2)
red, needle
0.10 ꢄ 0.12 ꢄ 0.70
dried in vacuo. Yield: 0.074 g (56%). Anal. Calc. for C34
N O S B F Fe: C, 49.28; H, 3.38; N, 10.15; Fe, 6.74. Found: C,
6 6 3 2 2
H
28
-
+Å
1
4
9.41; H, 3.41; N, 10.04; Fe, 6.59%. MS(PD): m/z 828 [M] .
NMR (CD Cl ): d (ppm) 3.00 (m, 4H, SCH ), 3.61 (m, 4H, CltSCH
.23 (m, 20H, Ph). C{ H} NMR (CD ): d (ppm) 34.7 (s, CH
8.4 (s, CH
H
2
2
2
2
),
),
1
3
1
7
3
2
Cl
2
2
13.746(6)
17.532(8)
16.451(7)
95.233(8)
3948(3)
4
monoclinic
P21/n
1.437
20.823(5)
12.082(3)
21.180(5)
104.664(4)
5155(2)
4
monoclinic
P21/n
1.439
2
), 128.3 (s, Ph), 129.4 (s, Ph), 130.1 (s, Ph), 130.7 (s,
ꢀ1
b (Å)
c (Å)
Ph), 151 (s, SC@N), 157.2 (s, PhC@N). IR (cm , KBr): 1542 m(SC@N),
1
Vis (CH
2
577 m(PhC@N), 928m, 1064 m(N–O), 1212m m(B–O) + m(B–F). UV–
b (°)3
ꢀ
3
ꢀ1
ꢀ1
2
2
Cl ):
k
max (10 e/mol l cm
)
236(33), 263(7.7),
V (Å )
Z
84(13), 303(8.2), 424(4.5), 485(26) nm.
Crystal system
Space group
3
.7. ((n-C N) [((FeBd (S Gm))(BF) Pt
4
H
9
)
4
2
2
2
2
)
2
2
Cl
2
] (7)
ꢀ3
D
calc. (g cm
)
ꢀ
1
l (mm
)
0.551
0.597
Complex 2 (0.36 g, 0.5 mmol) and ((n-C
.5 mmol) were dissolved/suspended in nitromethane (10 ml).
4 9
H )
N)
4 2
PtCl
4
(0.38 g,
Minimum/
0.711
0.734
maximum
transmission
coefficient
h Max (°)
0
The stirring reaction mixture was refluxed for 6 h, cooled to room
temperature, and filtered. The filtrate was rotary evaporated to
ꢂ2 ml and precipitated with diethyl ether (15 ml). The oily residue
was reprecipitated from chloroform with diethyl ether. The
precipitate was washed with methanol, diethyl ether, hexane,
and dried in vacuo. Yield: 0.060 g (20%). Anal. Calc. for
2
56.2
33195
58.7
47002
Reflections
collected
Independent
reflections
(R )
int
Data/restraints/
parameters
9410 (0.038)
13043 (0.051)
C
4
4
92
112
H N
14
O
12
S B
4 4
F
4
Fe
2 2
Pt Cl
2
: C, 45.55; H, 4.62; N, 8.09; Fe,
9410/91/562
13034/10/726
.60; Pt, 16.10; Cl, 2.93. Found: C, 45.64; H, 4.64; N, 8.16; Fe,
½rðF Þ þ 0:18ðF 2o þ 2F Þ=3ꢃ
2
2
2
c
ꢀ1
½rðF Þ þ 0:096ðF 2o þ 2F Þ=3ꢃ
2
2
2
c
ꢀ1
Weighting
.47; Pt, 15.90; Cl, 2.81. MS(MALDI-TOF): m/z (I, %) (negative re-
o
o
þ
2ꢀ
+
scheme
gion): ꢀ970 (100) ½M ꢀ 2NBu
ꢃ
; ꢀ1006(30) [Mꢀ2Bu
4
N ꢀFeBd
2
-
a
4
R
R
1
[I>2r(I)]
0.0849
0.2969
1768
0.932
1.58/ꢀ0.89
0.0572
0.1682
2320
1.272
1.27/ꢀ0.69
+
ꢀ 1
(
S
2
Gm)(BF)
2
Pt+H ] . H NMR (CD
2
Cl
2
): d (ppm) 0.83 (t, 24H, CH
3
),
b
w
1
(
(
1
.28 (m, 16H, CH
m, 20H, Ph). C{ H} NMR (CD
2
), 1.50 (m, 16H, CH
2
), 3.06 (m, 16H, NCH
): d (ppm) 13.7 (s, CH
), 127.9 (s, Ph), 129.4 (s, Ph),
30.0 (s, Ph), 130.7 (s, Ph), 154.8-153.3 (m, SC@N), 154.3 (s,
2
), 7.23
F(000)
1
3
1
c
2
Cl
2
3
), 19.9
Goodness-of-fit
Maximum/
minimum
s, CH ), 24.2 (s, CH ), 59.3 (s, NCH
2
2
2
residual peak
ꢀ1
PhC@N). IR (cm , KBr): 1520sh m(SC@N), 1595 m(PhC@N), 950m,
060 m(N–O), 1205m m(B–O) + m(B–F). UV–Vis (CH Cl ):
246(27), 277(14), 301(10), 362(2.9),
P
P
P
a
b
c
R
1
= ( kF
o
j ꢀ jF
c
k)/
ꢀ Fc
F
o
j.
1
(
4
2
2
k
max
P
P
ꢀ
3
ꢀ1
ꢀ1
Rw ¼ ½ ðwðFo
2
2
Þ Þ= wðF Þ ꢃ1=2.
2
2
2
10 e/mol l cm
)
o
2
o
2
c
Þ2Þ=ðNobs ꢀ NparamÞꢃ1=2.
78(16), 515(11) nm.
Goodness-of-fit ¼ ½ ðwðF
ꢀ F

1
52
Y.Z. Voloshin et al. / Inorganica Chimica Acta 362 (2009) 149–158
1
40.9 (both s, SC@N + SC@N(Pt)), 159.1, 159.3 (both s, PhC@N +
Single-crystal X-ray diffraction experiments for both the com-
pounds were carried out with a Bruker SMART 1K CCD area detec-
ꢀ
1
PhC@N(Pt)). IR (cm
,
KBr): 1510–1520m m(SC@N), 1595sh
m(PhC@N), 935–960 m, 1070 m(N–O), 1225m m(B–O) + m(B–F).
tor (graphite monochromated Mo Ka radiation, k = 0.71073 Å) [16]
ꢀ3
ꢀ1
ꢀ1
UV–Vis (CH
2
Cl
2
): kmax (10 e/mol l cm ) 258(43), 303(12),
equipped with Cryostream (Oxford Cryosystems) open-flow N
system. Reflection intensities were integrated using SAINT software
17] and corrected by a semi-empirical method (SADABS program)
[18].
The structures of 3 and 5 were solved by the direct method.
2
gas
3
90(8.6), 470(17), 518(16) nm.
[
4
. X-ray crystallography
Details for crystal data collection and refinement of FeBd
2
-
Refinement was done using full-matrix least squares method of
the SHELXTL software against F of all the data [19]. Non-hydrogen
atoms were refined in anisotropic approximation with the excep-
tion of benzene solvate molecules in crystal 5. The S(6) atom of
2
(
(
(n-C
5) ꢁ C
4
H
9
S)
2
Gm)(BF)
2
(3) and FeBd
2
((H
5
C
2
SC
2
H
4
SC
2
H
4
S)
2
Gm)(BF)
2
6
H
6
complexes are listed in Table 1. Single crystals of these
complexes were grown from chloroform–heptane (3) and ben-
zene–isooctane (5) mixtures at room temperature.
3
one of the two functionalizing S -containing substituents and ben-
F
B
O
N
O
N
O
S
S
N
Fe2+
F
N
O
N
N
O
B
O
O
O
O
N
B
S
S
S
S
S
S
Cl
Cl
N
Fe2+
N
Pt4+
F
F
Cl
Cl
B
trans-PtCl4(BzCN)2
n
N
N
O
N
O
O
N
O
N
O
N
O
CH NO
3
t˚
2
8
S
S
F
B
Fe2+
F
B
F
N
N
O
O
N
O
N
O
N
B
N
O
ICH2CH2I
Cs2CO3
O
S
S
OH
OH
O
N
O
O
N
DMF
Fe2+
N
Fe2+
S
S
S
S
S
S
B
F
N
O
N
N
O
F
B
3
O
N
O
N
N
O
C2H5I
TEA
B
F
O
N
O
O
N
O
CH2Cl2
S
S
S
SH
B
F
N
Fe2+
1
DMF
n-C4H9SH
TEA
F
5
B
O
O
N
O
N
N
O
N
O
N
O
S
SH
S
S
S
ICH CH I
Cs2CO3
N
HS
OH
2
2
Fe2+
B
F
F
HS
S
SH
DMF
N
O
N
N
O
S
4
O
B
F
F
F
O
O
O
N
B
F
B
B
B
Cl
Cl
N
N
O
N
O
N
O
O
N
O
O
N
O
N
O
O
Fe2+
Cd2+, – H+
S
S
S
S
S
S
S
N
N
N
N
Fe2+
F
Fe2+
Fe2+
N
O
N
N
O
S
B
O
N
N
N
O
N
O
N
O
N
N
O
N
O
S
N
O
N
O
N
O
N
O
HS
S
SH
O
O
B
F
O
S
S
S
S
B
F
B
B
F
Fe2+
F
N
O
N
N
O
O
6
B
F
CH3SH
TEA
CH2Cl2
F
F
F
B
2–
F
F
2–
B
B
B
B
O
O
N
O
N
O
O
N
O
O
N
O
O
O
N
O
N
O
O
N
O
N
O
N
SCH3
N
S
S
Cl
Cl
S
N
Fe2+
S
S
S
S
N
N
PtCl42–
N
N
Fe2+
Fe2+
Pt2+
Pt2+
Fe2+
Pt2+
Fe2+
CH3NO2
t˚
– CH3Cl
N
O
N
N
O
SCH3
N
O
N
N
O
S
N
O
N
O
N
O
N
O
N
N
O
N
O
N
N
O
O
O
O
O
B
F
B
F
B
F
B
F
B
F
2
7
9
Scheme 1.
H+
S
S
–
S
S
S
SH
S
S
S–
S
n
n
n
+
H+
S
S
SH
n
Scheme 2.

Y.Z. Voloshin et al. / Inorganica Chimica Acta 362 (2009) 149–158
153
F
F
B
B
O
N
O
N
O
N
O
N
O
N
O
N
S
S
S
S
SH
SH
S
S
S
S
SH
S
H+
–
Fe2+
Fe2+
N
O
N
N
O
N
O
N
N
O
O
O
B
F
B
F
F
F
B
B
O
N
S
S
SH
O
O
N
O
N
O
O
S
S
N
Fe2+
N
Fe2+
+
H+
N
S
S
HS
S
SH
N
O
N
N
O
S
N
O
N
N
O
S
O
O
B
F
B
F
Scheme 3.
Table 2
The 57Fe Mössbauer parameters (mm/s) for disulfide iron(II) clathrochelates
zene solvate molecules in 5 as well as the C(9), C(10), C(12), C(13)
and C(14) atoms of n-butyl substituents in 3 are equiprobably dis-
ordered at two positions. In molecule 3, the C–C bond lengths for
disordered n-butyl fragments were restricted to 1.54 Å and the
anisotropic displacement parameters (ADPs) at two alternative
positions were constrained to be equal. In molecule 5, the S–C bond
lengths in the disordered moiety were restricted to 1.82 Å, and
ADPs for two positions of the S(6) atom were restricted to be equal.
Benzene rings at two positions were constrained to keep their
shape as regular hexagons. The positions of hydrogen atoms were
calculated geometrically and refined using the riding model with
isotropic temperature factors Uiso = nUeq(C), where n = 1.5 for
Complex
IS
QS
u obtained (deduced)
°)
(
FeBd
FeBd
FeBd
FeBd
FeBd
2
2
2
2
2
((HOCH
((n-C
(((H
((HS(CH
(S -cwGm)(BF)
((n-C S) Gm)PtCl
N) [((FeBd (S Gm))(BF)
((CH S) Gm)(BF) [9]
2
CH
S) Gm)(BF)
)S(CH CH S)
CH S)
2
S)
2
Gm)(BF)
2
0.33
0.37
0.35
0.32
0.32
0.32
0.32
0.32
0.40
0.48
0.46
0.29
0.40
0.49
0.56
0.36
(23–28)
a
4
H
9
2
2
24.8
25.3
a
5
C
2
2
2
)
2 2
Gm)(BF)
2
2
2
2
2
) Gm)(BF)
2
(25–30)
(23–28)
(22–27)
(20–25)
3
2
[
(
FeBd
(n-C
2
4
H
9
2
4
]
4
H
9
)
4
2
2
2
2
)
2
Pt
2 2
Cl ]
a
FeBd
2
3
2
2
25.8
a
X-ray data.
Fig. 1. General view of the molecule 3.

1
54
Y.Z. Voloshin et al. / Inorganica Chimica Acta 362 (2009) 149–158
Fig. 2. General view of the molecule 5.
Table 3
5. Results and discussion
The main geometrical parameters for FeBd
2
((n-C
4
H
9
S)
2
Gm)(BF)
2
(3) and
FeBd
2
(((H
5
C
2
)S(CH
2 2
CH S)
2
)
2
Gm)(BF)
2
(5) ꢁ C
6 6
H complexes
5.1. The synthesis and reactivity of disulfide clathrochelates
Parameter
Fe–N (Å)
3
5
The nucleophilic substitution of the reactive chlorine atoms in
the FeBd (Cl Gm)(BF) molecule, resulting in disulfide clathroche-
2 2 2
1.900(3)–1.922(3)
av. 1.911
1.907(2)–1.919(2)
av. 1.912
B–F (Å)
B–O (Å)
N–O (Å)
N@C (Å)
1.351(5)–1.352(5)
av. 1.352
1.468(5)–1.502(5)
av. 1.488
1.357(4)–1.379(4)
av. 1.368
1.301(6)–1.317(5)
av. 1.309
1.429(7)–1.462(5)
av. 1.446
1.714(5)–1.716(5)
av. 1.715
78.3(1)–79.4(2)
av. 78.7
107.7(3)–109.0(3)
av. 108.4
109.5(4)–111.2(3)
av. 110.5
111.0(3)–112.8(3)
av. 112.0
116.6(3)–118.4(4)
av. 117.5
110.7(3)–113.7(4)
av. 111.8
123.3(3), 123.8(4)
7.4(6)–9.5(6)
av. 8.1
24.8
2.334
1.358(4)–1.365(4)
av. 1.362
1.473(4)–1.492(4)
av. 1.485
1.371(3)–1.379(3)
av. 1.375
1.300(4)–1.309(4)
av. 1.305
1.457(4)–1.465(4)
av. 1.462
1.735(3)–1.761(3)
av. 1.748
78.2(1)–78.4(1)
av. 78.3
106.8(2)–108.6(2)
av. 107.8
110.2(2)–111.7(2)
av. 111.1
111.4(2)–112.1(2)
av. 111.7
116.5(2)–117.1(2)
av. 116.8
110.5(2)–111.7(2)
av. 111.2
118.0(2), 120.9(2)
7.5(4)–12.2(4)
av. 9.1
25.3
2.320
lates 1–4, are shown in Scheme 1. We devised and implemented a
new approach for the synthesis of these iron(II) clathrochelates.
This new approach uses a RSH/triethylamine (TEA) system in
dichloromethane medium instead of the previously proposed
RSH/alkaline metal alcoholate system in donor solvents (DMF,
THF, and 1,4-dioxane). In the former case, the nucleophilic substi-
tution occurred under mild conditions in higher yield and required
neither the additional purification of the solvent from traces of
water nor the isolation of the alkaline metal alcoholate. This ap-
proach allowed us to significantly simplify the synthetic proce-
dures for monothiolate nucleophilic agents as well as to obtain
functionalized complexes in high yields. The use of an RSH/TEA/
@
@
C–C@ (Å)
C–S– (Å)
N–Fe–N (°)
F–B–O (°)
O–B–O (°)
N–O–B (°)
C@N–O (°)
N@C–C (°)
2 2
CH Cl system with bifunctional dithiolate nucleophilic agents
led to a reduction in a number of by-products that resulted from
the side intramolecular self-dealkylation via Scheme 2 (‘‘dragon
bitting its own tail” type), because in this case the thiolate anion/
thiol equilibrium was shifted to the protonated form. We
failed to obtain the thiocrown-containing clathrochelates by 1:1
condensation of the FeBd (Cl Gm)(BF) precursor with 3,5-dithia-
2 2 2
octane-1,8-dithiol and 3,6-dithianonane-1,9-dithiol because the
previously mentioned side reactions occured. Template condensa-
@
C–C–S– (°)
N@C–C@N (°)
tion of the (HSCH
precursor on the Cd ion in the presence of triethylamine gave a
mixture of the S -thiocrown- and S -thiocrown-containing mono-
and bis-clathrochelates, which we were unable to separate with
column chromatography. We attempted to synthesize the S -thio-
crown-etheric clathrochelate with step-by-step procedure.
2 2 2 2 2 2
CH ) S thiodithiol with the FeBd (Cl Gm)(BF)
a
2+
u
h
a
(°)
(Å)
(°)
b
3
6
c
39.2
39.4
a
Distortion angle.
6
b
Distance between the coordination polyhedron bases (the height of the dis-
a
torted trigonal prism).
Clathrochelate dithiol 4 was readily alkylated with the ethyl
iodide/OEA system in DMF to give product 5. Nevertheless, the
template condensation of complex 4 with 1,2-diiodoethane in the
c
Bite angle (half of chelate angle).
methyl groups and 1.2 for the other groups. Ueq are the equivalent
isotropic displacement parameters of the corresponding pivot car-
bon atoms.
presence of Cs
lone S -thiocrown-containing clathrochelate 6. It is evident that
the deprotonated monothiol group of molecule 4 attacks the
2 3
CO in DMF unexpectedly caused the formation of
3

Y.Z. Voloshin et al. / Inorganica Chimica Acta 362 (2009) 149–158
155
adjacent thiosulfide substituents, and this results in the dealkyla-
tion of this fragment and the formation of the nine-membered
S-demethylation reactions for the platinum(II) complexes were de-
scribed previously [20]. The dimeric tetranuclear bis-clathroche-
S
3
-cycle (Scheme 3). This is a major reaction pathway, whereas
2
late 7 with two l -bridging chlorine atoms was isolated and
the condensation of the monothiolate clathrochelate anion formed
with 1,2-diiodoethane is a minor reaction pathway.
characterized with both elemental analysis and spectral data.
The reaction of n-butylsulfide clathrochelate 3 with the plati-
4 6 5 2 2
num(IV) trans-PtCl (C H CH CN) complex afforded the binuclear
compound 8 with the disulfide iron(II) clathrochelate as a mono-
dentate ligand (Scheme 1).
2
+
5
.2. The complexation of clathrochelate disulfide ligands with Pt and
4
+
Pt ions
As mentioned previously, the disulfide macrobicyclic iron(II)
5.3. Structure and spectra
complexes are potential ligands for metal ions. We failed to ob-
serve the interaction of n-butylsulfide clathrochelate 3 with the
platinum(II) ion, but the reaction of the methylsulfide complex 2
The 57Fe Mössbauer parameters of the disulfide clathrochelates
2
+
4+
and their polynuclear complexes with Pt and Pt ions (Table 2)
characterized them as low-spin iron(II) complexes (isomeric shifts
[ISs] are in the range 0.32–0.37 mm/s) with their geometry
intermediate between that of a trigonal prism (TP) and a trigonal
antiprism (TAP) (quadrupole splittings [QSs] are in the range
0.29–0.48 mm/s). For several complexes that we synthesized, we
failed to obtain monocrystals suitable for direct X-ray crystallo-
graphic experiments. Their distortion angles u of the iron(II)
2ꢀ
with [PtCl
4
]
dianion produced the polynuclear complexes 7 and
9
of the dianionic clathrochelate dithiolate ligand with the elimina-
tion of methylchloride. These complexes were characterized both
by the MALDI-TOF mass (the intense peak m/z ꢀ970 of the
þ
2ꢀ
½
7 ꢀ 2NBu
ꢃ
dianion for clathrochelate 7 and the intense peak
4
þ
þ
ꢀ
m/z ꢀ1675 of the ½9 ꢀ 2NBu þ H ꢃ for compound 9) anion and
4
1
13
1
H, C{ H} NMR spectra (for clathrochelate 7, see Section 2). Such
Fig. 3. Projection of the molecular layer of the complex 3 to the crystallographic plane (001). Only one position for disordered groups is shown.

1
56
Y.Z. Voloshin et al. / Inorganica Chimica Acta 362 (2009) 149–158
Fig. 4. A fragment of the crystal packing of the complex 5 in projection to the crystallographic plane (100). Only one position for disordered groups is shown and benzene
solvate molecules are omitted for clarity.
coordination polyhedra (u = 0° for TP and u = 60° for TAP), listed in
Table 2, were deduced using the modern partial QS concept [21].
Despite the presence of two types of a-dioximate fragments in
the molecules of disulfide iron(II) clathrochelates that we synthe-
sized, the UV–Vis spectra of their solutions contained a single in-
carbon atoms). In particular, the monodentate coordination mode
4
+
of the n-butylsulfide clathrochelate ligand 3 to Pt ion manifested
1
13
1
itself in a double set of the H and C{ H} NMR signals in the spec-
tra of binuclear product 8: one of these two sets is closer to those in
the spectra of the initial clathrochelate 3, whereas the second set is
4
ꢀ1
ꢀ1
*
1
tense (e ꢂ 3 ꢄ 10 mol L cm ) Fed ? Lp charge transfer band
CTB) in the visible region. This suggests the high r- and p-conju-
gation in the clathrochelate framework. The position of this band
max ꢅ 483–486 nm) is practically unaffected by the nature of
the peripheral substituents in the functionalized sulfur-containing
dioximate fragments (i.e., their effects on the chromophore FeN
shifted significantly (up to 0.6 ppm) upfield in the H NMR spec-
1
3
1
(
trum and up(down)field shifted in the C{ H} NMR spectrum. In
the latter case, the most significant (approximately 10 ppm) down-
and up-field shifts were observed for the donor azomethine SC@N
fragment and adjacent to its methylene carbon atoms, respectively.
This indicates of the redistribution of electron density in the sulfur-
containing fragments due to the coordination of the sulfur donor
atoms to the platinum(IV) ion. The ratio of line integral intensity
(k
6
-
center are negligible). In the spectra of binuclear complexes 7
and 8, this CTB splits into two bands of similar intensity, which
clearly demonstrates the effect of coordination of the donor sulfur
atoms of disulfide clathrochelate ligands to the platinum(II) and
platinum(IV) ions on the electronic systems of these ligands.
The composition, symmetry and purity of the complexes we ob-
1
for the corresponding signals in the H NMR spectra approaches
1
3
1
1:1. In the solution C{ H} NMR spectra of the polynuclear com-
2
+
4+
plexes of disulfide clathrochelate ligands with Pt and Pt ions,
the signals of azomethine SC@N carbon atoms have multiplet char-
acter because of the spin–spin interactions of their nuclei with
nonzero-spin platinum isotopes.
1
13
tained were confirmed by their solution H and C NMR spectra
especially the line integral intensities of phenyl and functionali-
(
1
zing substituents protons in the H NMR spectra and the number
of the signals in the C NMR spectra assigned to the azomethine
Molecular structures of complexes 3 and 5, solved by X-ray
crystallography, are shown in Figs. 1 and 2. The main geometrical
1
3

Y.Z. Voloshin et al. / Inorganica Chimica Acta 362 (2009) 149–158
157
parameters of these molecules are listed in Table 3. Average bond
lengths and bond angles in the macrobicyclic frameworks for both
the complexes are the same and are close to the data found in the
literature for clathrochelate iron(II) tris-dioximates [1–11,21–28],
plex 5 as well as the differences between complexes 3 and 5 might
be caused by these disorders of functionalizing S-containing
substituents.
The main geometrical parameters of the coordination polyhedra
of complexes 3 and 5 are similar. The distortion angles u are
25.3(4) and 24.8(5)° for clathrochelates 3 and 5, respectively. These
angle u values are typical for monoribbed-functionalized a-benzyl-
dioximate clathrochelates [4,9–11,21]. The distances h between
the coordination polyhedron bases are 2.334 and 2.320 Å for com-
plexes 3 and 5, respectively.
except for sulfur-containing moieties. The average Csp
length in 5 seems to be slightly longer than that in 3 (1.748(3)
versus 1.715(5) Å, respectively), whereas the Csp —Csp —S angle is
slightly smaller (119.5(2) versus 123.6(4), respectively). Also, these
entities (two crystallographically independent Csp —S bonds and
two Csp —Csp —S angles) vary substantially in molecule 5.
Alkylsulfide substituents were disordered in both the crystals
see Section 2) and the previously mentioned differences for com-
2
—S bond
2
2
2
2
2
Clathrochelate 3 molecules form layered crystal packing: inside
the layer alkylsulfide substituents are located in the cavities of the
(
Table 4
EXAFS data on the distances (Å) from the encapsulated iron(II) ion for clathrochelate iron(II) dioximates
Fe ? N
Fe ? Pt
C
C
C
N
S
C
C
C
C
N
N
O
N
N
N
Fe
Fe
Fe
Fe
Compound
FeBd ((CH
cn = 6
cn = 6
2.78
2.78
2.88
2.84
cn = 6
2.88
2.88
3.05
2.99
cn = 4
cn = 2
cn = 1
2
3
S)
2
Gm)(BF)
2
1.91
4.08
4.21
4.35
4.48
4.61
4.69
a
a
a
a
a
1
.91
(
[
(n-C
FeBd
4
H
9
)
4
N)
2
[((FeBd
2
(S
2
Gm))(BF)
2
)
2
PtII
2
Cl
2
]
1.93
1.88
5.17
6.12
IV
2
((n-C
4
H
9
S) Gm)(BF)
2
2
4
Pt Cl ]
4.44
a
X-ray data [9].
Table 5
EXAFS data on the distances (Å) from the coordinating platinum ions for polynuclear clathrochelate iron(II) dioximates and X-ray crystallography data (Å) for several platinum(II)
and platinum(IV) compounds
Compound
Pt ? S
Pt ? Cl
Pt ? Fe
Pt ? Pt
Ref.
PtII
2.18
2.33
2.20
2.30
2.34
2.31
4.96
3.33
b
(
[
(n-C
FeBd
4
H
9
)
4
N)
2
[((FeBd
2
(S
2
Gm))(BF)
2
)
2
2
Cl
2
]
IV
b
2
((n-C
4
H
S)
9 2
2 4
Gm)(BF) Pt Cl ]
O
O
[29]
a
II
Pt Cl (PhSHC CHSPh)
2
II
-an-9-crown)a
Pt Cl
(S
2 3
2.22
2.23
2.34
2.32
[30]
[31]
F3C CF3
a
II
Pt Cl (MeSCHCHSMe)
2
II
SPh)a
Pt Cl
2
(PhSCH
2
CH
2
2.24
2.25
2.31
2.31
2.32
[32]
[33]
[34]
II
(3,3 -di(iPrS)
2
thiophen)a
0
Pt Cl
2
Cl
3.43
3.51
3.54
3.45
3.47
Cl
[
(2,6-diMePy) PtII Pt (2,6-diMePy)]
II
2+
a
Cl
Cl
Cl
F3C F3C
CF3 CF3
2.38
2.43
2.33
[35]
[36]
[37]
[38]
(
PCMePPtII PtII PCMeP) a
F3C
F3C
Cl
Cl
CF3 CF3
Cl
II
II
a
(
Et P)Pt
Pt (PEt )
3
3
Cl
Cl
Cl
II
PtII Cl2 ]2–
a
[
Cl Pt
2
Cl
O Cl
2.33
Cl
O
II
II
a
(
Et S) Pt
Pt (SEt )
2
2
Cl
Cl
(SMe
trans-PtIVCl
)
2
a
2.36
2.37
2.32
2.31
[39]
[40]
4
2
Et
a
trans-PtIVCl (SCH CHCH CH CH CH )
4
2
2
2
2
3 2
a
X-ray data.
This work.
b

1
58
Y.Z. Voloshin et al. / Inorganica Chimica Acta 362 (2009) 149–158
clathrochelate framework formed by means of hydrophobic inter-
action of phenyl substituents in a-benzyldioximate chelate frag-
ments (Fig. 3). The analysis of crystal packing of complex 5
reveals a similar feature: hydrophobic phenyl-containing substitu-
ents and sulfur-containing ones prefer to interact with the substit-
uents of the same type (Fig. 4). Benzene solvate molecules (not
shown in Fig. 4) play the role of spacers and fill up the cavities be-
tween the phenyl groups of the neighboring molecules.
www.ccdc.cam.ac.uk/data_request/cif. Supplementary data associ-
ated with this article can be found, in the online version, at
doi:10.1016/j.ica.2008.03.055.
References
[
1] Ya.Z. Voloshin, N.A. Kostromina, R. Krämer, Clathrochelates: Synthesis,
Structure and Properties, Elsevier, Amsterdam, 2002.
Because we failed to obtain single crystals of platinum-contain-
ing complexes 7 and 8, suitable for the X-ray crystallography
experiment, their structures were deduced from the EXAFS spectra,
which made it possible to calculate the radial distribution func-
tions of atoms (RDAs) that surround the scattering atoms. We ob-
tained the RDAs for both the encapsulated iron atoms and the
coordinating platinum atoms of complexes 7 and 8. The use of
two correlating EXAFS experiments for the same molecule in-
creases significantly the reliability of the results we obtained
[2] Y.Z. Voloshin, O.A. Varzatskii, T.E. Kron, V.K. Belsky, V.E. Zavodnik, A.V. Palchik,
Inorg. Chem. 39 (2000) 1907.
[
3] Y.Z. Voloshin, O.A. Varzatskii, T.E. Kron, V.K. Belsky, V.E. Zavodnik, N.G.
Strizhakova, V.A. Nadtochenko, V.A. Smirnov, Dalton Trans. (2002) 1203.
[4] Y.Z. Voloshin, O.A. Varzatskii, I.I. Vorontsov, M.Y. Antipin, A.Y. Lebedev, A.S.
Belov, N.G. Strizhakova, Russ. Chem. Bull., Int. Ed. 53 (2004) 92.
[
5] Y.Z. Voloshin, O.A. Varzatskii, A.V. Palchik, A.I. Stash, V.K. Belsky, New J. Chem.
3 (1999) 355.
2
[6] Y.Z. Voloshin, O.A. Varzatskii, A.V. Palchik, I.I. Vorontsov, M.Y. Antipin, E.G.
Lebed, Inorg. Chim. Acta 358 (2005) 131.
[
[
[
7] Y.Z. Voloshin, O.A. Varzatskii, A.V. Palchik, Z.A. Starikova, M.Y. Antipin, E.G.
Lebed, Y.N. Bubnov, Inorg. Chim. Acta 359 (2006) 553.
8] Y.Z. Voloshin, O.A. Varzatskii, A.V. Palchik, N.G. Strizhakova, I.I. Vorontsov, M.Y.
Antipin, D.I. Kochubey, B.N. Novgorodov, New J. Chem. 27 (2003) 1148.
9] Y.Z. Voloshin, V.E. Zavodnik, O.A. Varzatskii, V.K. Belsky, A.V. Palchik, N.G.
Strizhakova, I.I. Vorontsov, M.Y. Antipin, Dalton Trans. (2002) 1193.
[
23]. We also calculated the RDA for the encapsulated iron atom
in the model X-ray crystallographically characterized complex 3
9]. As seen from Table 4, the EXAFS data for this complex is in
[
good agreement with the direct X-ray crystallographic data.
The RDA curves for the encapsulated iron atom in complexes 7
and 8 contain the peaks from the atoms of iron nearest environ-
ment (six donor nitrogen atoms) and those of the second and third
coordination spheres (oxygen and carbon atoms of the clathroche-
late framework as well as the adjacent carbon and sulfur atoms of
the ribbed substituents). Moreover, RDAs for complexes 7 and 8
[
[
[
10] Y.Z. Voloshin, A.S. Belov, A.Y. Lebedev, O.A. Varzatskii, M.Y. Antipin, Z.A.
Starikova, T.E. Kron, Russ. Chem. Bull., Int. Ed. 53 (2004) 1171.
11] Y.Z. Voloshin, O.A. Varzatskii, Z.A. Starikova, M.Y. Antipin, A.Y. Lebedev, A.S.
Belov, Russ. Chem. Bull., Int. Ed. 53 (2004) 1439.
12] R.G. Pearson, J. Am. Chem. Soc. 85 (1963) 3533.
[13] V.Yu. Kukushkin, T.B. Pakhomova, Y.N. Kukushkin, R. Herrmann, G. Wagner,
A.J.L. Pombeiro, Inorg. Chem. 37 (1998) 6511.
[
14] A.N. Nekrasov, V.V. Yutchenko, SPECTRA Program, Karpov Institute of Physical
Chemistry, Moscow, Russia, 1996.
(
Table 4) contain peaks at 5.17 and 6.12 Å, respectively, which
[15] K.V. Klementev, Nucl. Instrum. and Meth. A 448 (2000) 299.
[
16] Bruker SMART, Bruker Molecular Analysis Research Tool, v. 5.059, Bruker AXS,
Madison, Wisconsin, USA, 1998.
were attributed to scattering on the heavy platinum atoms with
a high back scattering factor.
[
17] SMART and SAINT, Release 5.0, Area detector control and integration software,
Bruker AXS, Analitical X-ray Instruments, Madison, Wisconsin, USA, 1998.
The RDA curves for the coordinating platinum atoms in com-
plexes 7 and 8 contain the peaks that are caused by scattering on
the sulfur and chlorine atoms of the nearest environment. The dis-
tances to these atoms, obtained from the RDA curves (2.13–2.31 Å),
are in good agreement with those known from direct X-ray crystal-
lography data in the literature (Table 5). In the RDA curve for com-
plex 7, we observed a peak at 4.96 Å, caused by scattering on the
encapsulated iron atom. With allowance for the negligible contri-
bution of this peak to the overall spectrum, this value correlates
well with the distance equal to 5.13 Å, which was obtained from
the RDA curve for the encapsulated iron atom. The RDA curves
for the platinum atom in complex 7 also contain an intense peak
at 3.33 Å due to the scattering on the adjacent platinum atom in
Cl
[18] G.M. Sheldrick, SADABS: A Program for Exploiting the Redundancy of Area-
Detector X-ray Data, University of Gottingen, Gottingen, Germany, 1999.
[
19] G.M. Sheldrick, SHELXTL, Version 5.1, Bruker AXS, Inc., Madison, Wisconsin, USA,
997.
[20] L.F. Lindoy, S.E. Livingstone, T.N. Lockyer, Inorg. Chem. 6 (1967) 652.
1
[
21] Y.Z. Voloshin, E.V. Polshin, A.Y. Nazarenko, Hyperfine Interact. 141–142 (2002)
09.
3
[
22] A.B. Burdukov, E.G. Boguslavskii, V.A. Reznikov, N.V. Pervukhina, M.A.
Vershinin, Y.Z. Voloshin, O.A. Varzatskii, Y.N. Bubnov, Russ. Chem. Bull., Int.
Ed. (2005) 1097.
[
[
23] Y.Z. Voloshin, O.A. Varzatskii, S.V. Korobko, V.Y. Chernii, S.V. Volkov, L.A.
Tomachynski, V.I. Pehn’o, M.Y. Antipin, Z.A. Starikova, Inorg. Chem. 44 (2005)
822.
24] Y.Z. Voloshin, O.A. Varzatskii, S.V. Korobko, M.Y. Antipin, I.I. Vorontsov, K.A.
Lyssenko, D.I. Kochubey, S.G. Nikitenko, N.G. Strizhakova, Inorg. Chim. Acta
357 (2004) 3187.
[25] Y.Z. Voloshin, O.A. Varzatskii, A.I. Stash, V.K. Belsky, Y.N. Bubnov, I.I. Vorontsov,
K.A. Potekhin, M.Y. Antipin, E.V. Polshin, Polyhedron 20 (2001) 2721.
the Pt
2
Pt fragment with l -bridging chlorine atoms. The
[
[
[
26] Y.Z. Voloshin, O.A. Varzatskii, I.I. Vorontsov, M.Y. Antipin, A.Y. Lebedev, A.S.
Belov, A.V. Palchik, Russ. Chem. Bull., Int. Ed. 52 (2003) 1469.
27] Y.Z. Voloshin, V.E. Zavodnik, O.A. Varzatskii, V.K. Belsky, I.I. Vorontsov, M.Yu.
Antipin, Inorg. Chim. Acta 321 (2001) 116.
28] Y.Z. Voloshin, O.A. Varzatskii, A.S. Belov, A.Y. Lebedev, I.S. Makarov, M.E.
Gurskii, M.Y. Antipin, Z.A. Starikova, Y.N. Bubnov, Inorg. Chim. Acta 360 (2007)
Cl
X-ray crystallography data in the literature [34–38] indicate that
for the platinum(II) complexes with the same fragment this Ptꢁ ꢁ ꢁPt
distance is in the range 3.4–3.6 Å, which is in good agreement with
the value obtained from EXAFS experiment.
1543.
[29] C.A.L. Filgueiras, P.R. Holland, B.F.G. Johnson, P.R. Raithby, Acta Crystallogr.,
Sect. B 38 (1982) 954.
[
30] G.J. Grant, C.G. Brandow, D.F. Galas, J.P. Davis, W.T. Pennington, E.J. Valente, J.D.
Zubkowski, Polyhedron 20 (2001) 3333.
Acknowledgements
[
31] W.N. Hunter, K.W. Muir, D.W.A. Sharp, Acta Crystallogr., Sect. C 40 (1984)
37.
The authors gratefully acknowledge the support of the RFBR
[
[
32] G. Marangoni, B. Pitteri, V. Bertolasi, P. Gilli, Inorg. Chim. Acta 234 (1995) 173.
33] F. Goldoni, L. Antolini, G. Pourtois, A.P.H.J. Schenning, R.A.J. Janssen, R.
Lazzaroni, J.-L. Bredas, E.W. Meijer, Eur. J. Inorg. Chem. (2001) 821.
(
0
(
Grants 05-03-33184, 05-03-32953, 05-03-32759, 05-03-33268,
6-03-32626 and 06-03-90903), RAS (programme 7) and INTAS
project 04-83-4012). We thank Prof. V.Y. Kukushkin, who supplied
us with trans-PtCl (C CH CN)
[34] F.D. Rochon, R. Melanson, Acta Crystallogr., Sect.B 37 (1981) 690.
[
[
35] I.G. Phillips, R.G. Ball, R.G. Cavell, Inorg. Chem. 27 (1988) 4038.
36] A.J. Blake, R.O. Gould, A.M. Marr, D.W.H. Rankin, M. Schroder, Acta Crystallogr.,
Sect. C 45 (1989) 1218.
4
H
6 5
2
2
.
[
[
37] V.Y. Kukushkin, V.M. Tkachuk, I.A. Drol’, Z.A. Starikova, B.V. Zhadanov, N.P.
Kiseleva, Russ. J. Gen. Chem. 61 (1991) 51.
38] V.Y. Kukushkin, V.K. Belsky, V.E. Konovalov, R.R. Shifrina, A.I. Moiseev, R.A.
Vlasova, Inorg. Chim. Acta 183 (1991) 57.
39] P. Toffoli, P. Khodadad, N. Rodier, Acta Crystallogr., Sect. C 43 (1987) 1704.
40] Y. Qingchuan, T. Youqi, W. Hanzhang, Z. Qinhua, Chin. J. Struct. Chem. 7 (1988)
Appendix A. Supplementary data
CCDC 668667 and 668668 contain the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
[
[
95.