Nucleophilic addition of bifunctional sulfimidosulfides to platinum(IV)-coordinated nitriles

Article abstract of DOI:10.1007/s11172-005-0017-x

Reactions of the platinum(IV) nitrile complexes [PtCl₄(RCN) ₂] (R = Me, CH₂Ph, Ph) with 1,2- and 1,4-PhS(=NH)C ₆H₄SPh in CH₂Cl₂ afforded addition products of sulfimides and coordinated nitriles, viz., the [PtCl ₄{NH=C(R)N=S(Ph)(C₆H₄SPh)}₂] complexes. The latter were isolated in 75-90% yielks and characterized by elemental analysis, positive-ion FAB mass spectrometry, IR spectroscopy, and ¹H and ¹³C¹H NMR spectroscopy. The temperature dependence of the ¹H NMR spectra of the model [PtCl ₄{NH=C(R)N=SPh₂}₂] complexes (R = Me, Et) in CD₂Cl₂ studied in a temperature range from +40 to -70°C demonstrated that E-Z isomerization of the ligands is a dynamic process in a range from +40 to -10°C. The activation free energy of this process was calculated.

Full text of DOI:10.1007/s11172-005-0017-x

Russian Chemical Bulletin, International Edition, Vol. 53, No. 8, pp. 1681—1685, August, 2004
1681
Nucleophilic addition of bifunctional sulfimidosulfides
to platinum(IV)ꢀcoordinated nitriles
A. V. MakarychevaꢀMikhailova,a S. I. Selivanov,a N. A. Bokach,a
V. Yu. Kukushkin,aꢀ P. F. Kelly,b and A. J. L. Pombeiroc
aDepartment of Chemistry, St. Petersburg State University,
26 Universitetsky prosp., 198504 Stary Petergof, Russian Federation.
Fax: +7 (812) 428 6939. Eꢀmail: kukushkin@VK2100.spb.edu
bDepartment of Chemistry, Loughborough University, Loughborough LE11 3TU UK
cCenter of Structural Chemistry, Technical University of Lisbon,
Av. Rovisco Pais, 1049ꢀ001 Lisbon, Portugal*
Reactions of the platinum(IV) nitrile complexes [PtCl4(RCN)2] (R = Me, CH2Ph, Ph)
with 1,2ꢀ and 1,4ꢀPhS(=NH)C6H4SPh in CH2Cl2 afforded addition products of sulfimides
and coordinated nitriles, viz., the [PtCl4{NH=C(R)N=S(Ph)(C6H4SPh)}2] complexes. The
latter were isolated in 75—90% yields and characterized by elemental analysis, positiveꢀion
FAB mass spectrometry, IR spectroscopy, and 1H and 13C{1H} NMR spectroscopy. The
temperature dependence of the 1H NMR spectra of the model [PtCl4{NH=C(R)N=SPh2}2]
complexes (R = Me, Et) in CD2Cl2 studied in a temperature range from +40 to –70 °C
demonstrated that E—Z isomerization of the ligands is a dynamic process in a range from +40
to –10 °C. The activation free energy of this process was calculated.
Key words: nitriles, sulfimides, platinum(IV) complexes, nucleophilic addition, reactivity of
ligands, E—Z isomerization.
Nitriles are widely used in organic chemistry for the
synthesis of compounds containing C—O, C—N, C—S,
or C—C bonds by the addition of Oꢀ, Nꢀ, Sꢀ, or Cꢀ
nucleophiles, respectively, to the carbon atom of the niꢀ
trile group.1 Generally, for the reactions involving the
strong C≡N bond to occur, nitrile must be subjected to
additional electrophilic activation, which can be achieved,
for example, by coordination of the RCN molecule to a
metal ion. In this case, the reactivity of the RCN ligands
can be changed to an extent that the innerꢀsphere nitriles
become able to be involved in addition reactions even
with weak nucleophiles, for example, with oximes.2—4 An
additional advantage of activation of RCN upon its coorꢀ
dination to a metal ion is that the imine, which is derived
from the nitrile as a result of the innerꢀsphere transformaꢀ
tion, can usually be isolated in the free state by a substituꢀ
tion reaction.
Metalꢀpromoted reactions of coordinated nitriles with
Nꢀnucleophiles containing the sp3ꢀhybridized N atom
(ammonia,5 primary and secondary amines6,7), which give
rise to amidines, have been studied in sufficient detail. By
contrast, the reactions with Nꢀnucleophiles containing
the sp2ꢀhybridized N atom are poorly known. A few studꢀ
ies have been devoted to the addition of nitrogen heteroꢀ
cycles,8—10 benzophenone imine Ph2C=NH,11,12 and
sulfimide Ph2S=NH 13—15 to innerꢀsphere nitriles. The
present study is a continuation of our research on the
reactions of sulfimides with organonitrile complexes of
platinum(IV). The aim of the present study was to reveal
the type of reactivity of bifunctional sulfimidosulfides 1
and 2 in the reactions with the [PtCl4(RCN)2] complexes
(R = Me, CH2Ph, Ph).
Another purpose was to elucidate an exchange process
responsible for broadening of signals of the heterodiazaꢀ
diene ligands, which we have observed earlier15 in the
NMR spectra of the [PtCl4{NH=C(R)N=SPh2}2] comꢀ
plexes (R = Me, Et) prepared by the reactions of the
platinum(IV) nitrile complexes with Ph2S=NH.
Results and Discussion
The reactions of sulfimides 1 and 2 with nitriles in the
coordination sphere of platinum(IV) can, in principle, inꢀ
* Centro de Química Estrutural, Complexo I, Instituto Superior
Técnico, Av. Rovisco Pais, 1049ꢀ001 Lisbon, Portugal.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1618—1622, August, 2004.
1066ꢀ5285/04/5308ꢀ1681 © 2004 Springer Science+Business Media, Inc.

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MakarychevaꢀMikhailova et al.
volve several processes: first, the replacement of nitrile
with the HN=S 14 or —SPh groups of sulfimidosulfide 1
or 2;16 second, the nucleophilic addition of the HN=S
group at the nitrile C≡N bond resulting in the closure of
the chelate ring HN=C(R)—N=SAr through the S atom;13
and third, the nucleophilic addition of sulfimide to the
coordinated nitrile to form the monodentate heteroꢀ
diazadiene ligand HN=C(R)—N=SAr.15
pounds synthesized in the present study with the spectra
of the starting complexes shows the absence of an absorpꢀ
tion band ν(C≡N) at 2350—2300 cm–1, the presence of
an intense stretching band ν(C=N) at 1533—1523 cm–1
,
and the presence of weaker bands ν(N—H) at
3373—3319 cm–1
.
In the 1H NMR spectra recorded at room temperature,
all signals of the [PtCl4{NH=C(R)N=S(Ph)(C6H4SPh)}2]
complexes are noticeably broadened. Apparently, this is
associated with fast dynamic E—Z isomerization of the
heterodiazadiene ligands in solution, which occurs within
the NMR time scale (see below). The signal of the imine
group (δ 6.15—6.52) is shifted upfield compared to those
observed in the spectra of other platinum imine comꢀ
plexes (δ 8—9),2—4 in which hydrogen bonding was estabꢀ
lished. The position of the signal at such a high field is
indirect evidence that the proton of the C=NH group is
not involved in hydrogen bonding in solution.12,15 The
13C{1H} NMR spectra show a signal of the C=NH group
at δ 170—174, which corresponds to the characteristic
C=N resonances in platinum imine complexes.2—4,15,17,18
To prove the occurrence of equilibrium dynamic proꢀ
cesses in solutions of complexes 3—8 and elucidate their
nature, we studied the temperature dependence of the
1H NMR spectra of the [PtCl4{NH=C(R)N=SPh2}2]
complexes (R = Me (9), Et (10)) in solution in a temꢀ
perature range from +40 to –70 °C. Complexes 9 and 10
were chosen as model compounds because, unlike comꢀ
pounds 3—8, they are devoid of the sulfide group SPh.
Hence, an exchange process associated with inversion at
the S atom can be excluded from consideration. At room
temperature, the signals for the NH protons (δ 7.11—6.11)
and the protons of the alkyl group (δ 2.36—1.96 (Me);
3.13 and 1.27 (Et)) in complexes 9 and 10, like those in
compounds 3—8, are substantially broadened.15 An inꢀ
crease in the temperature to +40 °C is accompanied by
narrowing of these signals, whereas a decrease in the temꢀ
perature below –10 °C leads to the appearance of a triple
set of these signals corresponding to three forms of the
complexes, which are interconverted under conditions of
a slow (within the NMR time scale) equilibrium proꢀ
cess (Fig. 1).
The reactions of the platinum(IV) nitrile complexes
with sulfimides 1 and 2 proceed at room temperature
in a CH2Cl2 solution for 1 h (Scheme 1). Reaction prodꢀ
ucts 3—8 were isolated in 75—90% yields and characꢀ
terized by elemental analysis, positiveꢀion FAB mass specꢀ
1
trometry, IR spectroscopy, and H and 13C{1H} NMR
spectroscopy. In addition, small amounts of the
platinum(IV) iminol complexes with composition
transꢀ[PtCl4{NH=C(OH)R}2], which have been characꢀ
terized earlier,17 were detected by NMR spectroscopy,
FAB mass spectrometry, and TLC. Apparently, the forꢀ
mation of the latter complexes is attributable to hydrolysis
of the [PtCl4(RCN)2] complex by water, which is present
as an impurity in the solvents used.
Scheme 1
3
R Me
Position of
the SPh group
4
CH2Ph
2
5
Ph
2
6
7
8
Ph
4
Me CH2Ph
2
4
4
The results of elemental analysis for complexes 3—8
are indicative of the presence of two monodentate heteroꢀ
diazadiene ligands formed as a result of the nucleophilic
addition of sulfimides to nitriles. The observed fragmenꢀ
tation and the character of isotope distribution in the
FAB mass spectra of the complexes are close to those
expected for the [PtCl4{NH=C(R)N=S(Ph)(C6H4SPh)}2]
compounds.
The IR spectroscopic data also confirm the hypothesis
of the nucleophilic addition of sulfimides to the RCN
ligands and rule out the possibility of replacement of niꢀ
triles involved in platinum(IV) complexes with sulfimides.
For example, a comparison of the IR spectra of the comꢀ
To establish the structures of the complexes and make
the assignment of the signals, we used the data from the
NOESYꢀEXSY spectrum recorded under these conditions
(–40 °C). This spectrum has positive exchange crossꢀpeaks
along with crossꢀpeaks with negative polarity between the
signals for the NH protons and the protons of the alkyl
group for one of the isomers (Z configuration). Taking
into account the absence of this crossꢀpeak between the
analogous signals for the second isomer, it can be stated
with assurance that E—Z isomerization is a dynamic
process in a temperature range from +40 to –10 °C
(Scheme 2). The ratio between the E and Z isomers was
determined by the integration of the signals for the proꢀ

Nucleophilic addition of sulfimides to nitriles
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 8, August, 2004
1683
+40 °C
+10 °C
–10 °C
E,E
E,Z
Z,Z
–30 °C
–50 °C
–70 °C
6.8
6.6
6.4
6.2
6.0
5.8
5.6
δ
Fig. 1. Temperature dependence of the 1H NMR spectra of compound 10 in the region of the signal for the NH proton.
Scheme 2
R = Me (9), Et (10)
Configuration
Content (%)
9
77
22
1
10
E,E
E,Z
Z,Z
51
45
4

1684
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 8, August, 2004
MakarychevaꢀMikhailova et al.
1
Table 1. Activation free energies (∆G≠) for the equilibria 1 and 2
in solutions of complexes 9 and 10 (see Scheme 2)
variableꢀtemperature H NMR experiment was carried out in a
temperature range from +40 to –70 °C in CD2Cl2. The NOESY
experiment was performed at –40 and –70 °C (τ = 0.5 s).
mix
Equiꢀ
Confiꢀ
∆G≠/kcal mol–1
Functionalized sulfimides 1 and 2 were prepared according
to known procedures.22 The platinum(IV) complexes were
synthesized according to a procedure described earlier:2 the
[PtCl4(MeCN)2] complex was prepared by chlorination of a
mixture of the cis and trans isomers of [PtCl2(MeCN)2] giving
rise to a mixture of cis—transꢀ[PtCl4(MeCN)2] in a ratio of 1 : 5;
the pure trans isomers of [PtCl4(RCN)2] (R = CH2Ph, Ph) were
prepared by heating [PtCl2(MeCN)2] in the corresponding niꢀ
trile followed by chlorination.
librium guration
I*
II**
9
10
9
10
1
1
2
2
E,E
E,Z
E,Z
Z,Z
15.2
16.2
15.2
17.2
15.1
15.1
15.0
16.5
15.5
16.6
15.5
17.5
15.1
15.1
14.9
16.4
Addition of sulfimides 1 and 2 to the platinum(IV) acetonitrile
complex (general procedure). Sulfimide 1 or 2 (0.100 mmol)
was added with stirring to a suspension of [PtCl4(MeCN)2]
(0.05 mmol) in CH2Cl2 (2 mL) at ~20 °C. The reaction mixture
turned brightꢀyellow during 1—2 min. After 30 min, the solution
was concentrated to dryness. The orange oily residue was washed
with Et2O (5 mL) and crystallized from Et2O (5 mL) at ~20 °C.
The precipitate that formed was filtered off on a Hirsh funnel
and dried in air at 20—25 °C. The yield was 75—90%.
Addition of sulfimides 1 and 2 to the platinum(IV) benzoꢀ and
benzylonitrile complexes (general procedure). Sulfimide 1 or 2
(0.100 mmol) was added with stirring to a suspension of
[PtCl4(RCN)2] (R = CH2Ph, Ph) (0.05 mmol) in CH2Cl2 (2 mL)
at ~20 °C. The reaction mixture turned brightꢀyellow during
1—2 min, after which a precipitate formed. The latter was filꢀ
tered off on a Hirsh funnel, washed with Et2O (3×5 mL), and
dried in air at 20—25 °C. The yield was 75—90%. Complexes 4,
5, 7, and 8 are poorly soluble in most organic solvents. The
13C{1H} NMR spectra were not recorded because of a very long
signal accumulation time.
* The calculations were based on the integration of the signals
for the NH protons in the H NMR spectra.
** The calculations were based on the integration of the signals
for the Alk protons in the 1H NMR spectra.
1
tons of NH and the alkyl group at –10 °C (see Scheme 2).
The activation free energy was also calculated from
these data.19 The calculated values are in a range of
15—17 kcal mol–1 (Table 1).
A further decrease in the temperature (from –10 to
1
–70 °C) causes analogous changes in the H NMR specꢀ
tra. This fact is indicative of the second exchange process.
The latter is, apparently, associated with inversion at the
S atom or hindered rotation of the —N=SPh2 group about
a single bond.
We believe that broadening of the signals in the
1H NMR spectra of complexes 3—8 recorded at room
temperature,15 like that observed in the spectra of model
compounds 9 and 10, is attributable to E—Z isomerizaꢀ
tion of the heterodiazadiene ligands.
Separate experiments demonstrated that sulfimides 1
and 2 do not react with free nitriles even on heating (10 h,
50 °C). This observation indicates that the reagents add to
innerꢀsphere nitriles.
To summarize, we established that bifunctional sulfꢀ
imidosulfides are selectively involved in the metalꢀproꢀ
moted nucleophilic addition to nitrile ligands in platiꢀ
num(IV) complexes to form new Nꢀmonodentate ligands.
This reaction can be used as a simple procedure for the
synthesis of heterodiazadienes NH=C(R1)N=SR2R3,
which are difficult to prepare according to conventional
procedures without the involvement of metal comꢀ
plexes.20,21
Tetrachloro[bis(Nꢀ{phenyl[2ꢀ(phenylsulfanyl)phenyl]ꢀ
λ ꢀsulfanylidene}ethanimideꢀκ Nꢀamide)]platinum(I V ),
4
[PtCl4{NH=C(Me)N=S(Ph)(oꢀC6H4SPh)}2] (3). M.p. 172 °C,
Rf 0.53 (Me2CO—CHCl3, 1 : 6, as the eluent). Found (%):
C, 46.43; H, 3.51; N, 5.15. C40H36Cl4N4PtS4. Calculated (%):
C, 46.29; H, 3.50; N, 5.40. MS, m/z: 930 [M – 2 Cl]+. IR,
ν/cm–1
: 3319 (ν(N—H)); 3049, 2922 (ν(C—H)); 1533
(ν(C=N)); 1439 (ν(C=C arom.)). 1H NMR (CDCl3), δ: 7.5—7.2
(m, 14 H, H arom.); 6.18 (br.s, 1 H, NH); 2.67 (br.s, 3 H, Me).
13C{1H} NMR (CDCl3), δ: 170.77 (C=N); 139.57, 133.14,
132.64, 130.03, 129.85, 129.66, 129.66, 127.63, 127.56 (Ph and
C arom.); 24.77 (Me).
4
Tetrachloro[bis(Nꢀ{phenyl[2ꢀ(phenylsulfanyl)phenyl]ꢀλ ꢀ
sulfanylidene}ꢀ2ꢀphenylethanimideꢀκNꢀamide)]platinum(IV),
[PtCl4{NH=C(CH2Ph)N=S(Ph)(oꢀC6H4SPh)}2] (4). M.p.
150 °C, Rf 0.74 (Me2CO—CHCl3, 1 : 5, as the eluent).
Found (%): C, 51.35; H, 3.85; N, 4.41. C52H44Cl4N4PtS4. Calꢀ
culated (%): C, 52.48; H, 3.73; N, 4.71. MS, m/z: 1118
[M – 2 Cl]+, 1083 [M – 3 Cl]+. IR, ν/cm–1: 3321 (ν(N—H));
3054, 2922 (ν(C—H)); 1523 (ν(C=N)); 1442 (ν(C=C arom.)).
1H NMR (CDCl3), δ: 8.0—7.0 (br.m, H arom.); 6.15 (br.s, 1 H,
NH); 4.81, 4.40, 4.03 (br.s, 2 H, CH2Ph).
Experimental
The melting points were determined in a capillary. The TLC
analysis was carried out on Silufol UV254 plates. The positiveꢀ
ion FAB mass spectra were obtained on a Trio 2000 instrument
using bombardment of a nitrobenzyl alcohol matrix with Xe
atoms (8 keV; ~1.28•1015 J). The IR spectra were measured in
KBr pellets on a BIOꢀRAD FTS 3000MX instrument in a range
of 4000—400 cm–1. The 1H and 13C{1H} NMR spectra were
recorded on a Varian UNITY 300 spectrometer at ~20 °C. The
4
Tetrachloro[bis(Nꢀ{phenyl[2ꢀ(phenylsulfanyl)phenyl]ꢀλ ꢀ
sulfanylidene}carboximideꢀκNꢀamidobenzene)]platinum(IV),
[PtCl4{NH=C(Ph)N=S(Ph)(oꢀC6H4SPh)}2] (5). M.p. 164 °C
(decomp.), Rf 0.72 (Me2CO—CHCl3, 1 : 5, as the eluent).
Found (%): C, 51.36; H, 3.55; N, 4.82. C50H40Cl4N4PtS4. Calꢀ
culated (%): C, 51.68; H, 3.47; N, 4.82. MS, m/z: 1031
[M – 3 Cl]+, 996 [M – 4 Cl]+. IR, ν/cm–1: 3326 (ν(N—H));

Nucleophilic addition of sulfimides to nitriles
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 8, August, 2004
1685
3052, 2924 (ν(C—H)); 1529 (ν(C=N)); 1444 (ν(C=C arom.)).
1H NMR (CDCl3), δ: 8.06—6.97 (br.m, H arom.); 6.15
(br.s, 1 H, NH).
3. V. Yu. Kukushkin, T. B. Pakhomova, N. A. Bokach,
G. Wagner, M. L. Kuznetsov, M. Galanski, and A. J. L.
Pombeiro, Inorg. Chem., 2000, 39, 216.
Tetrachloro[bis(Nꢀ{phenyl[4ꢀ(phenylsulfanyl)phenyl]ꢀ
λ ꢀsulfanylidene}ethanimideꢀκ Nꢀamide)]platinum(I V ),
4. A. V. MakarychevaꢀMikhailova, M. Haukka, N. A. Bokach,
D. A. Garnovskii, M. Galanski, B. K. Keppler, A. J. L.
Pombeiro, and V. Yu. Kukushkin, New J. Chem., 2002,
26, 1085.
4
[PtCl4{NH=C(Me)N=S(Ph)(pꢀC6H4SPh)}2] (6). M.p. 166 °C,
Rf 0.54 (Me2CO—CHCl3, 1 : 6, as the eluent). Found (%):
C, 46.51; H, 3.72; N, 5.24. C40H36Cl4N4PtS4. Calculated (%):
C, 46.29; H, 3.50; N, 5.40. MS, m/z: 1060 [M + Na – H]+, 1038
[M ]+. IR, ν/cm–1: 3323 (ν(N—H)); 3052, 2923 (ν(C—H));
1528 (ν(C=N)); 1439 (ν(C=C arom.)). 1H NMR (CDCl3), δ:
7.7—7.2 (br.m, 14 H, H arom.); 6.52 (br.s, 1 H, NH); 2.76 (br.s,
3 H, Me). 13C{1H} NMR (CDCl3), δ: 174.69 (C=N); 134.55,
131.13, 130.27, 129.95, 129.29, 128.28, 127.91, 127.18 (Ph and
C arom.); 24.77 (Me).
5. Yu.
N.
Kukushkin,
Reaktsionnaya
sposobnost´
koordinatsionnykh soedinenii [Reactivity of Coordination
Compounds], Khimiya, Leningrad, 1987, 148 pp. (in
Russian).a
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Michelin, M. Mozzon, A. J. L. Pombeiro, and F. C. Guedes
da Silva, Inorg. Chim. Acta, 2002, 330, 229.
7. U. Belluco, F. Benetollo, R. Bertani, G. Bombieri, R. A.
Michelin, M. Mozzon, O. Tonon, A. J. L. Pombeiro,
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4
Tetrachloro[bis(Nꢀ{phenyl[4ꢀ(phenylsulfanyl)phenyl]ꢀλ ꢀ
sulfanylidene}ꢀ2ꢀphenylethanimideꢀκNꢀamide)]platinum(IV),
[PtCl4{NH=C(CH2Ph)N=S(Ph)(pꢀC6H4SPh)}2] (7). M.p.
151 °C, Rf 0.51 (Me2CO—CHCl3, 1 : 6, as the eluent).
Found (%): C, 51.46; H, 3.95; N, 4.56. C52H44Cl4N4PtS4. Calꢀ
culated (%): C, 52.48; H, 3.73; N, 4.71. MS, m/z: 1082 [M –
3 Cl – H]+, 1048 [M – 4 Cl]+. IR, ν/cm–1: 3319 (ν(N—H));
3052, 2926 (ν(C—H)); 1525 (ν(C=N)); 1439 (ν(C=C arom.)).
1H NMR (CDCl3), δ: 7.9—7.0 (br.m, H arom.); 6.32 (br.s, 1 H,
NH); 4.40, 4.23 (br.s, 2 H, CH2Ph).
4
Tetrachloro[bis(Nꢀ{phenyl[4ꢀ(phenylsulfanyl)phenyl]ꢀλ ꢀ
sulfanylidene}carboximideꢀκNꢀamidobenzene)]platinum(IV),
[PtCl4{NH=C(Ph)N=S(Ph)(pꢀC6H4SPh)}2] (8). M.p. 152 °C
(decomp.), Rf 0.58 (Me2CO—CHCl3, 1 : 6, as the eluent).
Found (%): C, 51.70; H, 3.51; N, 4.83. C50H40Cl4N4PtS4. Calꢀ
culated (%): C, 51.68; H, 3.47; N, 4.82. MS, m/z: 1054 [M –
3 Cl + Na]+, 1018 [M – 4 Cl – H + Na]+. IR, ν/cm–1: 3373
(ν(N—H)); 3052, 2929 (ν(C—H)); 1516 (ν(C=N)); 1440
(ν(C=C arom.)). 1H NMR (CDCl3), δ: 8.1—7.0 (br.m, Ph);
6.17 (br.s, 1 H, NH).
12. D. A. Garnovskii, V. Yu. Kukushkin, M. Haukka, G. Wagner,
and A. J. L. Pombeiro, J. Chem. Soc., Dalton Trans.,
2001, 560.
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2001, 263.
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Kukushkin, P. F. Kelly, M. L. Kuznetsov, K. E. Holmes,
M. Haukka, J. Parr, J. M. Stonehouse, M. R. J. Elsegood,
and A. J. L. Pombeiro, Inorg. Chem., 2003, 42, 301.
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81, 365.aaa
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Dalton Trans., 2002, 1882.
This study was financially supported by the Russian
Foundation for Basic Research (Project No. 03ꢀ03ꢀ32362)
and the Competitive Center of Fundamental Natural
Sciences (Grants A03 2.11ꢀ61, M03ꢀ2.5Kꢀ91, and
PD 03ꢀ1.3ꢀ28). S. I. Selivanov acknowledges support from
the NATO Scientific Council (NATO Science Fellowꢀ
ship OUTREACH Program). V. Yu. Kukushkin acknowlꢀ
edges support of the Royal Society of Chemistry (Journals
Grant for International Authors).
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Received December 22, 2003;
in revised form March 31, 2004