Synthesis, structure, and hydrophosphorylation of π-complexes of hexacarbonyltungsten(0) with cyclohexanone, cyclohexanethione, and N-cyclohexylideneaniline

Article abstract of DOI:10.1007/s11178-005-0334-4

New carbonyl π-complexes of tungsten(0) with cyclohexanone, cyclohexanethione, and N-cyclohexylideneaniline were synthesized. Geometric and electronic parameters of the ligands, as well as energy parameters of the complex formation process, were determine

Full text of DOI:10.1007/s11178-005-0334-4

Russian Journal of Organic Chemistry, Vol. 41, No. 9, 2005, pp. 1271–1279. Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 9, 2005,
pp. 1298–1306.
Original Russian Text Copyright © 2005 by Kuramshin, Pavlova, Cherkasov.
Dedicated to Full Member of the Russian Academy of Sciences
N.S. Zefirov on His 70th Anniversary
Synthesis, Structure, and Hydrophosphorylation
of π-Complexes of Hexacarbonyltungsten(0) with Cyclohexanone,
Cyclohexanethione, and N-Cyclohexylideneaniline
A. I. Kuramshin, I. V. Pavlova, and R. A. Cherkasov
Kazan State University, ul. Kremlevskaya 18, Kazan, 420008 Tatarstan, Russia
e-mail: arcady.kuramshin@ksu.ru
Received April 28, 2005
Abstract—New carbonyl π-complexes of tungsten(0) with cyclohexanone, cyclohexanethione, and N-cyclo-
hexylideneaniline were synthesized. Geometric and electronic parameters of the ligands, as well as energy
parameters of the complex formation process, were determined by quantum-chemical calculations. Hydro-
phosphorylation with diethyl phosphonate changed the reactivity of coordinated N-cyclohexylideneaniline,
while no analogous effect was observed for cyclohexanone and cyclohexanethione.
An actual problem of modern chemistry is selective
functionalization of compounds possessing several
potential reaction centers; solution of this problem
makes it possible to develop procedures for target-
oriented synthesis of polyfunctional organic and or-
ganometallic compounds with a specified structure.
A promising method for design of new organophos-
phorus compounds is based on hydrophosphorylation
reactions involving multiple carbon–heteroelement
bonds in α,β-unsaturated oxo, thioxo, and imino
derivatives. These reactions lead to formation of the
corresponding unsaturated α-hydroxy, α-amino, and
α-sulfanyl phosphonates which attract interest from the
viewpoint of their practical applications. In addition,
they are convenient intermediate products for further
modifications [1]. However, the synthesis of such com-
pounds is often complicated due to competition be-
tween carbon–carbon and carbon–heteroelement bonds
in the hydrophosphorylation processes [1–4].
phosphorylation of unsaturated compounds as free
ligands follows mainly the Pudovik scheme: P–H com-
pounds add as a rule at the carbon–carbon bond. Our
x
studies on numerous η -heterodiene complexes with
various x values showed that the reasons for change in
the reactivity of heteropolyenes coordinated to a transi-
tion metal include not only steric factors (shielding of
a potential reaction center by the metal–ligand moiety)
but primarily variation of the electronic structure of the
ligand due to its coordination to metal. First of all, this
is distortion of conjugation in the heterodiene system
of unsaturated ketones and their analogs within the
coordination sphere of transition metals, as was
confirmed by the results of nonempirical quantum-
chemical calculations [9].
In the present work we examined variations in the
geometric and electronic structure of unsaturated sys-
tems possessing double carbon–oxygen, carbon–sulfur,
and carbon–nitrogen bonds due to their coordination to
metal complexes. We also studied the effect of coor-
dination with metals on the reactions of the ligands
with diethyl phosphonate. The study was performed
using IR spectroscopy and empirical and nonempirical
quantum-chemical calculations.
Chemo- and regioselectivity in reactions of poly-
enes and heteropolyenes may be controlled via their
functionalization within the coordination sphere of
organometallic compounds [5]. We previously reported
that oxo, aza, and thioxo dienes coordinated to zero-
valent chromium subgroup metals take up dialkyl
phosphonates at the double carbon–heteroelement
bond, regardless of the mode of heterodiene coordina-
tion to the metal center [4, 6–8]. On the other hand,
It is known that vibrations of multiple carbon–
heteroelement bonds give rise to characteristic absorp-
tion bands in the IR spectra and that the position and
intensity of these bands are sensitive to the coordina-
1
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1
272
KURAMSHIN et al.
(
a)
(b)
Fig. 1. (a) HOMO and (b) LUMO of cyclohexanone.
a)
(
(b)
Fig. 2. (a) HOMO and (b) LUMO of cyclohexanethione.
a)
(
(b)
Fig. 3. (a) HOMO and (b) LUMO of N-cyclohexylideneaniline.
tion mode [10]. Functional groups like C=X can be
involved in coordination in two modes: terminal
C=X bond induces a smaller change of the vibration
frequency than does lateral coordination [10].
(
through the X heteroelement) and lateral (through the
As model unsaturated compounds having a C=X
bond, we selected cyclohexanone (I), cyclohexane-
thione (II), and N-cyclohexylideneaniline (III). The
electronic and steric structures of their molecules were
determined by PM3 semiempirical calculations. The
carbon–heteroelement π-bond) [11]. Each of the above
coordination modes is characterized by reduction of
vibration frequency of the corresponding multiple
bond in the IR spectrum, but terminal coordination of
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 9 2005

SYNTHESIS, STRUCTURE, AND HYDROPHOSPHORYLATION OF π-COMPLEXES
1273
frontier orbitals in molecules I–III are localized
mainly on the multiple carbon–heteroelement bonds,
and the lowest unoccupied molecular orbitals (LUMO)
are characterized by low energies: 0.8532 (I), 0.1121
2.60 eV (W); i.e., their LUMOs are readily accessible
for interaction with HOMOs of ligands. The HOMO
energy may stimulate π-dative metal–ligand interac-
tion. Analysis of the structure and energy of frontier
orbitals of potential ligands and pentacarbonylmetal
fragments led us to conclude that the C=O and C=N
groups are capable of coordinating in both lateral and
terminal modes and that terminal coordination is pre-
ferred for the C=C fragment.
(
II), and –1.309 eV (III). However, their highest
occupied molecular orbitals (HOMO) are located at
a fairly deep level, the corresponding energies being
equal to –10.48, –9.062, and –8.991 eV, respectively.
The frontier orbital fragments localized on the C=O,
C=N, and C=S groups become less symmetric in the
series I > III > II. The electron and orbital densities
in the frontier orbitals of cyclohexanone are distributed
almost symmetrically over the carbonyl carbon and
oxygen atoms. The orbital density of both HOMO and
LUMO of cyclohexanethione is localized almost com-
pletely on the sulfur atom (Figs. 1–3).
Table contains the Gibbs energies of formation of
the W(CO) L complexes (where L is cyclohexanone,
5
cyclohexanethione, or N-cyclohexylideneaniline) with
different modes of coordination of the ligand. These
data confirm the conclusion drawn from analysis of the
frontier orbital structure: only the complexes with
cyclohexanethione show a considerable difference in
the Gibbs energies of formation of coordination com-
pounds with n- and π-bonding of the metal with the
ligand. The difference in the Gibbs energies of forma-
tion of complexes with participation of C=O and C=N
groups is so small that we can suppose competing
formation of compounds with terminal and lateral
modes of coordination for ketone I and Schiff base III.
According to [12, 13], replacement of carbonyl
ligands in hexacarbonyl complexes of chromium sub-
group metals is a dissociative process which begins
with fast elimination of carbon(II) oxide from the
metal coordination sphere [13]. The subsequent forma-
tion of coordination compound (R–C=X–R')M(CO)5
involves interaction between the π-system of the C=X
bond or lone electron pair (LEP) of the X heteroatom
and metal-containing fragment M(CO) (M = Cr,
5
6 5
Gibbs energies of the reaction W(CO) + L → W(CO) L +
Mo, W). We examined the localization and energies of
frontier orbitals of pentacarbonyl metal-containing
fragments formed by elimination of CO ligand from
the coordination sphere of chromium subgroup metal:
CO, where L is cyclohexanone, cyclohexanethione, or
N-cyclohexylideneaniline coordinated in different modes
Complex W(CO)
5
L
ΔG, kJ/mol
O
M(CO)
6
→ M(CO)
5
+ CO
–7.8
W(CO)5
The structure and energy parameters were calculat-
ed in terms of the Hartree–Fock theory using the ECP
O
–
–
8.1
5.3
(
SBK) basis set in which inner-shell electrons are de-
scribed by the Stevens–Basch–Krauss model potential.
Hydrogen atoms were treated at the 6-31G level, and
valence shells of heavy atoms were described using
quadruple and triple zeta basis sets for s, p, and d
electrons, respectively; d-polarizing function was also
used for heavy atoms. This basis set was used to per-
form full geometry optimization of the complexes [14].
The applicability of the above approach to analysis of
the structure and energy of formation of π-organo-
metallic compounds was substantiated by us pre-
viously [9].
W(CO)5
S
W(CO)5
S
–
12.00
W(CO)5
N
–8.0
W(CO)5
The results of calculations showed that the structure
of frontier orbitals of the M(CO) fragments is almost
similar to that of d orbitals of transition metals. The
5
N
–
8.5
LUMO energies of coordinately unsaturated 16-elec-
W(CO)5
tron M(CO) species are –2.57 (Cr), –2.85 (Mo), and
5
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 9 2005

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274
KURAMSHIN et al.
a)
(
(b)
1
Fig. 4. (a) HOMO (E = –4.34 eV) and (b) LUMO (E = –1.28 eV) of the complex (η -C
6 5
H10O)Mo(CO) , .
(a)
(b)
1
6 5
Fig. 5. (a) HOMO (E = –4.27 eV) and (b) LUMO (E = –3.42 eV) of the complex (η -C H10S)Mo(CO) .
Moreover, interconversion between isomeric com-
plexes with η - and η -coordinated ligands seems to
be possible.
ligand) provided that the reaction is orbital-controlled.
This is consistent with our previous conclusion that
the metal center not only acts as a protecting group but
strongly affects the electronic properties of the reaction
center in the coordinated unsaturated reagent [4, 6–8].
Charge distribution between the carbon and hetero-
element atoms in η - and η -coordinated C=X groups
in the complexes derived from compounds I and II
should also favor attack by nucleophile on the electro-
philic carbonyl (or thiocarbonyl) carbon atom when
the reaction is charge-controlled. For example, the
charge on the oxygen atom in free cyclohexanone
1
2
Figures 4 and 5 show the structure of frontier
orbitals of the complexes formed by unsaturated com-
pounds I and II and pentacarbonylmetal fragment. The
HOMOs of these complexes are localized almost com-
pletely on the metal-containing fragments, while their
LUMOs reside mainly on the double C=X bonds of the
ligands. We can thus presume that HOMO of a nu-
cleophile should interact with LUMO of the metal
complex (which is localized on the double bond of the
1
2
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SYNTHESIS, STRUCTURE, AND HYDROPHOSPHORYLATION OF π-COMPLEXES
1275
Scheme 1.
O
MeCN, 80°C
W(CO)5
O
+
W(CO)6
IV
–
CO
O
W(CO)5
V
molecule is –0.323 a.u., and the charge on the carbonyl
carbon atom is +0.298 a.u. η -Coordination of cyclo-
hexanone to tungsten only slightly changes these
charges, the C=O bond polarization remaining un-
changed: –0.287 (O) and +0.231 a.u. (C).
complex V. Uncoordinated cyclohexanone is charac-
1
terized by a carbonyl stretching vibration frequency
–
1
of 1710 cm .
The above assignment is supported by the follow-
2
ing considerations. Lateral (η ) coordination of the
According to the calculations, coordinated ligand
III is characterized by a different distribution of
electron density. In uncoordinated Schiff base III, the
negative end of the C=N dipole is the nitrogen atom
double bond induces not only electron density redis-
tribution but also extension of that bond, leading to
considerable variation of its stretching vibration fre-
quency. Terminal coordination of the C=X group
through the heteroatom is accompanied by insignif-
icant variation of the electronic structure, and the
vibration frequency should change only slightly. Ap-
proximately equal intensities of the bands at 1610 and
(
q = –0.051, q = +0.017 a.u.); in going to the
N C
1
η -coordinated ligand, the charges on the carbon and
nitrogen atoms change their signs so that excess elec-
tron density is localized on the carbon atom (q =
C
–
1
–
0.115 a.u.), while the nitrogen atom becomes elec-
1
660 cm in the IR spectrum suggest equal or (at
tron-deficient (q = +0.098 a.u.). Such charge distribu-
N
least) comparable amounts of complexes IV and V in
the product mixture. This is consistent with the equi-
librium constant for isomerization of complex IV into
V, calculated from the Gibbs energies of formation of
tion in the coordinated Schiff base leads to inversion of
the direction of nucleophilic attack: nucleophile adds
at the nitrogen atom rather than at the carbon atom, as
in reactions with the free ligand. Analogous inversion
of polarization of the C=N bond as a result of coor-
dination was observed for 1-aza-1,3-diene complexes
with chromium subgroup metals [8].
these complexes (see table), K = 1.14.
eq
The mixture of coordination compounds obtained
from cyclohexanone and hexacarbonyltungsten(0) was
analyzed by thin-layer chromatography. Elution with
In order to obtain experimental support to the
results of theoretical calculations we examined reac-
tions of cyclohexanone (I) and its analogs II and III
with hexacarbonyltungsten(0), which were performed
according to the procedure developed by us previously
for thermochemical activation of complex formation
processes [6–8]. In the reaction with cyclohexanone
we succeeded in isolating a mixture of crystalline
acetonitrile revealed two compounds with R values
f
of 0.100 and 0.154. The first of these was assigned to
2
1
η -complex IV, and the second, to η -(cyclohexanone)-
pentacarbonyltungsten(0) (V). The assignment was
based on the calculated dipole moments of compounds
IV and V, 0.302 and 2.93 D, respectively. Unfortu-
nately, we failed to isolate individual complexes IV
and V by column chromatography due to their sen-
sitivity to atmospheric oxygen and moisture.
1
2
products corresponding to η - and η -coordination to
tungsten. The products were unstable in the presence
of atmospheric oxygen and moisture, and their com-
position implied replacement of one carbonyl ligand
Crystalline products obtained by the reaction of
cyclohexanethione with hexacarbonyltungsten(0) were
isomeric coordination compounds of the general
in W(CO) by the ketone (Scheme 1). The IR spectrum
6
of the isolated mixture contained two well defined
absorption bands in the region of carbonyl stretching
vibrations, at 1610 and 1660 cm . These bands were
assigned, respectively, to the π-coordinated C=O group
in complex IV and n-coordinated C=O group in
formula L W(CO) (Scheme 2). However, in this case,
2 4
lateral coordination of the C=S fragment to the metal
center may be ruled out. Both initial cyclohexane-
thione and mixture of products of its reaction with
–
1
W(CO) showed in the IR spectra a weak absorption
6
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276
KURAMSHIN et al.
Scheme 2.
S
OC
OC
S
W
CO
CO
MeCN, 82°C
VI
S
+
W(CO)6
–
2CO
CO
W
OC
S
S
CO
CO
VII
–
1
band at 1140 cm corresponding to the C=S bond. We
thus concluded (in keeping with the results of quan-
tum-chemical calculations), that cyclohexanethione
coordinates to the metal through the sulfur atom to
allow us to assign them a definite formula. The ligand–
metal ratio in the products varies from 1:1.2 to 1:1.6.
The IR spectrum contained poorly resolved absorption
bands in the region corresponding to terminally coor-
dinated carbonyl groups, while no absorption typical of
bridging carbonyl groups was observed. These data led
us to presume that the product mixture contains mono-
nuclear coordination compounds with the composi-
tions LW(CO) and L W(CO) (Scheme 3).
1
give isomeric cis- and trans-bis(η -cyclohexanethione)
tetracarbonyltungsten(0) VI and VII. In the IR spec-
trum of a crystalline mixture of complexes VI and VII
we observed a system consisting of 4 well resolved
absorption bands in the region 2100–1950 cm ; these
bands were assigned to carbon(II) oxide molecules
coordinated to tungsten in the terminal mode. No
bands assignable to bridging C=O groups were pres-
ent. The long-wave region of the spectrum contained
two strong bands at 374 and 364 cm , which are likely
to arise from vibrations of the sulfur–tungsten dative
bond. Insofar as the sulfur atom is known to exert
a stronger trans effect than CO, the band at 374 cm
was assigned to trans isomer VI, and the band at
–
1
5
2
4
Two absorption bands in the IR spectrum of the
products belong to stretching vibrations of the C=N
–1
bond: the band at 1610 cm belongs to the uncoordi-
–1
nated double C=N bond, and that located at 1580 cm
–
1
corresponds to the π-coordinated C=N bond. In the
long-wave region we observed absorption bands at
–1
5
67, 582, and 588 cm due to vibrations of the dative
–
1
nitrogen-–metal bond [8]. A complex absorption pat-
tern in the carbonyl ligand region and the presence of
several W–N bands suggest the occurrence of different
coordination modes in the complexes, presumably due
to strongly reduced symmetry of the C=N bond or-
bitals. Unfortunately, the products were very unstable
in the presence of atmospheric oxygen and moisture,
–
1
1
3
64 cm , to cis-bis(η -cyclohexanethione)tetracar-
bonyltungsten(0) (VII).
In the reaction of N-cyclohexylideneaniline with
hexacarbonyltungsten(0) we isolated a mixture of crys-
talline products VIII whose elemental analysis did not
Scheme 3.
NPh
NPh
–
CO
W(CO)5
MeCN, 82°C
W(CO)
5
NPh
+
W(CO)6
CO
CO
W
OC
OC
N
N
–
2CO
Ph
Ph
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SYNTHESIS, STRUCTURE, AND HYDROPHOSPHORYLATION OF π-COMPLEXES
1277
Scheme 4.
O
W(CO)5
IV
OH
(EtO) PHO, Et N
2 3
+
W (CO)
x y
P(O)(OEt)2
O
IX
W(CO)5
V
and we failed to isolate individual complexes and even
to analyze the composition of the product mixture by
thin-layer chromatography.
contained a singlet at δ 65 ppm. Hydrophosphoryla-
P
tion of uncoordinated cyclohexanethione gives a prod-
3
1
uct with the same P chemical shift (Scheme 7). As
with complexes IV and V, reactions of diethyl phos-
phonate with cyclohexanethione complexes VI and
VII are accompanied by decomposition of the coor-
dination compounds and formation of a solid metal-
containing residue with the composition W (CO) .
We examined the behavior of complexes IV–VIII
with different modes of coordination of the C=X
groups in reactions with diethyl phosphonate in the
presence of triethylamine. In all cases, addition of the
P–H reagent at the double bond occurred. Hydrophos-
phorylation of cyclohexanone complexes IV and V
was accompanied by decomposition of the coordina-
tion compounds with liberation of diethyl 1-hydroxy-
cyclohexylphosphonate (IX) and formation of a metal-
containing residue with the composition W (CO)
x
y
Scheme 6.
HS
P(O)(OEt)2
(EtO) PHO, Et N
2 3
VI, VII
x
y
(
Scheme 4); the latter product results from increase
XI
in the nuclearity due to formation of coordinately un-
saturated species W(CO) . Phosphonate IX showed
in the P NMR spectrum a singlet at δ 24 ppm; the
P(O)(OEt)2
P(S)(OEt)2
5
S
O
31
P
same signal was observed in the spectrum of a product
obtained by model reaction of uncoordinated cyclo-
hexanone with diethyl phosphonate in the presence of
triethylamine (Scheme 5).
XII
X
Scheme 7.
Scheme 5.
S
(
EtO) PHO, Et N
(EtO) PHO
Et N
3
2
3
2
O
IX
XI
XII
X
Under analogous conditions, hydrophosphorylation
of a mixture of complexes VI and VII in benzene also
involved addition of diethyl phosphonate at the double
C=S bond (Scheme 6). However, in this case we iso-
lated O-cyclohexyl O,O-diethyl thiophosphate (X) as
product of two successive rearrangements: sulfanyl-
phosphonate–thiophosphate XI → XII and thiol–
thione XII → X. Analogous ligand transformations
were observed previously while studying hydrophos-
phorylation of 1,3-diphenyl-2-propenethione in the
coordination sphere of carbonyl and carbonyl cyclo-
pentadienyl complexes of chromium subgroup metals
A mixture of tungsten complexes VIII with N-cy-
clohexylideneaniline also reacted with diethyl phos-
phonate in benzene, resulting in decomposition of the
coordination compounds and increase in the nuclearity
of carbonyltungsten complexes. In the P NMR spec-
trum of the reaction mixture we observed two singlets.
One of these is typical of α-aminophosphonates
3
1
(δ 14.7 ppm); obviously, it belongs to diethyl 1-(phen-
P
ylamino)cyclohexylphosphonate (XIII). The other
signal was located in the amidophosphate region,
δ 2.3 ppm; it was assigned to diethyl N-cyclohexyl-
P
31
[
14]. The P NMR spectrum of the hydrophosphoryla-
N-phenylamidophosphate (XIV) (Scheme 8). Uncoor-
dinated N-cyclohexylideneaniline III reacted with di-
tion product of coordination compounds VI and VII
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KURAMSHIN et al.
Scheme 8.
Ph
P(O)(OEt)2
N
PhNH
P(O)(OEt)2
(
EtO) PHO, Et N
2 3
VIII
+
XIII
XIV
ethyl phosphonate to give exclusively the correspond-
ing Pudovik reaction product, α-aminophosphonate
XIII, which was identified by the presence of a singlet
free ketones and thioketones. However, coordination
to a metal induces some specificity in the synthetic
results. α-Sulfanylphosphonates readily undergo intra-
molecular rearrangements within the coordination
sphere of a metal. The effect of coordination is es-
pecially strong in the case of Schiff bases: inversion of
polarization of the C=N bond, induced by the car-
bonylmetal fragment, changes the regioselectivity of
hydrophosphorylation, and the reaction proceeds in
a direction untypical of the free ligand. Here, apart
from the expected formation of α-aminophosphonate
according to the imine version of the Pudovik reaction,
nucleophile adds to the C=N bond in the inversed
mode, leading to amidophosphate. Therefore, involve-
ment of oxo compounds and their analogs in inner-
complex functionalization opens new prospects in the
purposeful synthesis of substances with a specified
structure.
31
at δ 14.8 ppm in the P NMR spectrum.
P
Our experimental data are very consistent with the
above described charge distribution in coordinated
Schiff base, determined by quantum-chemical calcula-
tions. Change in the polarization of the nitrogen–
carbon bond, leading to increased electrophilicity of
the nitrogen atom, makes the latter the target for attack
by nucleophile. It should be noted that we have already
observed formation of P–N bond via addition of di-
ethyl phosphonate at the C=N bond of 1-aza-1,3-diene
in the coordination sphere of a carbonylmetal complex
[
8]. Moreover, we have shown that the amidophos-
phate ligand undergoes rearrangement into the corre-
sponding unsaturated α-aminophosphonate on prolong-
ed storage at room temperature. As concerns the
formation of α-aminophosphonate XIII, the available
experimental data do not allow us to distinguish be-
tween alternative pathways including the imine version
of the Pudovik reaction and the isomerization XIV →
XIII. Also, we cannot rule out simultaneous formation
The results obtained in the present work, together
with our previous data on the addition of dialkyl phos-
phonate to alkenes coordinated to chromium subgroup
metals [15], cast doubt on the assumption [7–9, 15, 16]
that change in the reactivity of coordinated hetero-
dienes is induced by the metal acting as protecting
group. We believe that the most probable reason is
profound geometric and electronic reorganization of
ligands as a result of coordination with transition
metal.
of isomeric products via inner-sphere Ad reaction
N
since the difference between the charges on the nitro-
gen and carbon atoms in the coordinated Schiff base is
very small, 0.007 a.u.
Thus the results of our theoretical and experimental
studies on the structure and reactivity of ligands having
a multiple carbon–heteroelement bond and coordinated
in different modes to carbonyl-containing complexes
of Group VI metals showed almost complete similarity
in the behavior of heterocumulenes, on the one hand,
and cyclic ketones and their sulfur and nitrogen ana-
logs, on the other. In both cases, the carbonylmetal
fragment strongly affects the electronic (and, in the
case of heterodienes, steric [8, 9]) structure of unsatu-
rated ligands, stimulating their regioselective func-
tionalization exclusively at the carbon–heteroelement
multiple bond. Hydrophosphorylation of oxo and
thioxo ligands follows the Abramov reaction pattern,
leading to the corresponding phosphorylated alcohols
and thiols. The same reaction pattern is typical of the
EXPERIMENTAL
The following commercial reagents and solvents
were used: pentane, hexane, benzene, toluene, acetone,
acetonitrile, tetrahydrofuran, ethanol, and triethyl-
amine; they were additionally purified according to
standard procedures [17]. Initial hexacarbonyltung-
sten(0) was purified by vacuum sublimation (0.05 mm)
at 60–80°C. The complexes were purified by reprecip-
itation with hexane or pentane from benzene or by
recrystallization from hexane or pentane.
The IR spectra were recorded on Specord M-80
(from samples dispersed in mineral oil or films) and
Bruker Vector 2-2 Fourier spectrometers (from
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SYNTHESIS, STRUCTURE, AND HYDROPHOSPHORYLATION OF π-COMPLEXES
1279
–
1
samples prepared as KBr pellets; resolution 1 cm ,
REFERENCES
–
1
scan number 64, frequency range 200 to 4000 cm ).
3
1
1
. Konovalova, I.V. and Burnaeva, L.M., Reaktsiya
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The P NMR spectra were measured on a Varian
Unity-300 spectrometer (121.4 MHz) using 85% phos-
phoric acid as external reference. TLC analysis was
performed on Silufol plates using 2-propanol–benzene
2
3
4
. Arbuzov, B.A., Tudrii, G.A., and Fuzhenkova, A.V., Izv.
Akad. Nauk SSSR, Ser. Khim., 1979, p. 1585.
(
3:1) as eluent; development with iodine vapor. All
. Tudrii, G.A. and Fuzhenkova, A.V., Zh. Obshch. Khim.,
experiments were carried out under dry argon. Quan-
tum-chemical calculations were performed with the aid
1
978, vol. 48, p. 490.
. Galkin, V.I., Galkina, I.V., Kurdi, Kh.A., Denisov, B.V.,
and Cherkasov, R.A., Metalloorg. Khim., 1990, vol. 3,
p. 1429.
of GAMESS 98 program [18].
2
(
η -Cyclohexanone)pentacarbonyltungsten(0)
1
(
IV) and η -(cyclohexanone)pentacarbonyltung-
5
6
7
8
9
. Beletskaya, I.P. and Kazankova, M.A., Russ. J. Org.
Chem., 2002, vol. 38, p. 1391.
sten(0) (V). A mixture of 1 g of hexacarbonyltung-
sten(0) and 5 ml of cyclohexanone was heated for 15 h
at the boiling point under argon. The colorless needle-
shaped crystals were filtered off. Yield 66.3%,
mp 165°C (decomp.). IR spectrum (mineral oil), ν,
. Kuramshin, A.I., Karpenko, E.A., and Cherkasov, R.A.,
Russ. J. Gen. Chem., 2001, vol. 71, p. 191.
. Kuramshin, A.I., Pavlova, I.V., and Cherkasov, R.A.,
Russ. J. Org. Chem., 2004, vol. 40, p. 45.
–1
cm : 1600 (C=O, π-coordinated), 1660 (C=O, n-coor-
. Kuramshin, A.I., Kuramshina, E.A., and Cherka-
sov, R.A., Russ. J. Org. Chem., 2004, vol. 40, p. 1265.
dinated). Found, %: C 31.80; H 2.37. C H O W. Cal-
11
10
6
culated, %: C 31.31; H 2.39.
. Kuramshin, A.I., Mushkin, V.B., Karpenko, E.A., and
Cherkasov, R.A., Russ. J. Gen. Chem., 2001, vol. 71,
p. 348.
1
cis- and trans-Bis(η -cyclohexanethione)tetracar-
bonyltungsten(0) (VI/VII). A solution of 0.16 g of
cyclohexanethione in 5 ml of 2-propanol was added
to a solution of 0.50 g hexacarbonyltungsten(0) in 5 ml
of 2-propanol. The pale yellow crystals were filtered
off. Yield 75.6%, mp 183°C (decomp.). IR spectrum
10. Faller, J.W., Ma, Y., Smart, C.J., and Di Verdi, M.J.,
J. Organomet. Chem., 1991, vol. 420, p. 237.
11. Caldarelli, J.L., Wagner, L.E., White, P.S., and Temple-
ton, J.L., J. Am. Chem. Soc., 1994, vol. 116, p. 2878.
–
1
(
3
mineral oil), ν, cm : 1140 (C=S, uncoordinated); 374,
64 (W–S); 1950, 1980, 2000, 2100 (CO ligands).
Found, %: C 36.48; H 4.37; S 12.09. C H O SW.
12. Comprehensive Organometallic Chemistry, Wilkin-
son, G., Ed., Oxford: Pergamon, 1980, vol. 3, p. 799.
16
24
4
13. Pardue, J.E. and Dobson, G.R., Inorg. Chim. Acta, 1976,
Calculated, %: C 36.37; H 4.58; S 12.14.
vol. 20, p. 207.
1
4. Kuramshin, A.I., Pavlova, I.V., Sokolov, Yu.A., and
Cherkasov, R.A., Karbonil’nye soedineniya v sinteze
geterotsiklov (Carbonyl Compounds in the Synthesis of
Heterocycles), Saratov, 2004, p. 223.
Reactions of free ligands and coordination
compounds with diethyl phosphonate. The reactions
were carried out at 20°C in benzene in the presence of
1
0 mol % of triethylamine. Diethyl phosphonate was
1
5. Kuramshin, A.I., Kuramshina, E.A., and Cherka-
taken in an amount equimolar to the coordinated sub-
strate containing a C=X bond. After 24 h, the reaction
sov, R.A., Russ. J. Gen. Chem., 2001, vol. 71, p. 354.
3
1
16. Schmidt, Th., Bienewald, F., and Goddard, R., J. Chem.
Soc., Chem. Commun., 1994, vol. 35, p. 1857.
mixtures were analyzed by P NMR spectroscopy.
This study was performed under financial support
by the Ministry of Education and Science of the
Russian Federation (programs “Universities of Russia–
Basic Research,” project no. ur.05.01.081), by the
Academy of Sciences of Tatarstan (project no. 03-12),
and by the joint program of CRDF and the Ministry
of Education and Science of the Russian Federation
1
7. Organikum. Organisch-chemisches Grundpraktikum,
Berlin: Wissenschaften, 1976, 15th ed. Translated under
the title Organikum, Moscow: Mir, 1979, vol. 2, p. 353.
1
8. Schmidt, M.W., Baldridge, K.K., Boatz, J.A., El-
bert, S.T., Gordon, M.S., Jensen, J.H., Koseki, S., Mat-
sunaga, N., Nguyen, K.A, Su, S.J., Windus, T.L.,
Dupuis, M., and Montgomery, A., J. Comput. Chem.,
1993, vol. 14, p. 1347.
“
Basic Research and Higher Education” (REC-007).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 9 2005