2-Phosphinothioyl- and 2-phosphinoylethylcyclopentadienyl zirconium and titanium complexes. Crystal structure of [η5:η1- C5H4CH2CH2P(O)Ph2] TiCl3

Article abstract of DOI:10.1007/s11172-005-0226-3

The intracomplex conversion of (2-diphenylphosphanoethyl)cyclopentadienyl zirconium and titanium complexes into the corresponding 2-phosphinothioyl and 2-phosphinoyl derivatives, viz., (η⁵-C₅H ₅)[η⁵-C₅

Full text of DOI:10.1007/s11172-005-0226-3

Russian Chemical Bulletin, International Edition, Vol. 54, No. 1, pp. 117—123, January, 2005
117
2ꢀPhosphinothioylꢀ and 2ꢀphosphinoylethylcyclopentadienyl
zirconium and titanium complexes.
Crystal structure of [η5:η1ꢀC5H4CH2CH2P(O)Ph2]TiCl3
a
b
c
D. P. Krut´ko,a M. V. Borzov, E. N. Veksler, and A. V. Churakov
ꢀ
aDepartment of Chemistry, M. V. Lomonosov Moscow State University,
1 Leninskie Gory, 119992 Moscow, Russian Federation.
Fax: +7 (095) 932 8846. Eꢀmail: kdp@org.chem.msu.su
bN. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences,
4 ul. Kosygina, 119991 Moscow, Russian Federation.
Fax: +7 (095) 137 8284. Eꢀmail: veksler@chph.ras.ru
cN. S. Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences,
31 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (095) 954 1279. Eꢀmail: churakov@igic.ras.ru
The intracomplex conversion of (2ꢀdiphenylphosphanoethyl)cyclopentadienyl zirconium
and titanium complexes into the corresponding 2ꢀphosphinothioyl and 2ꢀphosphinoyl derivaꢀ
5
5
5
tives, viz., (η ꢀC5H5)[η ꢀC5H4CH2CH2P(S)Ph2]ZrCl2, [η ꢀC5H4CH2CH2P(S)Ph2]ZrCl3,
5
1
5
1
[η :η ꢀC5H4CH2CH2P(O)Ph2]ZrCl3•THF, and [η :η ꢀC5H4CH2CH2P(O)Ph2]TiCl3 (7), was
performed. The NMR spectroscopy data revealed the following order of the coordination
ability of the functional groups with respect to the Zr center: Ph2P=O > Ph2P > Ph2P=S. An
analogous order was found for the monodentate ligands (Ph3P=O > Ph3P > Ph3P=S) with
5
respect to (η ꢀC5H5)ZrCl3. The molecular structure of complex 7 was established by Xꢀray
diffraction analysis. Coordination of the Ph2P=O group to the titanium atom was found
retained both in the crystalline state and solution.
Key words: zirconium, titanium, 2ꢀthiophosphanoylethylcyclopentadienes, 2ꢀphosphanoylꢀ
ethylcyclopentadienes, intramolecular coordination, NMR spectroscopy, Xꢀray diffraction
analysis.
Phosphanes are widely used as ligands in organomeꢀ
tallic chemistry. However, the number of studies devoted
to transition metal complexes with phosphane sulfide and
phosphane oxide ligands is at least two orders of magniꢀ
tude smaller. A few complexes of Group 4 metals with
such ligands are known.1—4 Of cyclopentadienyl comꢀ
plexes, only titanium derivatives, in which the P(S)Ph2 or
P(O)Ph2 group is directly bound to the Cp ring and canꢀ
not be coordinated to the metal atom, were described.4 At
the same time, cyclopentadienyl transition metal comꢀ
plexes containing various functional groups (OR,5
NRR´,6,7 SR,8 PRR´ 8) in the side chain of the Cp ring
are being intensively studied.
We attempted to modify the following complexes:
(η5ꢀC5H5)(η5ꢀC5H4CH2CH2PPh2)ZrCl2 (1)9, (η5:η1ꢀ
C5H4CH2CH2PPh2)ZrCl3•THF (2)9, and (η5:η1ꢀ
C5H4CH2CH2PPh2)TiCl3 (3)10, which have been synꢀ
thesized earlier, directly in the coordination sphere of
metal to prepare the corresponding P(S)Ph2 and P(O)Ph2
derivatives. It was also of interest to compare the coordiꢀ
nation ability of these groups and the PPh2 group with
respect to the Zr and Ti atoms. We also studied the reacꢀ
tion of the (η5ꢀC5H5)ZrCl3 complex as a model comꢀ
pound with Ph3P, Ph3PS, and Ph3PO.
A downfield shift of the signal in the 31P NMR specꢀ
trum (no less than 10 ppm) of a complex compared to that
of the uncoordinated ligand can serve as a reliable criteꢀ
rion for the coordination of the phosphorusꢀcontaining
functional group to the metal atom. Therefore, we used
31P NMR spectroscopy as the main method to study the
ability of phosphane sulfides and phosphane oxides to be
coordinated to the metal atom.
Results and Discussion
Cyclopentadienyl zirconium complexes
The reaction of bisꢀcyclopentadienyl complex 1 with
elemental sulfur in toluene proceeds smoothly and afꢀ
fords the corresponding phosphane sulfide derivative 4 in
nearly 100% yield (Scheme 1).
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 116—122, January, 2005.
1066ꢀ5285/05/5401ꢀ0117 © 2005 Springer Science+Business Media, Inc.

118
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 1, January, 2005
Krut´ko et al.
Scheme 1
with comparable intensities in a δ range from 42.7 to 44.5
upon a decrease in the temperature to –70 °C. An analoꢀ
gous splitting of the multiplets is observed in the 1H NMR
spectrum. Both at room and lower temperatures, the
31P chemical shifts provide evidence that the P(S)Ph2
group remains uncoordinated to the Zr atom in both cases.
The observed dynamic processes are, apparently, associꢀ
ated with diꢀ and oligomerization of complex 5 when
solvating molecules are absent. It is known that the
(η5ꢀC5H5)ZrCl3 complex containing no coordinated
solvent exists as a linear polymer with the repeating
{Cl[(η5ꢀC5H5)ClZr(µꢀCl)2ZrCl(η5ꢀC5H5)]}n structural
fragment.12
Unlike the reaction with elemental sulfur, which proꢀ
ceeds readily and affords diphenylphosphane sulfide deꢀ
rivatives 4 and 5 in approximately 100% yields, the oxidaꢀ
tion of complexes 1 and 2 with molecular oxygen did not
give satisfactory preparative results (Scheme 2). Unlike
well known oxidation of phosphanes with hydrogen perꢀ
oxide, which evidently cannot be used in the case under
consideration, oxidation of the PPh2 group in the comꢀ
plexes with molecular oxygen occurs very slowly (stirring
for several days is required). In the latter case, side proꢀ
cesses (for example, oxidation of Cp rings) prevail with
the result that mixtures of unidentifiable, including inꢀ
soluble, products are produced. We observed this situaꢀ
tion in the reaction of sandwich 1 with molecular oxygen
both in toluene and THF.
Conditions and yields: toluene, ~100% yield.
Scheme 2
As expected, coordination of the P(S)Ph2 group to the
Zr atom was not observed. The 31P chemical shift is
43.8 ppm and appears in the region characteristic of
RCH2CH2P(S)Ph2 compounds.11
The reaction of complex 2 with one equivalent of
sulfur in toluene followed by complete removal of the
solvent gave halfꢀsandwich 5 containing no THF solvate
molecules in virtually quantitative yield (see Scheme 1).
The 31P NMR spectra of complex 5 were recorded in
two solvents, viz., in THFꢀd8 and CD2Cl2. The 31P chemiꢀ
cal shift in the spectrum of complex 5 in THFꢀd8 (δ 43.5)
is virtually identical to that observed for sandwich 4 and
indicates that the P(S)Ph2 group is not coordinated to the
1
Zr atom. All signals in the H and 13C NMR spectra of
complex 5, like those for complex 4, appear as narrow
multiplets with wellꢀresolved spinꢀspin coupling constants.
Apparently, this is attributable to the fact that the equilibꢀ
rium in a THF solution is completely shifted to 5a, in
which two coordination vacancies are occupied by THF
molecules (see Scheme 1).
Conditions and yields: i. 1 atm, toluene or THF; ii. 1 atm,
THF, ~15% yield.
At room temperature, the 31P NMR spectrum of comꢀ
plex 5 in CD2Cl2 shows a broadened signal at δ 43.3. In
1
the H NMR spectrum of complex 5 in CD2Cl2, all mulꢀ
Nevertheless, oxidation of halfꢀsandwich 2 afforded
(although in low yield) the corresponding phosphane oxꢀ
ide complex 6 (see Scheme 2), which was isolated in pure
tiplets are strongly broadened. The broadened signal in
the 31P NMR spectrum splits into five narrow singlets

C5H4CH2CH2P(E)Ph2 Zr and Ti complexes
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 1, January, 2005
119
1
form and characterized by H, 31P, and 13C NMR specꢀ
troscopy.
(Zr)—C5Me4—CH2—CH2—S(Me)→ZrCl3 metallacycle,
for which the corresponding energy was estimated to be
10—12 kcal mol–1 and the degenerate interconversion of
the metallacycle became slow on the NMR time scale at
temperatures lower than –70 °C.15
Hence, halfꢀsandwich 6 differs from complex 5, in
which the phosphinothioyl group remains uncoordinated
even in a nonsolvating solvent, and from complex 2, in
which the phosphane ligand is reversibly replaced with
the THF molecule, in that its phosphinoyl group has the
highest affinity for the ZrIV atom compared to the PPh2
and P(S)Ph2 functional groups.
In the 31P NMR spectra of complex 6 in THFꢀd8 and
CD2Cl2, δ(31P) are 49.6 and 50.2, respectively, whereas
the corresponding signal for phosphane oxides
RCH2CH2P(O)Ph2 is observed at δ ~30 (for three isoꢀ
mers of C5Me4(H)CH2CH2P(O)Ph2, δ(31P) = 30.0, 30.1,
and 31.713). The substantial (~20 ppm) shift of δ(31P) for
the phosphane oxide group unambiguously indicates the
formation of the Ph2P=O→Zr coordination bond in comꢀ
plex 6 (analogous changes in the 31P chemical shifts were
observed also for phosphane oxide and phosphane sulfide
complexes of other transition metals14). The H NMR
To verify this conclusion, we studied the reaction of
the (η5ꢀC5H5)ZrCl3•nTHF complex (n = 0.6) with Ph3P,
1
spectrum in CD2Cl2 shows signals of THF (1 equiv. with
respect to the complex based on the integral intensities of
the signals) at δ 3.94 (OCH2) and 1.76 (OCH2CH2), which
is evidence that in solution the THF molecule also reꢀ
mains coordinated to the Zr atom.
It was of interest to compare the dynamic behavior of
halfꢀsandwich 6 and its precursor 2 in solution. Earlier,9
we have revealed the occurrence of equilibrium for
phosphane complex 2 in a THF solution, which is associꢀ
ated with the replacement of the coordinated phosphane
group with the second THF molecule at low temperature
(Scheme 3).
1
Ph3PS, and Ph3PO in CD2Cl2 by H and 31P NMR
spectroscopy. Unlike the stoichiometric (η5ꢀC5H5)ZrCl3•
•DME adduct,16 the adduct of (η5ꢀC5H5)ZrCl3 with THF
has a variable composition. This allows one to achieve the
required Zr : THF ratio in the halfꢀsandwich. In this case,
it is desirable to use the starting complex with the Zr : THF
ratio varying from 0 to 1 in order that both vacancies at
the Zr atom be partially free, while THF be present in the
1
system as a competitive donor. The parameters of the H
and 31P NMR spectra of these model systems are given in
Table 1.
It can be seen that phosphane sulfide is uncoordinated
to the Zr atom, while THF remains completely coordiꢀ
nated even in the presence of a tenfold excess of Ph3PS
with respect to (η5ꢀC5H5)ZrCl3 (see Table 1, δ(1H) for
the OCH2 fragment in the THF molecule). The opposite
situation is observed for triphenylphosphane oxide. The
1H NMR spectrum shows signals of free THF, and the
31P NMR spectrum exhibits three broadened signals in a
ratio of 1 : 1 : 3. The first two signals most likely correꢀ
spond to two coordinated Ph3P=O molecules in the apiꢀ
cal and equatorial positions, and the third signal belongs
to free phosphane oxide.
Scheme 3
Study of the dynamic behavior of complex 6 in THFꢀd8
by lowꢀtemperature 1H and 31P NMR spectroscopy
demonstrated that the 31P NMR spectrum has two sinꢀ
glets at δ 50.2 and 47.1 in a ratio of 3 : 1, respectively,
already at –20 °C. A further decrease in the temperature
to –80 °C leads only to narrowing of these signals, whereas
their relative intensities remain unchanged. Signals at
δ ~30 corresponding to the uncoordinated P(O)Ph2
Triphenylphosphane is intermediate between phosꢀ
phane sulfide and phosphane oxide. Tetrahydrofuran
5
Table 1. Parameters of the NMR spectra of the (η ꢀC5H5)ZrCl3•
•0.6THF + L system (L = Ph3P, Ph3PS, Ph3PO) in CD2Cl2
at 25 °C
L
L : Zr
10
3.5 25.2 (~0.5)
–3.4 (~3)
δ(31P)a
δ(31P)b
δ(1Н)c
1
group are absent. The H NMR spectrum shows two sets
of signals in the cyclopentadienyl region (signals in
the region of the phenyl and bridging protons overlap
with each other). These results can most likely be interꢀ
preted as a decrease in the rate of interconversion beꢀ
tween two conformations of the pseudoꢀsixꢀmembered
(Zr)—C5H4—CH2—CH2—P=O→ZrCl3 metallacycle
characterized by close but different energies. The
energy barrier to their interconversion should be
higher than that for the pseudoꢀfiveꢀmembered
Ph3P=S
Ph3P
44.7
45.0
–3.6
4.21
4.18
Ph3P=O
5
43.1 (~1)
39.6 (~1)
29.4 (~3)
29.6
3.70
a Relative intensities of the signals are given in parentheses.
b For free L.
c For OCH2 in THF.

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Russ.Chem.Bull., Int.Ed., Vol. 54, No. 1, January, 2005
Krut´ko et al.
C(4)
(0.6 equiv.) completely remains in the coordination sphere
of the metal atom, whereas only ~0.5 equiv. of Ph3P are
coordinated. Taking into account large steric hindrance
due to the presence of the triphenylphosphane molecule,
Ph3P can presumably be coordinated only at one vacancy
in the complex, which is already partially occupied
by THF. Therefore the total ratio of the coordinated THF
and Ph3P molecules with respect to zirconium should
be 1 : 1. This ratio was actually observed within the accuꢀ
racy of the integration.
Therefore, the aboveꢀconsidered data agree well with
the results obtained for complexes 2, 5, and 6 with chelatꢀ
ing phosphorusꢀcontaining cyclopentadienyl ligands.
Hence, the functional groups under consideration can be
arranged with a high degree of assurance in the following
series of decreasing coordination ability in monocycloꢀ
pentadienyl zirconium complexes: Ph2P=O > Ph2P >
> Ph2P=S.
C(3)
C(2)
C(5)
C(1)
C(6)
Cl(1)
Ti(1)
Cl(2)
P(1)
C(7)
C(26)
C(25)
C(24)
O(1)
Cl(3)
C(21)
C(22)
C(23)
C(31)
C(36)
C(32)
C(33)
C(34)
C(35)
[η5:η1ꢀ(2ꢀDiphenylphosphinoylethyl)cyclopentaꢀ
dienyl]trichlorotitanium
Fig. 1. Molecular structure of complex 7. The second crystalloꢀ
graphically independent molecule, the toluene molecule, and
the hydrogen atoms are omitted.
In addition to the aboveꢀdescribed Zr complexes, we
prepared an analogous phosphane oxide halfꢀsandwich of
titanium and studied its structure in the crystalline state
and solution. The [η5:η1ꢀC5H4CH2CH2P(O)Ph2]TiCl3
complex (7) was prepared in relatively low yield by the
oxidation of halfꢀsandwich 3 with dry oxygen in THF
(Scheme 4).
known phosphane oxide complexes of titanium (2.009(7)
and 2.023(8) Å in HN≡TiCl2(OPPh3)2;1 2.008(6) and
2.047(6) Å in ButN≡TiCl2(OPPh3)2;2 2.061(2) and
2.062(2) Å in TiCl2[η2ꢀ(O)PPh2—CH2CH(Me)—O]2 3).
It should be noted that the Ti←O distance in complex 7
is substantially shorter than that in the [η5:η1ꢀ
C5H4CH2CH2OMe]TiCl3 complex (8) (2.214(10) Å).17
Apparently, this fact is associated with the character of
hybridization of the oxygen atom. In complex 7, hybridꢀ
ization of the oxygen atom is intermediate between sp2
and sp, whereas hybridization of the oxygen atom in 8 is
intermediate between sp2 and sp3. This is also evidenced
by the bond angles at the oxygen atom. In complex 8,
these bond angles are in a range of 112.6(11)—119.8°.17,18
In complex 7, the Ti—O—P angle averaged over two
molecules is 140.0(1)°. This value is smaller than that
in the RN≡TiCl2(OPPh3)2 complex (R = H, But)
(148.7(5)—162.5(5)°),1,2 which is, apparently, associated
with the cyclic structure of complex 7. The phosphorus
atom has a nearly tetrahedral environment. All bond angles
are in a range of 107.2(2)—112.0(0)°. By contrast, the
bond angles at the phosphorus atom in phosphane comꢀ
plex 3 vary from 100.2(2)° to 119.2(1)°,10 which is attribꢀ
utable to stronger strain of the sixꢀmembered metallacycle
compared to the fiveꢀmembered ring.
Scheme 4
Conditions and yields: 1 atm, THF, 30% yield.
Crystallization from toluene afforded single crystals of
complex 7 suitable for Xꢀray diffraction study. There are
two independent geometrically similar molecules 7 per
asymmetric unit. The crystal structure contains also a
toluene solvate molecule disordered over two positions
and located on a crystallographic inversion center. The
configuration of the complex can be described as a disꢀ
torted tetragonal pyramid (fourꢀlegged piano stool) conꢀ
taining the apical Cp ring (Fig. 1). Selected bond lengths
and bond angles are given in Table 2.
The Ti—Cpcent and Ti—Cl bond lengths averaged over
two molecules (2.045 and 2.352(1) Å, respectively)
are slightly larger than those in complex 3 (2.035 and
2.322(1) Å, respectively).10 The Ti←O bond length
(1.990(2) Å) correlates well with those observed in a few
In a solution of complex 7, as in a solution of its
zirconium analog 6, coordination of the phosphane oxide
group to the Ti atom is retained both in solvating and
nonsolvating media. The signal δ(31P) for complex 7 in

C5H4CH2CH2P(E)Ph2 Zr and Ti complexes
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 1, January, 2005
121
Table 2. Selected bond lengths (d) and bond angles (ω) for two independent molecules of complex 7*
Molecule A Molecule B Molecule A
d/Å Bond
Ti(2)—O(2)
Molecule B
Bond
d/Å
Angle
ω/deg
Angle
ω/deg
Ti(1)—O(1) 1.978(3)
Ti(1)—C(3) 2.331(4)
Ti(1)—C(2) 2.375(4)
Ti(1)—C(4) 2.326(5)
Ti(1)—C(5) 2.358(4)
Ti(1)—C(1) 2.405(4)
Ti(1)—Cl(1) 2.342(2)
Ti(1)—Cl(3) 2.393(1)
Ti(1)—Cl(2) 2.344(2)
P(1)—C(31) 1.791(4)
P(1)—C(7) 1.788(4)
P(1)—C(21) 1.790(4)
O(1)—P(1) 1.509(3)
2.001(2)
O(1)—Ti(1)—Cl(2)
O(1)—Ti(1)—Cl(3)
81.13(8)
81.94(8)
O(2)—Ti(2)—Cl(22)
O(2)—Ti(2)—Cl(21)
Cl(22)—Ti(2)—Cl(21)
O(2)—Ti(2)—Cl(23)
81.28(8)
139.39(8)
86.19(6)
81.11(8)
Ti(2)—C(43) 2.336(4)
Ti(2)—C(42) 2.370(5)
Ti(2)—C(44) 2.327(4)
Ti(2)—C(45) 2.359(4)
Ti(2)—C(41) 2.399(4)
Ti(2)—Cl(21) 2.340(2)
Ti(2)—Cl(23) 2.357(1)
Ti(2)—Cl(22) 2.338(2)
Cl(2)—Ti(1)—Cl(3) 142.96(5)
O(1)—Ti(1)—Cl(1) 135.60(9)
Cl(1)—Ti(1)—Cl(2)
Cl(1)—Ti(1)—Cl(3)
O(1)—P(1)—C(7)
C(7)—P(1)—C(21)
C(7)—P(1)—C(31)
O(1)—P(1)—C(21)
O(1)—P(1)—C(31)
C(21)—P(1)—C(31)
P(1)—O(1)—Ti(1)
84.54(6)
84.94(5)
110.4(2)
108.3(2)
110.8(2)
108.2(2)
111.9(2)
107.2(2)
140.1(2)
Cl(22)—Ti(2)—Cl(23) 140.05(5)
Cl(21)—Ti(2)—Cl(23)
O(2)—P(2)—C(47)
O(2)—P(2)—C(61)
C(47)—P(2)—C(61)
O(2)—P(2)—C(51)
C(47)—P(2)—C(51)
C(61)—P(2)—C(51)
P(2)—O(2)—Ti(2)
84.34(6)
110.0(2)
108.0(2)
108.7(2)
112.0(2)
110.6(2)
107.4(2)
139.8(2)
P(2)—C(47)
P(2)—C(61)
P(2)—C(51)
O(2)—P(2)
1.779(5)
1.787(4)
1.791(4)
1.510(3)
* The Ti(1)—PL(1) and Ti(2)—PL(2) distances are 2.035(2) and 2.039(2) Å, respectively; PL(1) and PL(2) are the mean planes
through the C(1)—C(5) and C(41)—C(45) atoms, respectively.
1
standard for the H and 13C NMR spectra, respectively. The
CD2Cl2 (51.1) and THFꢀd8 (49.8) is shifted downfield by
31P NMR spectra were measured with 85% H3PO4 as the exterꢀ
nal standard. The temperature calibration was performed using
a standard methanol sample. The mass spectra were recorded on
a KratosꢀMSꢀ890 spectrometer. Elemental analysis was carried
out on an automated CarloꢀErba analyzer.
~20 ppm relative to that observed for free phosphane
oxide (δ(31P) ≈ 30). For comparison, the downfield shift
1
of the signal in the spectrum of HN≡TiCl2(OPPh3)2
(δ(31P) = 42.4) is approximately 15 ppm with respect to
uncoordinated Ph3PO (δ(31P) ≈ 27).
5
(η ꢀCyclopentadienyl)trichlorozirconium; an adduct with
To summarize, we demonstrated the possibility of subꢀ
jecting the phosphane ligand in cyclopentadienyl zircoꢀ
nium complexes to preparative innerꢀsphere modificaꢀ
tion with elemental sulfur giving rise to the corresponding
phosphane sulfide derivatives. Analogous oxidation of
phosphane complexes with molecular oxygen is accomꢀ
panied by side processes and affords the target phosphane
oxide complexes in low yields. Study by 31P NMR specꢀ
troscopy demonstrated that the coordination ability of the
functional groups in monocyclopentadienyl zirconium
complexes decreases in the series Ph2P=O > Ph2P >
> Ph2P=S.
0.6 THF molecules was prepared starting from CpZrCl3•2THF,
which was synthesized according to a known procedure19 by the
20
reaction of ZrCl4 with CpSiMe3 in toluene. Then CpZrCl3•
•2THF (11.9 g, 29.3 mmol) was suspended in toluene (100 mL).
The suspension was heated at 100 °C for 30 min, the solvent was
distilled off into a liquid nitrogen cooled trap and dried in high
vacuum. The procedure was repeated. The reaction product was
1
analyzed by H NMR spectroscopy, which demonstrated that
the THF : complex ratio was ~0.6. The yield was 8.9 g (virtually
quantitative yield with respect to CpZrCl3•2THF).
5
5
[η ꢀ(2ꢀDiphenylphosphinothioylethyl)cyclopentadienyl][η ꢀ
cyclopentadienyl]dichlorozirconium (4). A solution of sulfur
(53 mg, 1.65 mmol) in toluene (25 mL) was added to a solution
of complex 1 (830 mg, 1.65 mmol) in toluene (50 mL). The
reaction mixture was stirred for 4 h and then kept for 16 h. The
solvent was removed, the product was twice washed on a filter
with pentane, and dried in high vacuum. The product was obꢀ
tained as a white powder in a yield of 840 mg (1.57 mmol, 95%).
Found (%): C, 53.45; H, 4.46. C24H23Cl2PSZr. Calculated (%):
Experimental
All reactions were carried out and samples for NMR specꢀ
troscopy were prepared in Schlenkꢀtype allꢀsealed evacuated
apparatus. The starting phosphane complexes of zirconium 1
and 2 9 and titanium 3 10 were prepared according to known
procedures. Commercial triphenylphosphane and triphenylꢀ
phosphane oxide were used. Triphenylphosphane sulfide was
synthesized by the reaction of equimolar amounts of Ph3P and
sulfur in toluene. The solvents were dried according to standard
procedures.
The 1H, 13C, and 31P NMR spectra were recorded on a
Varian VXRꢀ400 spectrometer at 400, 100, and 162 MHz, reꢀ
spectively. The chemical shifts of Me4Si or the residual protons
of the corresponding deuterated solvents (δ 5.32 and 53.8 for
CD2Cl2, δ 1.73 and 25.3 for THFꢀd8) were used as the inner
1
C, 53.72; H, 4.32. H NMR (THFꢀd8, 25 °C), δ: 2.89 (m, 2 H,
CH2P); 3.00 (m, 2 H, CH2CH2P); 6.28 (virt. t, 2 H, H(2), H(5),
3+4
3+4
J
= 5.2 Hz); 6.36 (virt. t, 2 H, H(3), H(4),
J
=
H,H
H,H
5.2 Hz); 6.47 (s, 5 H, C5H5); 7.43 (m, 6 H, Hm, Hp); 7.93 (m,
1
4 H, Ho). 13C NMR, δ: 23.71 (t, CH2CH2P, JC,H = 131 Hz);
1
1
32.61 (dt, CH2P, JC,H = 131 Hz, JC,P = 56.5 Hz); 113.44 (d,
1
1
C(3)H, C(4)H, JC,H = 174 Hz); 116.63 (d, C5H5, JC,H
174 Hz); 117.77 (d, C(2)H, C(5)H, JC,H = 173 Hz); 129.17
(dd, Cm, JC,H = 160 Hz, JC,P = 11.5 Hz); 131.87 (d, Cp,
1JC,H = 160 Hz); 131.98 (dd, Co, JC,H = 160 Hz, JC,P
9.7 Hz); 134.27 (d, C(1), JC,P = 18.2 Hz); 134.53 (d, Cipso
1JC,P = 79.0 Hz). 31P—{1H} NMR: 43.2 (s). 1H NMR (CD2Cl2,
=
1
1
3
1
2
=
3
,

122
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 1, January, 2005
Krut´ko et al.
25 °C), δ: 2.83 (m, 2 H, CH2P); 3.01 (m, 2 H, CH2CH2P); 6.22
moved from the filtrate to a liquid nitrogen cooled trap, and the
crystalline precipitate was dried in high vacuum.
3+4
(virt. t, 2 H, H(2), H(5),
J
= 5.6 Hz); 6.29 (virt. t, 2 H,
H,H
3+4
5
1
H(3), H(4),
J
= 5.6 Hz); 6.45 (s, 5 H, C5H5); 7.48 (m,
[η :η ꢀOꢀ(2ꢀDiphenylphosphinoylethyl)cyclopentadienyl]triꢀ
chlorozirconium (6). The reaction with the use of complex 2
(280 mg, 0.51 mmol) in THF afforded the target complex in a
yield of 40 mg (0.08 mmol, 15%) as a powdered white comꢀ
pound (>95% purity based on the NMR spectroscopic data).
H,H
6 H, Hm, Hp); 7.85 (m, 4 H, Ho). 13C NMR, δ: 23.17 (t,
1
1
CH2CH2P, JC,H = 131 Hz); 32.29 (dt, CH2P, JC,H = 131 Hz,
1JC,P = 56.8 Hz); 112.55 (d, C(3)H, C(4)H, JC,H = 174 Hz);
1
1
116.17 (d, C5H5, JC,H = 174 Hz); 117.43 (d, C(2)H, C(5)H,
1JC,H = 173 Hz); 128.94 (dd, Cm, JC,H = 160 Hz, JC,P
1
3
=
1H NMR (THFꢀd8, 25 °C), δ: 2.89—3.05 (m, 4 H, CH2CH2P);
1
2
3+4
11.8 Hz); 131.37 (dd, Co, JC,H = 160 Hz, JC,P = 10.1 Hz);
131.80 (d, Cp, 1JC,H = 160 Hz); 132.98 (d, Cipso, 1JC,P = 80.2 Hz);
6.40 (virt. t, 2 H, H(2), H(5),
J
= 5.2 Hz); 6.46 (virt. t,
H,H
2 H, H(3), H(4), 3+4JH,H = 5.2 Hz); 7.60 (m, 4 H, Hm); 7.69 (m,
2 H, Hp); 8.00 (m, 4 H, Ho). 13C NMR, δ: 21.39 (dt, CH2CH2P,
3
133.60 (d, C(1), JC,P = 17.7 Hz). 31P—{1H} NMR: 43.8 (s).
MS (EI, 70 eV), m/z (Irel (%)): 534 [M]+ (0.4), 499 [M – Cl]+
(3.4), 469 [M – C5H5]+ (24.5), 309 [C5H4CH2CH2P(S)Ph2]+
(5.8), 277 [C5H4CH2CH2PPh2]+ (23.3), 225 [C5H5ZrCl2]+
(41.5), 218 [HP(S)Ph2]+ (100), 185 [PPh2]+ (52.1), 183
[C12H8P, 9ꢀphosphafluorene]+ (64.1), 140 [PhP(S)]+ (51.4),
121 [HCPh]+ (32.1), 108 [PPh]+ (17.6), 91 [C7H7]+ (18.4), 77
[Ph]+ (15.8), 65 [C5H5]+ (11.3), 63 [P=S]+ (14.8).
1JC,H = 133 Hz, JC,P = 5.2 Hz); 25.04 (dt, CH2P, JC,H
=
=
2
1
1
1
134 Hz, JC,P = 70 Hz); 118.19 (d, C(3)H, C(4)H, JC,H
176 Hz); 120.23 (d, C(2)H, C(5)H, JC,H = 174 Hz); 126.39 (s,
C(1)); 128.18 (d, Cipso, 1JC,P = 106 Hz); 129.90 (dd, Cm, 1JC,H
1
=
3
1
164 Hz, JC,P = 12.5 Hz); 132.93 (dd, Co, JC,H = 164 Hz,
2JC,P = 11.3 Hz); 134.27 (dd, Cp, JC,H = 163 Hz, JC,P
=
1
4
3.1 Hz). 31P—{1H} NMR: 49.6 (s). H NMR (CD2Cl2, 25 °C),
δ: 1.76 (m, 4 H, THF); 2.87—3.03 (m, 4 H, CH2CH2P);
3.94 (m, 4 H, THF); 6.51 (virt. t, 2 H, H(2), H(5),
1
5
[η ꢀ(2ꢀDiphenylphosphinothioylethyl)cyclopentadienyl]triꢀ
chlorozirconium (5). A solution of sulfur (12.7 mg 0.40 mmol) in
toluene (20 mL) was added to a solution of complex 2 (200 mg,
0.40 mmol) in toluene (30 mL). The reaction mixture was stirred
for 4 h and then allowed to stand for 16 h. The solvent was
distilled off at 50 °C into a liquid nitrogen cooled trap, the
precipitate was washed with hexane (2×5 mL) by decantations
and dried in high vacuum. The product was obtained as a white
powder in a yield of 190 mg (0.37 mmol, 93%). Found (%):
C, 45.31; H, 3.71. C19H18Cl3PSZr. Calculated (%): C, 45.01;
3+4
3+4
J
= 5.6 Hz); 6.58 (virt. t, 2 H, H(3), H(4),
J
=
H,H
H,H
5.6 Hz); 7.60 (m, 4 H, Hm); 7.71 (m, 2 H, Hp); 7.84 (m, 4 H,
Ho). 31P—{1H} NMR: 50.2 (s).
5
1
[η :η ꢀOꢀ(2ꢀDiphenylphosphinoylethyl)cyclopentadienyl]triꢀ
chlorotitanium (7). The reaction with the use of complex 3
(300 mg, 0.65 mmol) in THF afforded phosphane oxide complex
7 in a yield of 94 mg (0.20 mmol, 30%) as an orange powdered
compound. Found (%): C, 50.87; H, 4.10. C19H18Cl3OPTi.
1
1
H, 3.58. H NMR (THFꢀd8, 25 °C), δ: 2.96 (m, 2 H, CH2P);
Calculated (%): C, 50.99; H, 4.05. H NMR (CD2Cl2, 25 °C),
3.15 (m, 2 H, CH2CH2P); 6.32 (virt. t, 2 H, H(2), H(5),
δ: 2.95—3.05 (m, 4 H, CH2CH2P); 6.87 and 7.03 (both virt. t,
3+4
3+4
3+4
J
= 5.2 Hz); 6.40 (virt. t, 2 H, H(3), H(4),
J
=
2 H each, H(2)—H(5),
J
= 5.4 Hz); 7.61 (m, 4 H, Hm);
H,H
H,H
H,H
5.2 Hz); 7.43 (m, 6 H, Hm, Hp); 7.95 (m, 4 H, Ho). 13C NMR, δ:
7.70 (m, 2 H, Hp); 7.86 (m, 4 H, Ho). 13C—{1H} NMR: 21.52
24.32 (t, CH2CH2P, 1JC,H = 131 Hz); 32.71 (dt, CH2P, 1JC,H
130 Hz, JC,P = 58.0 Hz); 119.06 and 119.15 (both d, C(2)H,
C(3)H, C(4)H, C(5)H, 1JC,H = 174 Hz); 129.13 (dd, Cm, 1JC,H
160 Hz, JC,P = 11.6 Hz); 131.80 (dd, Cp, JC,H = 161 Hz,
4JC,P = 3.1 Hz); 132.04 (dd, Co, 1JC,H = 161 Hz, 2JC,P = 9.8 Hz);
133.51 (d, C(1), JC,P = 18.2 Hz); 134.75 (d, Cipso
=
(br.s, CH2CH2P); 25.11 (d, CH2P, JC,P = 69 Hz); 124.99,
1
1
125.36 (C(2)H, C(3)H, C(4)H, C(5)H); 125.60 (C(1)); 128.93
(d, Cipso, 1JC,P = 81 Hz); 129.78 (d, Cm, 3JC,P = 13.5 Hz); 132.09
(d, Co, 2JC,P = 10.8 Hz); 134.24 (Cp). 31P—{1H} NMR: 51.1 (s).
1H NMR (THFꢀd8, 25 °C), δ: 2.99 (m, 2 H, CH2CH2P); 3.17
=
3
1
3
,
1JC,P
=
(m, 2 H, CH2P); 6.82 and 6.93 (both virt. t, 2 H each,
78.7 Hz). 31P—{1H} NMR: 43.5 (s). 1H NMR (CD2Cl2, 25 °C),
δ: 3.16 (br.m, 4 H, CH2CH2P); 6.51 and 6.61 (both br.s,
2 H each, H(2)—H(5)); 7.52 (br.m, 6 H, Hm, Hp); 7.84 (br.m,
4 H, Ho). 31P NMR, δ: 43.3 (br.s). MS (EI, 70 eV), m/z (Irel (%)):
504 [M]+ (0.4), 469 [M – Cl]+ (2.5), 252 [M – Cl – HP(S)Ph2]+
(4.5), 218 [HP(S)Ph2]+ (100), 185 [PPh2]+ (53.3), 183 [C12H8P,
9ꢀphosphafluorene]+ (68.2), 140 [PhP(S)]+ (61.4), 121 [HCPh]+
(34.8),108 [PPh]+ (36.0), 91 [C7H7]+ (85.4), 77 [Ph]+ (33.8), 63
[P=S]+ (34.5), 36 [HCl]+ (56.8).
H(2)—H(5),
J
= 5.3 Hz); 7.57 (m, 4 H, Hm); 7.65 (m,
H,H
3+4
2 H, Hp); 7.99 (m, 4 H, Ho). 31P—{1H} NMR: 49.8 (s). MS
(EI, 70 eV), m/z (Irel (%)): 411 [M – Cl]+ (0.2), 368
[M – C5H4=CH2]+ (0.3), 367 [M – C5H4Me]+ (0.3), 294
[C5H5CH2CH2P(O)Ph2]+ (21.4), 216 [C5H4CH2CH2P(O)Ph]+
(7.1), 215 [CH2P(O)Ph2]+ (38.9), 202 [HP(O)Ph2]+ (100), 201
[P(O)Ph2]+ (45.9), 183 [C12H8P, 9ꢀphosphafluorene]+ (11.4),
125 [HP(O)Ph]+ (18.9), 121 [CH=PPh]+ (2.9), 108 [PPh]+
(5.0), 91 [C7H7]+ (22.6), 77 [C6H5]+ (33.7).
Oxidation of complexes 1—3 with oxygen (general proceꢀ
dure). Oxidation of the complexes was carried out in an allꢀ
sealed glass apparatus equipped with two containers separated
by a Teflon stopcock. In one container (~1 L), molecular oxyꢀ
gen was predried over P2O5 for 7 days. A solution of the complex
(~300 mg) in THF or toluene (~5 mL) was placed in another
container, which was intially separated from the first one with a
breakable glass wall (better results were obtained in THF). The
glass wall was broken, and the solution of the complex was
stirred using a magnetic stirrer for 3 days, the apparatus being
protected from daylight. Then the apparatus was evacuated, the
reaction mixture was filtered off from insoluble products, and
the precipitate was extracted with THF. The solvent was reꢀ
Single crystals of complex 7 suitable for Xꢀray diffraction
analysis were prepared by slow crystallization from toluene.
Xꢀray diffraction study of compound 7 was carried out on an
automated EnrafꢀNonius CAD4 diffractometer at room temꢀ
perature using MoꢀKα radiation (λ = 0.71073 Å, graphite
monochromator). Crystals of 7 (C19H18Cl3OPTi•0.25C7H8,
M = 470.59) are triclinic, space group Р–1, a = 11.455(3),
b = 13.663(8), c = 14.050(6) Å, α = 78.82(4), β = 83.09(4),
γ = 89.44(4)°, V = 2141(2) Å3, Z = 4, dcalc = 1.460 g cm–3
,
µ(MoꢀKα) = 0.857 mm–1, F(000) = 962. Intensities of 7306 reꢀ
flections (5913 independent reflections, Rint = 0.0294) were
measured using the ωꢀscanning mode in the angle range
2.19 < θ < 24.97° (–13 ≤ h ≤ 8, –16 ≤ k ≤ 16, –3 ≤ l ≤ 16). The

C5H4CH2CH2P(E)Ph2 Zr and Ti complexes
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 1, January, 2005
123
intensities of reflections were corrected for the Lorentz and
polarization factors.21 Absorption was ignored. The structure
was solved by direct methods (SHELXSꢀ86).22 All nonhydrogen
atoms were refined anisotropically by the fullꢀmatrix leastꢀ
squares method against F 2 (SHELXLꢀ97).23 All hydrogen atꢀ
oms (except for the H atoms in the toluene solvate molecule)
were revealed from difference electron density maps and refined
isotropically. The hydrogen atoms of the C7H8 molecule were
placed in calculated positions and refined using a riding model.
The final reliability factors were R1 = 0.0425, wR2 = 0.1108 for
4795 reflections with I > 2σ(I ); 658 parameters were refined;
9. D. P. Krut´ko, M. V. Borzov, E. N. Veksler, A. V. Churakov,
and J. A. K. Howard, Polyhedron, 1998, 17, 3889.
10. D. P. Krut´ko, M. V. Borzov, E. N. Veksler, A. V. Churakov,
and K. Mach, Polyhedron, 2003, 22, 2885.
11. I. M. Aladzheva, O. V. Bykhovskaya, D. I. Lobanov, P. V.
Petrovskii, T. A. Mastryukova, and M. I. Kabachnik,
Zh. Obshch. Khim., 1995, 65, 1586 [Russ. J. Gen. Chem.,
1995, 65 (Engl. Transl.)].
12. L. M. Engelhardt, R. I. Papasergio, C. L. Raston, and A. H.
White, Organometallics, 1984, 3, 18.
13. D. P. Krut´ko, M. V. Borzov, E. N. Veksler, R. S. Kirsanov,
and A. V. Churakov, Eur. J. Inorg. Chem., 1999, 1973.
14. T. C. Blagborough, R. Davis, and P. Ivison, J. Organomet.
Chem., 1994, 467, 85.
GOOF = 0.997, min/max ∆ρ = –0.497/0.479 e Å–3
.
This study was financially supported by the Foundaꢀ
tion of the President of the Russian Federation (Program
for Support of Young Scientists, Grant MKꢀ3697.2004.3).
15. D. P. Krut´ko, M. V. Borzov, V. S. Petrosyan, L. G.
Kuz´mina, and A. V. Churakov, Izv. Akad. Nauk, Ser. Khim.,
1996, 984 [Russ. Chem. Bull., 1996, 45, 940 (Engl. Transl.)].
16. N. J. Wells, J. C. Huffman, and K. G. Caulton, J. Organomet.
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Received February 24, 2004;
in revised form June 10, 2004
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