Regioselectivity of reactions of vinyl- and isopropenylcyclopentadienide anions with electrophilic agents. Synthesis and crystal structures of complexes [C5H4C(Me)=CH2]ZrCl3·2THF and [C5Me4CH=CH2]ZrCl3·2THF

Article abstract of DOI:10.1007/s11172-005-0263-y

Regioselectivity of the reactions of lithium vinyl- and isopropenylcyclopentadienides C₅H₄C(R)=CH₂ ^-Li⁺(R = H, Me) and lithium tetramethylvinylcyclopentadienide C₅Me₄CH=CH₂ ^-Li⁺ with various electrophilic agents (Me ₃SiCl, Me₃SnCl, Et₂PCl, 2-chloro-1, 3-dioxaphospholane, and MeI) was studied. Two new monocyclopentadienyl zirconium complexes, [C₅H₄C(Me) = CH₂]ZrCl ₃·2THF and [C₅Me₄CH=CH ₂]ZrCl₃·2THF, were synthesized. Their crystal structures were established by X-ray diffraction. The results of quantum chemical calculations for the C₅H₄C(R) = CH₂ ^- (R = H, Me) and C₅Me₄CH=CH₂ ^- anions by the DFT method (RMPW1PW91) with the 6-311+G(d, p) split valence basis set are in good agreement with experimental data on the regioselectivity of their reactions with electrophilic agents.

Full text of DOI:10.1007/s11172-005-0263-y

390
Russian Chemical Bulletin, International Edition, Vol. 54, No. 2, pp. 390—399, February, 2005
Regioselectivity of reactions of vinylꢀ and isopropenylcyclopentadienide
anions with electrophilic agents. Synthesis and crystal structures of
complexes [C5H4C(Me)=CH2]ZrCl3•2THF and
[C5Me4CH=CH2]ZrCl3•2THF
a
a
b
a
D. P. Krut´ko,a M. V. Borzov, O. V. Dolomanov, A. V. Churakov, and D. A. Lemenovskii
ꢀ
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. 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
Regioselectivity of the reactions of lithium vinylꢀ and isopropenylcyclopentadienides
C5H4C(R)=CH2–Li+ (R = H, Me) and lithium tetramethylvinylcyclopentadienide
C5Me4CH=CH2–Li+ with various electrophilic agents (Me3SiCl, Me3SnCl, Et2PCl,
2ꢀchloroꢀ1,3ꢀdioxaphospholane, and MeI) was studied. Two new monocyclopentadienyl zirꢀ
conium complexes, [C5H4C(Me)=CH2]ZrCl3•2THF and [C5Me4CH=CH2]ZrCl3•2THF,
were synthesized. Their crystal structures were established by Xꢀray diffraction. The results of
–
quantumꢀchemical calculations for the C5H4C(R)=CH2– (R = H, Me) and C5Me4CH=CH2
anions by the DFT method (RMPW1PW91) with the 6ꢀ311+G(d,p) splitꢀvalence basis set are
in good agreement with experimental data on the regioselectivity of their reactions with elecꢀ
trophilic agents.
Key words: vinylcyclopentadienide anion, isopropenylcyclopentadienide anion, electroꢀ
philic agents, regioselectivity, zirconium, Xꢀray diffraction analysis, NMR spectroscopy, quanꢀ
tumꢀchemical calculations.
Scheme 1
Functionalized Cp ligands are widely used in organoꢀ
metallic chemistry. Of these compounds, various ethenylꢀ
cyclopentadienes containing a double bond directly conꢀ
jugated with the cyclopentadienyl ring are of great imporꢀ
tance. In particular, this class of compounds includes the
vinylꢀ and isopropenylcyclopentadienyl ligands, which
were used in the synthesis of various sandwich and halfꢀ
sandwich compounds with a wide range of transition and
mainꢀgroup metals.1—10 Investigations of reactions of the
vinylꢀ and isopropenylcyclopentadienide anions with elecꢀ
trophilic agents are of interest by themselves because these
compounds contain two centers accessible to electrophilic
attack, viz., the Cp ring and the Cβ atom of the ethenyl
substituent (Scheme 1). The attack of an electrophilic
organyl agent on the ethenyl group affords 7ꢀsubstituted
fulvene, which can be used to synthesize sideꢀchain
functionalized ligands. The attack on the ring gives rise to
the corresponding heterosubstituted ethenylcyclopentaꢀ
diene. Silylated, stannylated, and (with certain limitaꢀ
tions) thalylated cyclopentadienes proved to be conveꢀ
nient reagents for the preparation of transition metal comꢀ
plexes.
EX is an heteroorganic electrophilic agent
The aim of the present study was to investigate
the regioselectivity of reactions of lithium vinylꢀ and
isopropenylcyclopentadienides C5H4C(R)=CH2–Li+
(R = H (1), Me (2)) and lithium tetramethylvinylꢀ
cyclopentadienide C5Me4CH=CH2–Li+ (3) with heteroꢀ
organic electrophilic agents (Me3SiCl, Me3SnCl, Et2PCl,
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 383—391, February, 2005.
1066ꢀ5285/05/5402ꢀ0390 © 2005 Springer Science+Business Media, Inc.

Reactions of [C5R4C(R´)=CH2]– anions
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 2, February, 2005
391
Scheme 2
R = H (1, 4a—c), Me (2, 5a—c)
2ꢀchloroꢀ1,3ꢀdioxaphospholane) and, for comparison,
with iodomethane as the simplest Cꢀelectrophilic agent.
These reagents were used to synthesize two new monoꢀ
cyclopentadienyl zirconium complexes. The crystal strucꢀ
tures of these complexes were established.
isopropenylcyclopentadienide 2 occurs regioselectively
at the Cp ring (Scheme 2) to give equilibrium mixtures
of the corresponding isomeric cyclopentadienylsilanes
4a—c and 5a—c in total yields of 65 and 73%, reꢀ
spectively. These compounds undergo interconversions
through elementotropic and prototropic rearrangements.
For both silylated cyclopentadienes, the isomer ratio
(a + b) : (c + minor vinyl isomers) was ~3 : 1, the isomer c
prevailing (~80%) among isomers containing the Me3Si
group in the vinyl position. The structure analogous to
cyclopentadienylsilane 5c was assigned to isomer 4c,
whereas the structure of compound 5c was unambiguꢀ
ously established by NMR spectroscopy. It should be
noted that a mixture of silanes 4a—c is unstable to heating
and/or atmospheric oxygen. For example, product 4 was
coated with a polymer film upon storage in air for a few
hours. An attempt to distill compound 4 at high temperaꢀ
ture (~80 °C, 7 Torr) leads to its polymerization. In this
respect, silanes 5a—c are much more stable.
In addition, to reveal the electronic effect on the
direction of electrophilic attack, it was of interest to
carry out quantumꢀchemical calculations for the
–
–
C5H4C(R)=CH2 (R = H, Me) and C5Me4CH=CH2
anions and analyze the electron density distribution in
these anions.
Results and Discussion
The starting vinylcyclopentadienyl salts 1—3 were synꢀ
thesized according to known procedures2,6,11 by deꢀ
protonation of the corresponding fulvenes. Salts 1—3 were
isolated in the individual crystalline state. To obtain comꢀ
parable results, the reactions of lithium vinylcycloꢀ
pentadienides with heteroorganic electrophilic agents and
iodomethane were carried out in the same fashion: a soluꢀ
tion of the corresponding lithium salt was added with
cooling to solutions of electrophilic agents (10—20% exꢀ
cess) in THF. After removal of the solvent and extraction
with hexane, the products were distilled in vacuo. The
Unlike monosubstituted cyclopentadienides 1 and 2,
silylation of tetramethylvinylcyclopentadienide 3 under
the same conditions occurs regioselectively at the termiꢀ
nal C atom of the double bond to give one product, viz.,
the corresponding fulvene 6 (Scheme 3).
1
structures of the products were established by H, 13C,
Scheme 3
and 31P NMR spectroscopy, including 2D COSY experiꢀ
ments and NOE difference spectra.
The reactions under study (unless they were accomꢀ
panied by polymerization) proceeded smoothly and gave
products in high total yields. However, in the case of
salt 1, only products of the reaction with Me3SiCl were
isolated. This is, apparently, attributable to the fact that
the unsubstituted vinylcyclopentadienyl ring is highly
prone to polymerization. Products isolated in the reacꢀ
tions of salt 2 with chlorodiethylphosphine and 2ꢀchloroꢀ
1,3ꢀdioxaphospholane, were also polyꢀ or oligomers of
unidentified structures.
Reactions of salts 2 and 3 with Me3SnCl. Isopropenylꢀ
cyclopentadienide 2 reacts with Me3SnCl regioselectively
at the Cp ring to form stannylated isopropenylcyclopentaꢀ
diene 7 in 70% yield (Scheme 4). The reaction of tetraꢀ
methylvinylcyclopentadienide 3 affords both possible
Reactions of salts 1—3 with Me3SiCl. We found that
silylation of lithium vinylcyclopentadienide 1 and lithium

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Russ.Chem.Bull., Int.Ed., Vol. 54, No. 2, February, 2005
Krut´ko et al.
products, viz., 8a and 8b (in a total yield of 86%), with
fulveneꢀtype product 8a predominating (90%). Study of
stannylated cyclopentadienes 7 and 8b by NMR spectroꢀ
scopy at room temperature demonstrated that these
compounds exhibit dynamic behavior due to fast
[1,2]ꢀelementotropic shifts of the Me3Sn group over the
positions of the Cp ring.
pentadienide 3 with 2ꢀchloroꢀ1,3ꢀdioxaphospholane ocꢀ
curs regioselectively to give vinylcyclopentadiene 9 in 68%
yield (Scheme 5). The reaction product, like comꢀ
pound 8b, exists as an equilibrium mixture of isomers at
the dioxaphospholane substituent, which undergo rapid
interconversion through [1,2]ꢀelementotropic shifts.
A more complex situation is observed in the reaction
of salt 3 with chlorodiethylphosphine (see Scheme 5).
The reaction affords a mixture of products of the electroꢀ
philic attack on both the Cp ring (10a,b) and the terminal
C atom of the double bond (10c), with the attack on the
Cp ring predominating (~5 : 1 ratio). At room temperaꢀ
ture, the rate of the [1,2]ꢀelementotropic shift in products
10a,b is low, and the NMR spectra show narrow signals of
both isomers.
Scheme 4
In a solution at room temperature, compounds 10a,b
are slowly transformed into compound 10d containing
two exocyclic double bonds. We believe that this rearꢀ
rangement is catalyzed by acidic admixtures, because the
electrophilic reagent was used in excess.
It should be noted that the highꢀfield part of the aliꢀ
phatic region in the 1H and 13C NMR spectra of reaction
products 10a—d is difficult to interpret due to strong overꢀ
lap of the signals. However, the signals in the most inforꢀ
mative allyl and vinyl regions of the spectra were assigned
unambiguously, which made it possible to reliably estabꢀ
lish both the structures of the products and their ratios in
the mixtures.
Reactions of salts 2 and 3 with MeI. Study of the
reactions of salts 2 and 3 with iodomethane unambiguꢀ
ously demonstrated that both reactions involved excluꢀ
sively the attack on the Cp ring (NMR spectra show no
signals of the ethyl group) (Scheme 6). The reactions
Reactions of salt 3 with phosphorusꢀcontaining electroꢀ
philic agents. The reaction of tetramethylvinylcycloꢀ
Scheme 5

Reactions of [C5R4C(R´)=CH2]– anions
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 2, February, 2005
393
afford mixtures of isomeric (isopropenyl)methylcycloꢀ
pentadienes 11 (<11 isomers at the Me group and the
system of double bonds in a total yield of 72%) and
pentamethyl(vinyl)cyclopentadienes 12a—c (in a total
yield of 84%), respectively. For the latter reaction, we
made the complete assignment of the signals in the H
and 13C NMR spectra and determined the isomeric comꢀ
position of the mixture.
sidered, the product of the attack on the Cβ atom would
not, under any circumstances, be the major product, and
the attack on the ring is always the main process. Second,
the expected percentage of the product of the attack on
the C(7) atom can be predicted to increase with increasꢀ
ing rigidity of the electrophilic agent (sum of the squares
of the orbital coefficients of two or three highest occupied
molecular orbitals is taken into account), and this perꢀ
centage is maximum in the limiting case of charge conꢀ
trol. Third, the percentage of the product of the attack on
the C(7) atom would be expected to increase in the case
of the permethylated cyclopentadienide anion. Fourth,
the introduction of the Me substituent at position 6 has
virtually no effect on the expected product ratio.
1
Scheme 6
In actuality, the attack on the C(7) atom was observed
only in the reactions of sterically hindered lithium
tetramethylvinylcyclopentadienide (3) with Me3SiCl,
Me3SnCl, and Et2PCl (percentage of the product of the
attack on this atom was 100, 90, and 17%, respectively).
It should be noted that the relative rigidity of the heteroꢀ
organic electrophilic agent decreases in the same order.
However, even in the limiting case of charge control, the
predicted percentage of the reaction product at the C(7)
atom was at most 36%. Hence, in our opinion, the
regioselectivity of the electrophilic attack on salt 3 is deꢀ
termined primarily by steric hindrance of the reagent,
which decreases in the series Me3SiCl > Me3SnCl >
> Et2PCl >> 1,3ꢀdioxaphospholane ≈ MeI.
Synthesis of zirconium halfꢀsandwich complexes. We
synthesized two new monocyclopentadienyl zirconium
complexes, viz., [C5H4C(Me)=CH2]ZrCl3•2THF (13)
and [C5Me4CH=CH2]ZrCl3•2THF (14) (Scheme 7).
Complex 13 was prepared by the reaction of the
ZrCl4•2THT adduct (THT is tetrahydrothiophene) with
silylated cyclopentadiene 5. Since the reaction of lithium
tetramethylvinylcyclopentadienide with Me3SiCl did not
afford an analogous silane (see Scheme 3), halfꢀsandwich
complex 14 was synthesized starting from salt 3 and
ZrCl4•2THT. Both complexes were isolated as solvates
containing two THF molecules. The latter reaction
produced a small amount of the sandwich complex
[C5Me4CH=CH2]2ZrCl2 (15) as an impurity, and the tarꢀ
get product was purified by recrystallization from THF.
Sandwich 15 was not isolated in the pure form. Comꢀ
plexes 13 and 14 do not form stable solvates with tetraꢀ
hydrothiophene (integrated intensity of its signals in
Quantumꢀchemical calculations of anions 1—3 and
analysis of regioselectivity of their reactions with electroꢀ
philic agents. Quantumꢀchemical calculations for the
–
ground state of the C5H4CH=CH2–, C5H4C(Me)=CH2
,
–
and C5(Me)4CH=CH2 anions were carried out by the
DFT method (RMPW1PW91)12 with the 6ꢀ311+G(d,p)
splitꢀvalence basis set with the inclusion of diffusion and
polarization functions using the GAUSSIAN 98W proꢀ
gram package.13 To decrease the calculation time, the
geometry of the anion was optimized in the conformation
with the maximum possible symmetry (Cs). The waveꢀ
functions for this conformation were tested for stability
and then used to determine the Bader charges14 by inteꢀ
grating over atomic basins with the use of the AIMPAC
program package.15* The results of calculations are given
in Table 1.
1
the H NMR spectra corresponds to the composition
Cp´ZrCl3•~0.6THT). Therefore, these complexes were
isolated as stable adducts containing two THF molecules.
These complexes are very sensitive to atmospheric oxyꢀ
gen. Even short exposure of solid compounds 13 and 14
to atmospheric oxygen leads (during dissolution under
high vacuum) to their irreversible polymerization. The
same process occurs during melting accompanied by the
loss of the solvation solvent. In this case, autocatalysis
Analysis of the results of calculations revealed the folꢀ
lowing facts. First, if only the electronic factors are conꢀ
* The AIMPAC program package can be downloaded free of
charge from Internet at http//www.chemistry.mcmaster.ca/
aimpac/download/aimpac.zip.

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Krut´ko et al.
Table 1. Total Bader atomic charges (q) and the sums of the squares of the HOMO orbital coefficients (wavefunctions
RMPW1PW91 6ꢀ311+G(d,p)) in the competitive positions of the ring in anions 1—3 (the atomic numbering is given in
Schemes 2 and 3)
Atom
–q/e
Sum of squares of HOMO
orbital coefficientsa
Estimated ratio of alkylation products
charge control
orbital controla
Anion 1
C(1)
0.0451
0.2283b
0.2413b
0.0362
0.1611
0.1863/0.1520
0.3603/0.3435c
0.3840/0.3035c
0.1239/0.0028
0.2356/0.1270
1.00 (6.7%)
5.06 (33.8%)
5.35 (35.7%)
—
1.00 (16.0%)/1.00 (16.4%)
1.93 (30.9%)/2.26 (37.1%)
2.06 (32.9%)/2.00 (32.8%)
—
C(2) + C(5)
C(3) + C(4)
C(6)
C(7)
3.57 (23.8%)
1.26 (20.2%)/0.84 (13.7%)
Anion 2
Anion 3
C(1)
0.0571
0.2301b
0.2426b
0.0062
0.1575
0.1577/0.1486
0.3597/0.3483c
0.3712/0.3066c
0.1246/0.0043
0.2443/0.1216
1.00 (8.3%)
4.03 (33.5%)
4.23 (35.2%)
—
1.00 (13.9%)/1.00 (16.1%)
2.28 (31.8%)/2.34 (37.6%)
2.35 (32.8%)/2.06 (33.1%)
—
C(2) + C(5)
C(3) + C(4)
C(6)
C(7)
2.76 (23.0%)
1.55 (21.6%)/0.82 (13.1%)
C(1)
0.0537
0.1161b
0.1352b
0.0455
0.1710
0.1515/0.1477
0.4088/0.3775c
0.4586/0.3695c
0.1069/0.0014
0.2315/0.1296
1.00 (11.3%)
2.16 (24.4%)
2.52 (28.4%)
—
1.00 (12.1%)/1.00 (14.4%)
2.70 (32.7%)/2.56 (36.9%)
3.03 (36.7%)/2.50 (36.1%)
—
C(2) + C(5)
C(3) + C(4)
C(6)
C(7)
3.18 (35.9%)
1.53 (18.5%)/0.88 (12.7%)
a
The coefficients at AOs of three (E < 0.1 eV)/two (E < 0.015 eV) HOMOs with similar energies were taken into
account.
b
The total charges were summed for pairs of the equivalent atoms (C(2), C(5) and C(3), C(4)).
The squares of the orbital coefficients at AOs were summed for pairs of the equivalent atoms (C(2), C(5) and
c
C(3), C(4)).
Scheme 7
THT is tetrahydrothiophene

Reactions of [C5R4C(R´)=CH2]– anions
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 2, February, 2005
395
Table 2. Selected bond lengths (d) and bond angles (ω) in comꢀ
plexes 13 and 14
C(8)
C(7)
C(2)
C(1)
Bond
d/Å
Angle
ω/deg
C(3)
C(6)
C(5)
Complex 13
C(9)
Zr—O(1)
Zr—O(2)
Zr—Cl(3)
Zr—Cl(1)
Zr—Cl(2)
2.322(3)
2.369(3)
2.441(2)
2.474(1)
2.495(2)
O(1)—Zr—O(2)
O(1)—Zr—Cl(3)
O(2)—Zr—Cl(3)
O(1)—Zr—Cl(1)
O(2)—Zr—Cl(1)
Cl(3)—Zr—Cl(1)
O(1)—Zr—Cl(2)
O(2)—Zr—Cl(2)
Cl(3)—Zr—Cl(2)
Cl(1)—Zr—Cl(2)
75.2(1)
155.69(9)
80.46(9)
82.58(9)
77.36(9)
92.19(6)
83.62(9)
76.84(9)
90.95(6)
153.10(5)
C(4)
O(1)
Cl(1)
C(10)
Zr
Cl(3)
C(12)
Cl(2)
O(2)
C(16)
Cpcent*—Zr 2.242
C(11)
C(6)—C(7) 1.372(8)
C(6)—C(8) 1.446(8)
C(1)—C(6) 1.464(7)
C(13)
C(15)
C(7)—C(6)—C(8) 121.4(6)
C(7)—C(6)—C(1) 120.4(6)
C(8)—C(6)—C(1) 118.1(6)
C(14)
Fig. 1. Molecular structure of complex 13.
Complex 14
2.3033(13)
2.4168(13)
2.4695(5)
2.4841(5)
2.4963(5)
Zr—O(1)
Zr—O(2)
Zr—Cl(2)
Zr—Cl(3)
Zr—Cl(1)
O(1)—Zr—O(2)
O(1)—Zr—Cl(2)
O(2)—Zr—Cl(2)
O(1)—Zr—Cl(3)
O(2)—Zr—Cl(3)
Cl(2)—Zr—Cl(3)
O(1)—Zr—Cl(1)
O(2)—Zr—Cl(1)
Cl(2)—Zr—Cl(1)
Cl(3)—Zr—Cl(1)
73.64(5)
153.18(4)
79.76(4)
86.60(4)
76.27(4)
90.422(18)
83.78(4)
77.71(3)
87.371(17)
153.864(17)
C(7)
C(10)
C(11)
C(4)
C(5)
C(9)
C(2)
C(6)
C(1)
C(3)
C(8)
Cpcent*—Zr 2.268
C(6)—C(7) 1.331(3)
Zr
Cl(1)
C(12)
Cl(2)
O(1)
C(13)
* Cpcent is the center of the cyclopentadienyl ring.
Cl(3)
C(15)
O(2)
C(16)
apparently occurs (complex acts simultaneously as the
catalyst and the substrate), because the metal center is a
strong Lewis acid.
C(14)
C(19)
C(18)
Crystal structures of complexes 13 and 14. Selected
bond lengths and bond angles in complexes 13 and 14 are
given in Table 2. In these complexes, the central Zr atom
(Figs 1 and 2) is in a pseudooctahedral environment (asꢀ
suming that the Cp ligand occupies one coordination site).
The Cp fragment and one THF molecule occupy the
apical positions, whereas three Cl atoms and the second
THF molecule lie in the equatorial plane.
This coordination polyhedron is most favorable for
monocyclopentadienyl derivatives of ZrIV.16—20 Excepꢀ
tions are compounds, in which steric hindrance caused by
the functionalized Cp ligand is too high to form such a
structure.21 Analysis of the structures retrieved from
the Cambridge Structural Database22 demonstrated
that the Zr—Cl distances in complexes 13 and 14
(2.441(2)—2.4963(5) Å) fall in a range typical of the terꢀ
minal ZrIV—Cl bonds in monocyclopentadienyl derivaꢀ
tives of zirconium (2.357—2.542 Å). On the whole, the
coordination environment of the Zr atom in compounds
13 and 14 is similar to that observed earlier in the related
complexes (CpR)ZrCl3•2THF (R = H, Me).23
C(17)
Fig. 2. Molecular structure of complex 14.
The cyclopentadienyl ligands in complexes 13 and 14
are planar within 0.011 Å. The atoms of the double bonds
conjugated with the Cp ligands lie virtually in the plane of
the cyclopentadienyl rings. The C(7)—C(6)—C(1)—C(5)
torsion angle is 8.7 and 21.7° in compounds 13 and 14,
respectively.
Experimental
All operations associated with the synthesis, reactions with
electrophilic agents, and preparation of samples for NMR specꢀ
troscopy were carried out in an inert atmosphere or in allꢀsealed
evacuated Schlenk type vessels. The solvents (including deuterꢀ
ated solvents), iodomethane, and chlorotrimethylsilane were

396
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 2, February, 2005
Krut´ko et al.
purified according to standard procedures.24 Commercial
Me3SnCl, Et2PCl, and ZrCl4 were used. Chlorodiethylphosphine
was additionally purified by vacuum distillation. Lithium
vinylcyclopentadienide (1),2,11 lithium isopropenylcyclopentaꢀ
dienide (2),11 and 2ꢀchloroꢀ1,3ꢀdioxaphospholane25 were synꢀ
thesized according to known procedures. The ZrCl4•2THT adꢀ
duct26,27 was prepared by the reaction of ZrCl4 with tetraꢀ
hydrothiophene (2.5 equiv.) in CH2Cl2.
The 1H, 13C, and 31P NMR spectra were recorded on a
Varian VXRꢀ400 spectrometer (400, 100, and 162 MHz, respecꢀ
tively) at 25 °C. For the 1H and 13C NMR spectra, the chemical
shifts of the signals of the corresponding deuterated solvents
(δ 5.32 and 53.8 for CD2Cl2, δ 1.73 and 25.3 for THFꢀd8, δ 7.15
and 128.0 for C6D6) were used as the internal standards.
The mass spectra were measured on KratosꢀMSꢀ890 and Varian
MAT CH7a Fa spectrometers. Elemental analysis was carried
out on an automated CarloꢀErba analyzer.
NOE effects for isomer 5c (%):
η
3(H(5)) = 0.9;
SiMe
η
a(H(5)) = 6.9; ηH(2)(SiMe3) = 5.0; ηH(5)(SiMe3) = 2.0.
H
13C—{1H} NMR, δ: –2.11 (SiMe3 (5a, 5b)); –0.78 (SiMe3 (5c));
20.87 (Me (5c)); 21.27 (br.s, Me (5a, 5b)); 43.97 (>CH2 (5c));
52.06 (br.s, >CH (5a, 5b)); 110.94 (br.s, =CH2 (5a, 5b)); 111.25
(s, =CH2 (5c)); 129.02 and 133.96 (both br, =CH (5a, 5b));
129.68, 142.48 (=CH (5c)); 139.11 (br, MeC= (5a, 5b)); 139.37
(MeC= (5c)); 146.0 (br, =C— (5a, 5b)); 147.11, 153.38
(=C— (5c)). MS (GC/MS, EI, 70 eV, 280 °C), m/z (Irel (%)):
178 [M]+ (6.1), 163 [M – Me]+ (3.4), 73 [Me3Si]+ (100).
1,2,3,4ꢀTetramethylꢀ6ꢀ(trimethylsilylmethyl)fulvene (6). The
starting reagents: salt 3 (1.28 g, 8.3 mmol) in THF (15 mL),
Me3SiCl (1.00 g, 9.2 mmol) in THF (10 mL). After high vacuum
distillation, an orange oily product was obtained in a yield of
1.51 g (83%). Found (%): C, 76.28; H, 11.04. C14H24Si. Calcuꢀ
1
lated (%): C, 76.28; H, 10.97. H NMR (C6D6), δ: –0.01 (s,
9 H, SiMe3); 1.81 (s, 6 H, CMe); 2.04 (s, 3 H, CMe); 2.10 (d,
3
Lithium tetramethylvinylcyclopentadienide (3) was prepared
according to a known procedure6 by deprotonation of
1,2,3,4,6ꢀpentamethylfulvene with lithium diispropylamide in
2 H, CH2, JH,H = 10.0 Hz); 2.23 (s, 3 H, CMe); 6.24 (t, 1 H,
=CH, 3JH,H = 10.0 Hz). 13C NMR, δ: –1.63 (q, SiMe3, 1JC,H
=
=
1
119 Hz); 9.91, 11.03, 11.41, and 14.39 (all q, CCH3, JC,H
1
THF. The yield was 86% (white crystalline powder). H NMR
125 Hz); 21.84 (t, CH2, 1JC,H = 123 Hz); 122.49, 124.98, 133.97,
139.01, and 144.73 (all s, =C); 130.07 (d, =CH, 1JC,H = 148 Hz).
MS (GC/MS, EI, 70 eV, 280 °C), m/z (Irel (%)): 220 [M]+
(7.9), 205 [M – Me]+ (1.1), 147 [M – Me3Si]+ (4.5), 146
[M – Me3SiH]+ (21.9), 131 [M – Me – Me3SiH]+ (16.0), 73
[Me3Si]+ (100).
(THFꢀd8), δ: 1.78 and 1.92 (both s, 6 H, Me); 4.27 (dd, 1 H, Hb,
2JH,H = 2.8 Hz, cisꢀ3JH,H = 11.6 Hz); 4.67 (dd, 1 H, Ha, 2JH,H
2.8 Hz, transꢀ3JH,H = 17.6 Hz); 6.56 (dd, 1 H, Hc, transꢀ3JH,H
=
=
17.6 Hz, cisꢀ3JH,H = 11.6 Hz). 13C NMR, δ: 10.66 and 11.99
1
1
(both q, Me, JC,H = 124 Hz); 99.80 (br.t, =CH2, JC,H
=
160 Hz); 109.02 and 110.07 (both s, C(2)—C(5)); 111.33
(Trimethylstannyl)isopropenylcyclopentadiene (7). The startꢀ
ing reagents: salt 2 (0.25 g, 2.23 mmol) in THF (5 mL), Me3SnCl
(0.53 g, 2.68 mmol) in THF (5 mL). After high vacuum distillaꢀ
tion, a yellow oily product was obtained in a yield of 0.42 g
(70%). Found (%): C, 49.01; H, 6.64. C11H18Sn. Calculated (%):
1
(s, C(1)); 134.12 (d, =CH, JC,H = 143 Hz). The 1H NMR
spectrum agrees well with the published data.6
Reactions of salts 1—3 with electrophilic agents (general proꢀ
cedure). A solution of the corresponding lithium salt in THF was
added with vigorous stirring to a solution of the electrophilic
reagent (10—20% excess) in THF at –20 °C. The reaction mixꢀ
ture was heated to ~20 °C and allowed to stand for ~12 h. Then
the solvent was removed in vacuo, hexane was added in an
amount corresponding to oneꢀhalf of the volume of the THF
distilled, the inorganic salt was separated by filtration, and the
residue was concentrated. The product was isolated by high
vacuum distillation (molecular distillation; the residual pressure
of noncondensable gases <4•10–3 Torr) unless otherwise indiꢀ
cated.
1
C, 49.12; H, 6.75. H NMR (C6D6), δ: –0.06 (s, 9 H, SnMe3,
2JH,Sn = 53.7 Hz); 1.99 (m, 3 H, Me); 4.87 (m, 1 H, =CHH);
5.13 (m, 1 H, =CHH); 5.85 and 5.93 (both t, 2 H each,
3+4
H(2)—H(5),
J
= 3.6 Hz). 13C—{1H} NMR, δ: –8.73
H,H
(SnMe3, 1JC,Sn = 341 Hz); 21.47 (Me); 102.34, 114.04 (CH(2),
CH(5)); 109.28 (=CH2); 139.29, 144.76 (C(1), =CMe).
MS (GC/MS, EI, 70 eV, 280 °C), m/z (Irel (%)): 270 [M]+
(11.2), 255 [M – Me]+ (5.7), 225 [M – 3 Me]+ (18.7), 165
[Me3Sn]+ (100), 105 [M – Me3Sn]+ (15.1), 79 [M – Me –
Me3SnH]+ (26.5).
(Trimethylsilyl)vinylcyclopentadiene (4) (mixture of isomers).
The starting reagents: salt 1 (2.28 g, 23.2 mmol) in THF (10 mL),
Me3SiCl (2.77 g, 25.5 mmol) in THF (10 mL). After high vacuum
distillation, a yellow oily product was obtained in a yield of
Reaction of salt 3 with chlorotrimethylstannane (mixture of
isomers 8a and 8b). The starting reagents: salt 3 (0.34 g,
2.21 mmol) in THF (10 mL), Me3SnCl (0.48 g, 2.41 mmol) in
5 mL THF. After high vacuum distillation, an orange oily mixꢀ
ture of products was obtained in a yield of 0.59 g (86%).
Found (%): C, 54.37; H, 7.89. C14H24Sn. Calculated (%):
C, 54.06; H, 7.78. MS (GC/MS, EI, 70 eV, 280 °C),
m/z (Irel (%)): 312 [M]+ (74.8), 297 [M – Me]+ (19.8),
267 [M – 3 Me]+ (38.1), 165 [Me3Sn]+ (100), 147 [M – Me3Sn]+
(29.4), 146 [M – Me3SnH]+ (12.3), 131 [M – Me –
Me3SnH]+ (13.6).
1
2.48 g (65%). H NMR (C6D6), δ: –0.12 and –0.08 (both br,
SiMe3 (4a, 4b)); 0.11 (s, SiMe3 (4c)); 3.04 (t, >CH2 (4c), 4JH,H
=
1.2 Hz); 3.19 and 3.38 (both br, >CH (4a, 4b)); 4.95—5.53
(=CH2); 6.20—6.90 (=CH).
(Trimethylsilyl)isopropenylcyclopentadiene (5) (mixture of
isomers). The starting reagents: salt 2 (2.70 g, 24.1 mmol) in
THF (10 mL), Me3SiCl (3.01 g, 27.7 mmol) in THF (10 mL).
After high vacuum distillation, a yellow oily product was obꢀ
tained in a yield of 3.14 g (73%), b.p. 92—93 °C (7 Torr).
Found (%): C, 74.03; H, 10.07. C11H18Si. Calculated (%):
C, 74.08; H, 10.17. 1H NMR (C6D6), δ: –0.11 (br.s, SiMe3
(5a, 5b)); 0.13 (s, SiMe3 (5c)); 1.91 (m, Me (5c)); 1.98 (br, Me
Isomer 8a (90%). 1H NMR (C6D6), δ: 0.05 (s, 9 H, SnMe3,
2JH,Sn = 53.2 Hz); 1.84 (s, 6 H, CMe); 1.97 and 2.15 (both s,
3
2
3 H each, CMe); 2.26 (d, 2 H, CH2, JH,H = 10.4 Hz, JH,Sn
=
74.7 Hz); 6.30 (t, 1 H, =CH, 3JH,H = 10.4 Hz, 3JH,Sn = 11.7 Hz).
13C NMR, δ: –9.52 (q, SnMe3, 1JC,H = 128 Hz, 1JC,Sn = 323 Hz);
4
1
(5a, 5b)); 3.13 (t, >CH2 (5c), JH,H = 1.3 Hz); 3.23 and 3.53
9.95, 11.04, 11.46, and 14.59 (all q, CCH3, JC,H = 124 Hz);
(both br, >CH (5a, 5b)); 4.85 (m, Hb (5c)); 4.97 and 5.36
(both br, =CH2 (5a, 5b)); 5.14 (m, Ha (5c)); 6.33, 6.40, and 6.91
(all br, =CH (5a, 5b)); 6.37 (m, H(3) (5c)); 6.70 (m, H(2) (5c)).
17.26 (t, CH2, 1JC,H = 132 Hz, 1JC,Sn = 252 Hz); 122.14, 124.55,
133.27, 137.92, and 141.98 (all s, =C); 133.13 (d, =CH, 1JC,H
147 Hz, 2JC,Sn = 56 Hz).
=

Reactions of [C5R4C(R´)=CH2]– anions
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 2, February, 2005
397
Isomer 8b (10%). 1H NMR (C6D6), δ: –0.05 (s, 9 H, SnMe3,
2JH,Sn = 50.8 Hz); 1.79 and 1.83 (both s, 6 H, CMe); 5.07 (dd,
1JC,P = 16.8 Hz); 23.57 (d, >CCH3, 2JC,P = 22.2 Hz); 45.91 (d,
>CMe, 1JC,P = 22.9 Hz); 97.59 (=CH2); 114.05 (d, =CH(Me),
2
1 H, Hb, JH,H = 2.0 Hz, cisꢀ3JH,H = 11.6 Hz); 5.25 (dd, 1 H,
3JC,P = 5.7 Hz); 137.10, 140.62 (=CMe); 151.37 (d, >C=, 2JC,P
=
2
2
Ha, JH,H = 2.0 Hz, transꢀ3JH,H = 18.0 Hz); 6.67 (dd, 1 H, Hc,
7.2 Hz); 158.36 (d, >C=, JC,P = 5.6 Hz). 31P—{1H} NMR,
cisꢀ3JH,H = 11.6 Hz, transꢀ3JH,H = 18.0 Hz).
δ: 2.6 (s).
(1,3ꢀDioxaphospholanꢀ2ꢀyl)tetramethylvinylcyclopentadiene
(9). The starting reagents: salt 3 (1.42 g, 9.21 mmol) in THF
(20 mL), 2ꢀchloroꢀ1,3ꢀdioxaphospholane (1.40 g, 11.05 mmol)
in THF (10 mL). After high vacuum distillation, a yellowꢀorange
Reaction of salt 2 with iodomethane (mixture of isomers 11).
The starting reagents: salt 2 (0.139 g, 1.24 mmol) in THF (5 mL),
iodomethane (0.20 g, 1.41 mmol) in THF (5 mL). After high
vacuum distillation, a yellow oily product was obtained in a
yield of 0.106 g (72%). 1H NMR (C6D6), δ: 1.11 and 1.12 (both d,
1
oily product was obtained in a yield of 1.49 g (68%). H NMR
3
(C6D6), δ: 1.67 (br.s, 6 H, Me); 1.83 (s, 6 H, Me); 3.36 and 3.69
CHCH3, JH,H = 7.0 Hz); 1.66—2.10 (=CMe); 2.58—2.98
(>CH, >CH2); 4.70—5.24 (=CH2); 5.44—6.48 (=CH).
2
(both m, 2 H, CH2O); 5.24 (dd, 1 H, Hb, JH,H = 2.0 Hz,
2
cisꢀ3JH,H = 11.6 Hz); 5.47 (dd, 1 H, Ha, JH,H = 2.0 Hz,
Reaction of salt 3 with iodomethane (mixture of isomers
12a—c). The starting reagents: salt 3 (0.091 g, 0.59 mmol) in
THF (5 mL), iodomethane (0.10 g, 0.71 mmol) in THF (5 mL).
After high vacuum distillation, a yellow oily product was obꢀ
transꢀ3JH,H = 18.0 Hz); 6.78 (dd, 1 H, Hc, cisꢀ3JH,H = 11.6 Hz,
transꢀ3JH,H = 18.0 Hz). 13C NMR, δ: 11.40 and 12.25 (both q,
1
1
Me, JC,H = 127 Hz); 65.44 (td, CH2O, JC,H = 150 Hz,
2JC,P = 8.9 Hz); 113.71 (t, =CH2, JC,H = 157 Hz); 131.01 (d,
=CH, JC,H = 151 Hz); 134.1 (v.br, =C); 136.6 (br, =C).
tained in a yield of 0.081 g (84%). H NMR (C6D6), δ: 0.85
1
1
1
(s, 5ꢀMe (12c)); 1.01 (s, 5ꢀMe (12a)); 1.09 (s, 5ꢀMe (12b)); 1.64
(s, =CMe); 1.65 and 1.79 (both s, 1ꢀMe, 4ꢀMe (12c)); 1.67
(s, 4ꢀMe (12b)); 1.68 (s, 1ꢀMe, 4ꢀMe (12a)); 1.69, 1.76, and
1.86 (all s, =CMe); 5.00—5.20 (m, Hb (12a—c)); 5.06 (dd,
31P—{1H} NMR, δ: 164.3 (s). MS (GC/MS, EI, 70 eV, 280 °C),
m/z (Irel (%)): 238 [M]+ (15.7), 223 [M – Me]+ (17.8), 147
[M – (OCH2CH2O)P]+ (19.1), 146 [M – (OCH2CH2O)PH]+
(21.6), 131 [M – Me – (OCH2CH2O)PH]+ (18.7), 91
[(OCH2CH2O)P]+ (100).
2
Ha (12a), JH,H = 1.6 Hz, transꢀ3JH,H = 17.6 Hz); 5.18 (dd,
2
Ha (12b), JH,H = 1.2 Hz, transꢀ3JH,H = 18.0 Hz); 5.21 (dd,
Reaction of salt 3 with chlorodiethylphosphine (mixture of
isomers 10a—d). The starting reagents: salt 3 (2.25 g, 14.6 mmol)
in THF (20 mL), chlorodiethylphosphine (2.22 g, 17.8 mmol) in
THF (10 mL). After high vacuum distillation, an orange oily
mixture of products was obtained in a yield of 2.41 g (70%).
Hc (12a), cisꢀ3JH,H = 10.0 Hz, transꢀ3JH,H = 17.6 Hz); 5.41 (dd,
2
Ha (12c), JH,H = 2.0 Hz, transꢀ3JH,H = 18.0 Hz); 6.54 (dd,
Hc (12c), cisꢀ3JH,H = 11.6 Hz, transꢀ3JH,H = 18.0 Hz); 6.66 (dd,
Hc (12b), cisꢀ3JH,H = 11.6 Hz, transꢀ3JH,H = 18.0 Hz).
NOE effects (%): η1ꢀMe,4ꢀMe(5ꢀMe) = 4.3 (per Me group);
1
Isomer 10a. H NMR (C6D6), δ: 0.90—1.35 (P(CH2Me)2);
η
η
c(5ꢀMe)
=
4.0;
η
a(5ꢀMe)
=
6.5 (isomer 12a);
H
H
3
1.31 (d, >CMe, JH,P = 13.2 Hz); 1.69 and 1.85 (both br.s,
4ꢀMe(5ꢀMe) = 6.6; η (5ꢀMe) = 4.7; η (5ꢀMe) = 16.3 (isoꢀ
H H
a
=CMe); 1.77 (br.s, 4ꢀMe); 5.21 (dd, Hb, JH,H = 1.8 Hz,
mer 12b); η4ꢀMe(5ꢀMe)c= 3.7; η1ꢀMe(5ꢀMe) = 3.7 (isomer 12c).
13C—{1H} NMR, δ: 9.45, 9.52, 10.00, 10.56, 10.92, 11.27, 11.46,
12.59 (=CCH3); 15.95, 21.67, 23.08 (>CCH3); 52.06, 52.79,
60.01 (>CMe); 109.81, 112.69, 115.15 (=CH2); 129.28, 131.59,
142.35 (=CH); 131.02, 132.82, 134.75, 135.50, 139.53, 140.49,
143.28, 144.63, 147.57, 148.38 (=C).
2
cisꢀ3JH,H = 11.6 Hz); 5.52 (dd, Ha, 2JH,H = 1.8 Hz, transꢀ3JH,H
18.0 Hz); 6.59 (dd, Hc, transꢀ3JH,H = 18.0 Hz, cisꢀ3JH,H
=
=
11.6 Hz). NOE effects (%): η4ꢀMe(5ꢀMe) = 0.7; η (5ꢀMe) = 1.5;
H
c
η
(5ꢀMe) = 1.5. 13C—{1H} NMR, δ: 10.88—12.88 (=CCH3,
H
a
P(CH2CH3)2); 16.91 (d, P(CH2Me), 1JC,P = 20.1 Hz); 16.94 (d,
1
2
5
P(CH2Me), JC,P = 19.7 Hz); 18.82 (d, >CCH3, JC,P
=
Trichloro(η ꢀisopropenylcyclopentadienyl)zirconium (13).
1
17.9 Hz); 56.30 (d, >CMe, JC,P = 25.1 Hz); 113.28 (d, =CH2,
4JC,P = 8.8 Hz); 130.30 (=CH); 135.18, 139.25, 142.12, 144.06
(=C). 31P—{1H} NMR, δ: 15.3 (s).
A solution of silane 5 (1.22 g, 6.84 mmol) in CH2Cl2 (10 mL)
was added with stirring and cooling to 0 °C to a solution of
ZrCl4•2THT (2.14 g, 5.23 mmol) in CH2Cl2 (30 mL). The
reaction mixture was heated to ~20 °C and stirred for one day.
The solvent was distilled off until precipitation started and then
the solution was cooled to 0 °C. A finely crystalline product was
separated by filtration, washed with hexane (3×20 mL), and
dried under high vacuum. The intermediate product correspondꢀ
ing to the Cp´ZrCl3•~0.6THT formula (1H NMR spectroscopic
data) was recrystallized from THF (10 mL), twice washed with
cold THF, and dried under high vacuum. The yield of comꢀ
plex 13 (as an adduct with two THF molecules) was 1.14 g
(49%) (white crystalline powder). Found (%): C, 42.91; H, 5.60.
1
Isomer 10b. In the H NMR spectrum, only signals of the
vinyl group are given. 1H NMR (C6D6), δ: 5.20 (dd, Hb, 2JH,H
=
2.0 Hz, cisꢀ3JH,H = 11.6 Hz); 5.40 (dd, Ha, JH,H = 2.0 Hz,
transꢀ3JH,H = 18.0 Hz); 6.54 (dd, Hc, transꢀ3JH,H = 18.0 Hz,
cisꢀ3JH,H = 11.6 Hz). 31P—{1H} NMR, δ: 14.6 (s).
2
1
Isomer 10c. H NMR (C6D6), δ: 0.90—1.35 (P(CH2Me)2);
1.75 (2 Me); 1.90 and 2.16 (both br.s, =CMe); 2.63 (d,
3
3
CH2P(CH2Me)2, JH,H = 9.2 Hz); 6.13 (dt, =CH, JH,H
=
9.2 Hz, JH,P = 5.6 Hz). 13C—{1H} NMR, δ: 9.80—11.40
4
(=CCH3, P(CH2CH3)2); 14.40 (=CCH3); 19.40 (d,
1
1
P(CH2Me)2, JC,P = 14.8 Hz); 27.69 (d, CH2P(CH2Me)2,
C16H25Cl3O2Zr. Calculated (%): C, 43.00; H, 5.64. H NMR
1JC,P = 17.8 Hz); 122.98, 125.21, 135.24, 140.08 (=CMe); 147.17
(d, C=CH, 3JC,P = 6.4 Hz) (signal of =CH is overlapped with a
triplet of C6D6). 31P—{1H} NMR, δ: –14.1 (s).
(CD2Cl2), δ: 1.92 (br.m, 8 H, CH2CH2O in THF); 2.12 (s, 3 H,
Me); 4.11 (br.m, 8 H, CH2O in THF); 5.14 and 5.41 (both m,
3+4
1 H, =CH2); 6.52 and 6.60 (both t, 2 H, C5H4,
J
=
H,H
1
Isomer 10d. H NMR (C6D6), δ: 0.90—1.35 (P(CH2Me)2);
5.6 Hz). 13C—{1H} NMR, δ: 21.52 (Me); 25.62 (CH2CH2O
in THF); 73.37 (CH2O in THF); 114.32 (=CH2); 116.29, 118.97
(CH in C5H4); 134.47, 137.39 (C in C5H4, =CMe). MS (EI,
70 eV), m/z (Irel (%)): 265 [M – 2 THF – Cl]+ (0.3), 251
[C7H7ZrCl2]+ (1.8), 249 [M – 2 THF – HCl – Me]+ (1.2), 230
[M – 2 THF – 2 Cl]+ (0.7), 105 [C7H6(Me)]+ (4.5), 91 [C7H7]+
(7.8), 71 [C3H7CO]+ (100).
3
1.59 and 1.65 (both br.s, =CMe); 1.61 (d, >CMe, JH,P
=
3
12.3 Hz); 2.13 (d, =C(H)CH3, JH,H = 7.6 Hz); 4.45 (s, Ha);
4.82 (s, Hb); 5.30 (qd, Hc, JH,H = 7.6 Hz, JH,P = 2.8 Hz).
3
4
NOE effects (%):
η c(5ꢀMe) = 2.7; η a(5ꢀMe) = 1.2.
H H
13C—{1H} NMR, δ: 10.37—15.31 (=CCH3, P(CH2CH3)2); 16.07
1
(d, P(CH2Me), JC,P = 21.4 Hz); 17.60 (d, P(CH2Me),

398
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 2, February, 2005
Krut´ko et al.
5
[η ꢀTetramethyl(vinyl)cyclopentadienyl]trichlorozirconium
[M – 2 THF – Cl]+ (5.6), 292 [M – 2 THF – Cl – Me]+ (12.0),
147 [C7H3(Me)4]+ (52.4), 133 [C7H4(Me)3]+ (52.7), 119
[C7H5(Me)2]+ (44.1), 105 [C7H6(Me)]+ (44.9), 91 [C7H7]+
(56.2), 36 [HCl]+ (100).
(14). Salt 3 (1.14 g, 7.38 mmol) was added to a suspension of
ZrCl4•2THT (3.02 g, 7.38 mmol) in toluene (50 mL). The reacꢀ
tion mixture was stirred at 100 °C for 2 days. The precipitate was
filtered off and the mother liquor was concentrated. The crystalꢀ
line precipitate was washed with diethyl ether (3×20 mL) and
dried in vacuo. The intermediate corresponds to the formula
[C5Me4CH=CH2]ZrCl3•~0.6THT (1H NMR spectroscopic
data) and contains impurities of zirconocene dichloride 15. The
product was recrystallized from THF (2×10 mL), washed with
diethyl ether (3×15 mL), and dried under high vacuum. The
yield of complex 14 (as an adduct with two THF molecules) was
1.19 g (33%) (white crystalline powder). Found (%): C, 46.59;
H, 6.35. C19H31Cl3O2Zr. Calculated (%): C, 46.67; H, 6.39.
1H NMR (THFꢀd8), δ: 1.72 (m, 8 H, CH2CH2O in THF); 2.02
and 2.13 (both s, 6 H, Me); 3.59 (m, 8 H, CH2O in THF); 5.17
(dd, 1 H, Hb, JH,H = 2.0 Hz, cisꢀ3JH,H = 11.6 Hz); 5.22 (dd,
1 H, Ha, JH,H = 2.0 Hz, transꢀ3JH,H = 18.0 Hz); 6.59 (dd,
1 H, Hc, transꢀ3JH,H = 18.0 Hz, cisꢀ3JH,H = 11.6 Hz).
13C—{1H} NMR, δ: 13.56, 14.49 (Me); 26.36 (CH2CH2O
in THF); 68.59 (CH2O in THF); 116.32 (=CH2); 126.19
(CCH=CH2); 126.98, 128.99 (CMe); 132.26 (=CH).
MS (EI, 70 eV), m/z (Irel (%)): 342 [M – 2 THF]+ (0.6), 307
Xꢀray diffraction study of complexes 13 and 14. Xꢀray difꢀ
fraction data sets were collected on EnrafꢀNonius CAD4 (comꢀ
plex 13) and Bruker SMART (complex 14) diffractometers
(MoꢀKα radiation, λ = 0.71073 Å, graphite monochromator).
Crystallographic data, details of Xꢀray diffraction study, and
characteristics of structure refinement for complexes 13 and 14
are given in Table 3. The absorption corrections were applied
based on the measured intensities of equivalent reflections. The
structures were solved by direct methods (SHELXSꢀ86).28 All
nonhydrogen atoms were refined by the fullꢀmatrix leastꢀsquares
method with anisotropic displacement parameters against F 2
(SHELXLꢀ97).29 The H atoms in the structure of 14 were reꢀ
vealed from a difference electron density series and refined
isotropically. The hydrogen atoms in the structure of 13 were
placed in calculated positions and refined using a riding model.
2
2
This study was financially supported by the Foundaꢀ
tion of the President of the Russian Federation (Program
for Support of Young Doctors, Grant MKꢀ3697.2004.3).
Table 3. Crystallographic data, details of Xꢀray diffraction study,
and characteristics of structure refinement for complexes 13
and 14
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Parameter
13
14
Molecular formula
Molecular weight
T/K
C16H25Cl3O2Zr C19H31Cl3O2Zr
446.93
293
489.01
105(2)
Crystal system
Space group
a/Å
b/Å
c/Å
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Pbca
14.371(8)
15.482(5)
17.003(7)
—
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P21/c
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28.1232(7)
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1.569
Z
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0.905
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1824
1008
θ Scan range/deg
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–2 < h < 17,
–2 < k < 18,
–2 < l < 20
5161
1.45—27.00
–10 < h < 9,
–35 < k < 35,
–11 < l < 11
14919
Number of measured
reflections
Number of independent
3321
(0.0430)
201
4639
(0.0250)
342
reflections (Rint
)
Number of parameters
in refinement
R1 (I > 2σ(I ))
0.0349
0.1000
0.977
0.0260
0.0573
1.118
wR2 (all reflections)
Goodnessꢀofꢀfit on F 2
Residual electron
density
0.453/–0.355
0.572/–0.442
(max/min)/e Å–3

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