New bridging tridentate bis-cyclopentadienyl ligands [C5Me 4(CH2)n]2PPh (n = 1, 2) for organometallic synthesis

Article abstract of DOI:10.1007/s11172-007-0285-8

Preparative procedures were developed for the synthesis of new transmethylated bis-cyclopentadienyl ligands with phosphine-containing bridging fragments. These ligands were isolated as the dilithium salts Li ₂[(C₅Me₄CH₂)₂PPh] (1) and Li₂[(C₅Me₄CH₂CH₂) ₂PPh] (3). Phosphorus-substituted 3-ansa-zirconocene dichloride [(C₅Me₄CH₂)₂PPh]ZrCl₂ was synthesized starting from 1. The NMR spectroscopic data provide evidence for the absence of the Zr←P coordination interaction in solution. A straightforward approach to 5-ansa-zirconocene dichloride [(C₅Me ₄CH₂CH₂)₂PPh]ZrCl₂ starting from lithium salt 3 and ZrCl₄ was shown to be impossible.

Full text of DOI:10.1007/s11172-007-0285-8

Russian Chemical Bulletin, International Edition, Vol. 56, No. 9, pp. 1838—1842, September, 2007
1838
New bridging tridentate bisꢀcyclopentadienyl ligands
[C5Me4(CH2)n]2PPh (n = 1, 2) for organometallic synthesis
D. P. Krut´ko,ꢀ R. S. Kirsanov, and M. V. Borzov
Department of Chemistry, M. V. Lomonosov Moscow State University,
1 Leninskie Gory, 119992 Moscow, Russian Federation.
Fax: +7 (495) 932 8846. Eꢀmail: kdp@org.chem.msu.ru
Preparative procedures were developed for the synthesis of new transmethylated bisꢀ
cyclopentadienyl ligands with phosphineꢀcontaining bridging fragments. These ligands were
isolated as the dilithium salts Li2[(C5Me4CH2)2PPh] (1) and Li2[(C5Me4CH2CH2)2PPh] (3).
Phosphorusꢀsubstituted 3ꢀansaꢀzirconocene dichloride [(C5Me4CH2)2PPh]ZrCl2 was syntheꢀ
sized starting from 1. The NMR spectroscopic data provide evidence for the absence of the
Zr←P coordination interaction in solution. A straightforward approach to 5ꢀansaꢀzirconocene
dichloride [(C5Me4CH2CH2)2PPh]ZrCl2 starting from lithium salt 3 and ZrCl4 was shown to
be impossible.
Key words: phosphanediylꢀcontaining bisꢀcyclopentadienyl ligands, zirconium, NMR specꢀ
troscopy.
Among a vast number of heteroatomꢀfunctionalized
ligand were prepared. Three examples of this type of phosꢀ
phine ligands were reported: [PhP(CH2CH2C5H5)2]
(Zr14,15 and Fe16 complexes were synthesized),
[MeP(CH2CH2C5H5)2] (Y and Lu complexes were synꢀ
thesized),17 and [RP(CMe2C5H5)2] (R = Ph or Cy;
the corresponding ferrocenophanes were prepared).18
To complete the picture, let us mention the
[PhP(C13H8)2]MCl2 compounds (M = Zr or Hf; C13H8 is
fluorenyl);19 however, the phosphorus atom in these comꢀ
pounds in no case can be coordinated to the metal atom.
In the present study, we developed preparative
procedures for the synthesis of new tridentate
dicyclopentadienyl ligands, which were isolated as
the dilithium salts Li2[(C5Me4CH2)2PPh] and
Li2[(C5Me4CH2CH2)2PPh], and ansaꢀzirconocene diꢀ
chloride [(C5Me4CH2)2PPh]ZrCl2.
cyclopentadienyl ligands widely used in organometallic
chemistry, bisꢀcyclopentadienyl ligands containing a
heteroatom in the bridging fragment have received little
attention. However, their coordination ability toward tranꢀ
sition metal atoms can radically differ from that of conꢀ
ventional bidentate chelating monocyclopentadienyls.
This is associated with the possibility of the forced coordiꢀ
nation at the rear of the heteroatomic functional group of
the bridge to the metal atom in complexes with a particuꢀ
lar geometry.
Oxygenꢀ, nitrogenꢀ, arsenicꢀ, and phosphorusꢀconꢀ
taining derivatives are among the known tridentate bisꢀ
cyclopentadienyl ligands and metal complexes
with these ligands. The lanthanide complexes
[O(CH2CH2C5H4)2]LnCl (Ln = Y, Nd, Gd, Ho, Er, Yb,
or Lu) were prepared.1 The complexes of Ti,2 Zr,3—5
Cr,6 U,7 and lanthanides (Y, Pr, Nd, Sm, Dy, Er, Yb,
and Lu)8 with 2,6ꢀpyridineꢀcontaining dicyclopentadiene
[2,6ꢀC5H3N(CH2C5H5)2] were synthesized. The folꢀ
lowing derivatives of Group IV metals based on
dicyclopentadienes with aliphatic amino groups
were documented: [H3CN(CH2CH2C5H4)2]ZrCl2,3
[BunN(SiMe2C5H4)2]MCl2 (M = Ti, Zr, or Hf), and
[BunN(SiMe2C9H6)2]ZrCl2 (C9H6 is 2ꢀindenyl).9 The arꢀ
senicꢀcontaining complexes [PhAs(CH2CH2C5H4)2]ꢀ
TiCl2 (see Ref. 10) and [PhAs(CH2CH2C5H4)2]Fe
Results and Discussion
Synthesis of dilithium salts of ligands
The
synthesis
of
the
dilithium
salt
Li2[(C5Me4CH2)2PPh] (1) was based on the nucleophilic
addition of phosphides at position 6 of the fulvene molꢀ
ecule. Salt 1 was prepared by the successive addition
of 1,2,3,4ꢀtetramethylfulvene (2) (1 equiv.), BunLi
(1 equiv.), and 2 (1 equiv.) to a solution of PhPHLi in
THF (Scheme 1). The target compound was isolated in
(see
Ref.
11)
were
prepared.
The
only
dicyclopentadiene transalkylated at both rings,
[2,6ꢀC5H3N(CH2CH2C5Me4H)2], has been synthesized
rather long ago;12,13 however, no complexes with this
1
good yield and characterized by H, 13C, and 31P NMR
spectroscopy.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1775—1779, September, 2007.
1066ꢀ5285/07/5609ꢀ1838 © 2007 Springer Science+Business Media, Inc.

Bridging tridentate ligands
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 9, September, 2007
1839
Scheme 1
because of very low solubility of dilithium salt 5. The
reaction requires drastic conditions (heating at 100 °C
for 18 h), and the target compound is contaminated with
cleavage products of the THF molecule. To exclude the
cleavage of THF as the side reaction and provide milder
reaction conditions, we performed the last reaction step
in pyridine, in which salt 5 is much more readily soluble.
Preliminary experiments showed that pyridine is resistant
against PhPHLi (and, consequently, against 5) at room
temperature for 7 days. As a result, dilithium salt 3 was
isolated in satisfactory yield and was characterized by 1H,
13C, and 31P NMR spectroscopy. It should be noted that 3
has very poor solubility in THF, which is insufficient even
1
for the measurement of the H NMR spectrum, but has
very good solubility in pyridine.
In the synthesis of the zirconium complexes, we used,
along with lithium salt 3, the potassium derivative
K2[(C5Me4CH2CH2)2PPh] (6). The latter was prepared
in good yield (79%) by the exchange reaction of salt 3
with ButOK.
The development of a preparative procedure for the
synthesis of the dilithium salt Li2[(C5Me4CH2CH2)2PPh]
(3) with the aim of adapting the known oneꢀpot synthesis
of nonmethylated analog of 3, Li2[(C5H4CH2CH2)2PPh],
was a more complex problem (Scheme 2). In the present
study, the synthesis was performed in three successive
steps: (1) cyclopropane ring opening in 4,5,6,7ꢀtetraꢀ
methylspiro[2.4]heptaꢀ4,6ꢀdiene (4) with lithium phenylꢀ
phosphide, (2) treatment of the resulting monolithium
derivative with nꢀbutyllithium in the cold, and (3) reacꢀ
tion of the dilithium salt Li2[C5Me4CH2CH2PPh] (5) with
another equivalent of spirane 4. The last step involving
the opening of the second cyclopropane ring caused most
problems. In this case, THF was of little use as the solvent
Synthesis of zirconium ansaꢀcomplexes
The synthesis of ZrIV ansaꢀcomplexes starting from
dilithium salts 1 and 3 appeared to be a very laborious
problem. Prolonged heating of lithium salt 1 with zircoꢀ
nium tetrachloride in toluene allowed us to prepare the
sandwich complex [(C5Me4CH2)2PPh]ZrCl2 (7) in low
yield (Scheme 3). The target compound was isolated in
the pure form and was characterized by mass spectroꢀ
metry, 1H, 13C, and 31P NMR spectroscopy, and elemenꢀ
tal analysis.
Scheme 2
Scheme 3
Reaction conditions: i. 25 °C, 72 h.
Reaction conditions: toluene.

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Russ.Chem.Bull., Int.Ed., Vol. 56, No. 9, September, 2007
Krut´ko et al.
Scheme 4
M = Li (3), K (6)
Reaction conditions: THF, DME, or toluene.
Due to the fact that the inversion of the pyramid at the
phosphorus atom is hindered, molecule 7 has the symꢀ
metry group Cs (rather than C2v), which is manifested in
the nonequivalence of all Me groups in the rings as well as
of the hydrogen atoms of the methylene bridge (AB spin
ing on the nature of the substituent in the bridge.24 At
the same time, the δ(31P) signal in the spectrum of the
ansaꢀcomplex [(C5H4CH2CH2)2PPh]ZrCl2, for which the
coordination of the phosphine group to the Zr atom was
established, is shifted downfield with respect to that of the
free ligand by 39.9 ppm.15
1
system in the H NMR spectrum). An interesting feature
of the 13C NMR spectrum is that the signal of one of four
Me groups is split on the 31P nucleus with JC,P = 15.1 Hz.
This large fourꢀbond spinꢀspin coupling constant is not
typical of organophosphorus compounds. Apparently, the
throughꢀspace interaction between the 31P nucleus and
the nearest Me group makes the main contribution to the
spinꢀspin coupling constant.
Noteworthy is high sensitivity of 7 to oxygen, which is
characteristic of phosphine derivatives. This is manifested
in the mass spectrum of this compound. Thus, upon the
exposure of a solution of complex 7 to air, the most inꢀ
tense peak corresponds to the [M – Cl + 16]+ ion belongꢀ
ing to the phosphine oxide complex.
We failed to synthesize the complex with the second
bisꢀcyclopentadienyl ligand in spite of numerous attempts.
Prolonged heating of the lithium (3) or potassium (6) salt
with zirconium tetrachloride in nonsolvating (toluene) or
solvating (THF or dimethoxyethane) solvents afforded
a mixture of unidentified products, apparently, with a
polymeric structure (Scheme 4) instead of the target
ansaꢀcomplex.
In our opinion, this is associated with the difficulties
of the ansaꢀring closure in the intermediate halfꢀsandꢀ
wich complex due to the strong coordination of the phosꢀ
phine substituent to the Zr atom. This is evidenced by the
fact that the yield of even the nontransmethylated comꢀ
plex [(C5H4CH2CH2)2PPh]ZrCl2 is only 22%.15 Apparꢀ
ently, a substantial increase in steric crowding of the
cyclopentadienyl rings leads to a decrease in this rather
low yield virtually to zero.
In solution, the coordination of the phosphine subꢀ
stituent to the Zr atom in complex 7 should be, apparꢀ
ently, excluded. In three known examples of halfꢀsandꢀ
wich zirconium complexes with C5R4CR1R2P(R3)2ꢀ type
ligands, this coordination is absent,20 which is, apparꢀ
ently, associated with the insufficient length of the bridgꢀ
ing fragment. The coordination of the phosphine group
was observed only in the cationic sandwich complexes
{[C5R4CR1R2P(R3)2]2ZrX}+.21—23 The downfield shift
(by ~14.5 ppm) of δ(31P) in complex 7 (δ –20.1) comꢀ
pared to salt 1 (δ –34.5), which generally serves as a
criterion of the coordination of the phosphine substituent
to the metal atom, is accounted for by other factors. Most
likely, this shift is associated with substantial changes in
the nature of the substituent in the β position with respect
to the phosphorus atom upon the coordination of the
cyclopentadienyl ring to the Zr atom. For example,
the change in δ(31P) in the sandwich complexes
[C5H4CR1R2PPh2]2ZrCl2 (R1, R2 = Me; R1 = H,
R2 = Me, R2 = But; R2 = Ph, R2 = pꢀTol) compared
to the starting lithium salts varies from +12 ppm
(R1, R2 = Me) to –15 ppm (R1 = H, R2 = pꢀTol) dependꢀ
Experimental
All reactions and the preparation of samples for NMR specꢀ
troscopic studies were carried out in allꢀsealed evacuated
Schlenkꢀtype vessels. The solvents were purified according to

Bridging tridentate ligands
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 9, September, 2007
1841
1
known procedures,25 degassed in vacuo (residual pressure of
noncondensable gases was 10–3 Torr), and introduced into reacꢀ
tion vessels by vacuum recondensation. Commercially availꢀ
able (Aldrich) phenylphosphine was dried over calcium
hydride; ZrCl4 was purified by sublimation in a dry hydrogen
stream. 1,2,3,4ꢀTetramethylfulvene26 and 4,5,6,7ꢀtetramethylꢀ
spiro[2,4]heptaꢀ4,6ꢀdiene27 were synthesized according to known
procedures.
The 1H, 13C, and 31P NMR spectra were recorded on Varian
VXRꢀ400 and Bruker Avanceꢀ400 spectrometers operating at
400, 100, and 162 MHz, respectively. For the 1H and 13C NMR
spectra, the chemical shifts of the deuterated solvents were used
as the internal standard (7.19 and 123.5 ppm for C5D5N;
1.73 and 25.3 ppm for THFꢀd8, respectively). For the 31P NMR
spectra, 85% H3PO4 was used as the external standard. The
mass spectra were obtained on a Bruker Autoflex II instrument
(MALDI, N2 laser, 337 nm). The elemental analysis was carried
out on an automated Carlo—Erba analyzer.
Lithium phenylphosphide. A solution of BunLi in hexane
(2.45 mol L–1, 12.6 mL) was added to a solution of phenylꢀ
phosphine (3.38 g, 30.7 mmol) in hexane (50 mL) at 0 °C, after
which a yellow precipitate rapidly formed. The reaction mixture
was stirred for 30 min and kept for 12 h. The precipitate was
separated by decantation, washed with hexane, and dried in
high vacuum. Lithium phenylphosphide was obtained as a yelꢀ
low powder in a yield of 3.12 g (26.9 mmol, 88%). 1H NMR
(THFꢀd8, 25 °C), δ: 2.09 (d, 1 H, PH, 1JH,P = 162 Hz); 6.23 (t,
29.06 (d, CH2P, JCP = 19.0 Hz); 105.6 (br, CCH2P); 106.66,
3
107.51 (CCH3); 127.29 (pꢀCH); 128.33 (d, mꢀCH, JC,P
=
4.8 Hz); 132.16 (d, oꢀCH, 2JC,P = 16.5 Hz); 146.4 (br.d, ipsoꢀC,
1JC,P = 24 Hz). 31P—{1H} NMR (C5D5N), δ: –34.5.
Dilithium
1,1´ꢀ[2,2´ꢀphenylphosphanediylbis(ethyl)]ꢀ
b i s ( 2 , 3 , 4 , 5 ꢀ t e t r a m e t h y l c y c l o p e n t a ꢀ 2 , 4 ꢀ d i e n i d e ) ,
{[C5(CH3)4CH2CH2]2PPh}Li2 (3). A solution of PhPHLi
(0.485 g, 4.18 mmol) and spiroheptadiene 4 (0.65 g, 4.38 mmol)
in THF (70 mL) was kept at 25 °C for 1 day and then heated at
50 °C for 4 h. The resulting orange solution was cooled to –20 °C,
and then a 2.45 M solution of BunLi in hexane (1.75 mL,
4.29 mmol) was added. The reaction mixture rapidly turned red.
A yellow precipitate of 5 was formed within a few minutes. The
precipitate was filtered off, washed with THF, dried, and treated
with a solution of spirane 4 (0.52 g, 3.51 mmol) in pyridine
(40 mL). The resulting blackꢀred mixture was kept at 25 °C for
three days and then heated at 60—70 °C for 3 h. The solvent was
removed, and the oily residue was dissolved in THF. The preꢀ
cipitate that formed within a few minutes was separated from
the intensely colored solution by decantation and washed with
the solvent in the cold. Salt 3 was obtained as a greenish powder
in a yield of 470 mg. An additional amount of the product
(275 mg) was isolated from the mother liquor in THF remained
after the isolation of 5. The total yield was 745 mg (1.78 mmol,
43%). 1H NMR (C5D5N, 25 °C), δ: 2.22 and 2.25 (both br,
28 H (a total), CCH3, CH2P); 2.98 (br, 4 H, CH2CH2P);
7.27 (br.t, 1 H, pꢀCH); 7.39 (br, 2 H, mꢀCH); 7.78 (br, 2 H,
oꢀCH). 13C—{1H} NMR (C5D5N), δ: 11.54 (CCH3); 23.4 (br,
CH2CH2P); 31.5 (br, CH2P); 105.87, 106.53 (CCH3); 113.07
3
3
1 H, pꢀCH, JH,H = 6.7 Hz); 6.52 (t, 2 H, mꢀCH, JH,H
=
6.9 Hz); 7.05 (dd, 2 H, oꢀCH, 3JH,H = 6.9 Hz, JH,P = 5.1 Hz).
13C—{1H} NMR (THFꢀd8), δ: 116.44 (s, pꢀCH); 126.75 (d,
3
3
(d, CCH2CH2P, JC,P = 12.0 Hz); 127.77 (pꢀCH); 128.40 (d,
3
2
3
2
mꢀCH, JC,P = 4.7 Hz); 129.82 (d, oꢀCH, JC,P = 15.5 Hz);
161.69 (d, ipsoꢀC, 1JC,P = 44.0 Hz). 31P—{1H} NMR (THFꢀd8),
δ: –111.2. 1H NMR (C5D5N, 25 °C), δ: 3.28 (d, 1 H, PH,
mꢀCH, JC,P = 5.6 Hz); 132.61 (d, oꢀCH, JC,P = 15.8 Hz);
142.4 (br, ipsoꢀC). 31P—{1H} NMR (C5D5N), δ: –23.0.
Dipotassium 1,1´ꢀ[2,2´ꢀphenylphosphanediylbis(ethyl)]ꢀ
b i s ( 2 , 3 , 4 , 5 ꢀ t e t r a m e t h y l c y c l o p e n t a ꢀ 2 , 4 ꢀ d i e n i d e ) ,
{[C5(CH3)4CH2CH2]2PPh}K2 (6). Salt 3 (0.74 mg, 1.77 mmol)
was added with stirring to a solution of ButOK (0.6 g, 5.35 mmol)
in THF (40 mL). The lithium salt was completely dissolved, and
a yellow substance precipitated from the solution within a few
minutes. The precipitate was successively washed with THF and
diethyl ether and then dried under high vacuum. Target comꢀ
pound 6 was obtained in a yield of 670 mg (1.39 mmol, 79%).
1JH,P = 160 Hz); 6.60 (t, 1 H, pꢀCH, JH,H = 7.1 Hz); 6.90 (t,
3
3
3
2 H, mꢀCH, JH,H = 7.5 Hz); 7.70 (dd, 2 H, oꢀCH, JH,H
=
6.9 Hz, JH,P = 5.2 Hz). 13C—{1H} NMR (C5D5N), δ: 116.17
3
3
(s, pꢀCH); 127.24 (d, mꢀCH, JC,P = 4.4 Hz); 129.64 (d,
oꢀCH, JC,P = 15.3 Hz); 162.67 (d, ipsoꢀC, JC,P = 45.6 Hz).
31P—{1H} NMR (C5D5N), δ: –99.0.
2
1
5
Dilithium 1,1´ꢀ[phenylphosphanediylbis(methyl)]bis(η ꢀ
2 , 3 , 4 , 5 ꢀ t e t r a m e t h y l c y c l o p e n t a ꢀ 2 , 4 ꢀ d i e n i n d e ) ,
{[C5(CH3)4CH2]2PPh}Li2 (1). A 0.66 M solution of 1,2,3,4ꢀtetraꢀ
methylfulvene (4.55 mmol) in toluene (6.9 mL) was added to a
solution of PhPHLi (0.523 g, 4.51 mmol) in THF (50 mL)
at 25 °C. The resulting yellow solution was stirred at 25 °C
for 1 h. Then the solution was cooled to –20 °C, and a 2.45 M
solution of BunLi (4.53 mmol) in hexane (1.85 mL) was added.
The solution rapidly turned orange, and a small amount of an
orange precipitate was obtained. A 0.66 M solution of fulvene 2
(4.55 mmol) in toluene (6.9 mL) was added to the reaction
mixture, and the mixture was stirred at 25 °C for 2 h. The
solvents were removed, and the precipitate was washed with a
1 : 2 THF/Et2O mixture and dried under high vacuum. Salt 1
was obtained as a white powdered substance in a yield of 1.40 g
5
{1,1´ꢀ[Phenylphosphanediylbis(methyl)]bis(η ꢀ2,3,4,5ꢀ
tetramethylcyclopentaꢀ2,4ꢀdienyl)}dichlorozirconium,
{η ꢀ[C5(CH3)4CH2]2PPh}ZrCl2 (7). A suspension of lithium salt
5
1 (0.86 g, 2.20 mmol) and zirconium tetrachloride (0.53 g,
2.27 mmol) in toluene (60 mL) was stirred with heating on a
boiling water bath for 20 h. The yellow solution was separated
from the precipitate. The precipitate was extracted three times
with toluene, the mother liquor and the extracts were combined,
and the solvent was distilled off. The product was extracted
three times from the oily residue with diethyl ether. The ethereal
solution was concentrated. The precipitate that formed was sepaꢀ
rated from the solution by decantation and washed with cold
diethyl ether. Complex 7 was obtained as a yellow powder in a
yield of 119 mg (0.22 mmol, 10%). Found (%): C, 57.47; H, 6.08.
C26H33Cl2PZr. Calculated (%): C, 57.98; H, 6.18. 1H NMR
(THFꢀd8, 27 °C), δ: 1.87, 1.95, 2.02, and 2.14 (all s, 6 H,
CCH3); 2.78 (A part of an ABX system, 2 H, CHHP, JH,H
14.0 Hz, JH,P = 7.2 Hz); 2.94 (B part of an ABX system, 2 H,
CHHP, JH,H = 14.0 Hz, JH,P = 5.7 Hz); 7.41 (m, 3 H,
mꢀ, pꢀCH); 7.72 (m, 2 H, oꢀCH). 13C—{1H} NMR (THFꢀd8), δ:
1
(3.58 mmol, 79%). H NMR (C5D5N, 25 °C), δ: 2.19 and 2.47
(both s, 12 H, CCH3); 3.38 (A part of an ABX system, 2 H,
2
2
CHHP, JH,H = 13.6 Hz, JH,P = 8.6 Hz); 3.64 (B part of an
2
2
2
ABX system, CHHP, 2 H, JH,H = 13.6 Hz, JH,P = 6.4 Hz);
=
3
2
7.26 (t, 1 H, pꢀCH, JH,H = 7.4 Hz); 7.38 (t, 2 H, mꢀCH,
3JH,H = 7.4 Hz); 7.90 (dd, 2 H, oꢀCH, JH,H = 7.4 Hz, JH,P
=
3
3
2
2
5.6 Hz). 13C—{1H} NMR (C5D5N), δ: 11.19, 12.87 (CCH3);

1842
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 9, September, 2007
Krut´ko et al.
12.04, 12.08, and 13.66 (all s, CCH3); 14.43 (d, CCH3, JC,P
=
8. G. Paolucci, R. D`Ippolito, C. Ye, C. Qian, J. Graper, and
D. R. Fischer, J. Organomet. Chem., 1994, 471, 97.
9. H. G. Alt, K. Föttinger, and W. Milius, J. Organomet. Chem.,
1998, 564, 109.
10. T. Kauffmann, J. Ennen, and K. Berghus, Tetrahedron Lett.,
1984, 25, 1971.
11. T. Kauffmann, K. Berghus, and J. Ennen, Chem. Ber., 1985,
118, 3724.
12. U. Siemeling, U. Vorfeld, B. Neumann, and H.ꢀG.
Stammler, Chem. Ber., 1995, 128, 481.
1
15.1 Hz); 26.02 (d, CH2P, JC,P = 13.9 Hz); 117.86 (d, CCH2
2
3
or CCH32, JC,P or JC,P = 3.8 Hz); 118.42 (d, CCH3 or CCH2,
3JC,P or JC,P = 5.0 Hz); 127.12 and 127.19 (both s, CCH3);
129.43 (d, mꢀCH, 3JC,P = 6.2 Hz); 129.92 (s, pꢀCH); 132.29 (d,
2
3
oꢀCH, JC,P = 18.5 Hz); 132.56 (d, CCH3, JC,P = 1.5 Hz);
139.97 (d, ipsoꢀC, 1JC,P = 18.3 Hz). 31P—{1H} NMR (THFꢀd8),
δ: –20.1. 1H NMR (C5D5N, 27 °C), δ: 1.82, 2.02, 2.15, and 2.26
(all s, 6 H, CCH3); 2.87 (A part of an ABX system, 2 H, CHHP,
2JH,H = 14.0 Hz, 2JH,P = 7.2 Hz); 3.01 (B part of an ABX system,
2
2
2 H, CHHP, JH,H = 14.0 Hz, JH,P = 6.0 Hz); 7.49 (m, 3 H,
mꢀ, pꢀCH); 7.83 (m, 2 H, oꢀCH). 13C—{1H} NMR (C5D5N), δ:
13. P. Jutzi and U. Siemeling, J. Organomet. Chem., 1995,
500, 175.
11.92, 12.13, and 13.68 (all s, CCH3); 14.48 (d, CCH3, JC,P
=
14. O. J. Curnow, G. Huttner, S. J. Smail, and M. M. Turnbull,
J. Organomet. Chem., 1996, 524, 267.
15. J. R. Butchard, O. J. Curnow, and S. J. Smail, J. Organomet.
Chem., 1997, 541, 407.
16. J. J. Adams, O. J. Curnow, G. Huttner, S. J. Smail, and
M. M. Turnbull, J. Organomet. Chem., 1999, 577, 44.
17. H. H. Karsch, V. W. Graf, and W. Scherer, J. Organomet.
Chem., 2000, 604, 72.
18. T. Höcher, A. Cinquantini, P. Zanello, and E. HeyꢀHawkins,
Polyhedron, 2005, 24, 1340.
1
14.9 Hz); 25.45 (d, CH2P, JC,P = 13.9 Hz); 117.84 (d, CCH2
2
3
or CCH32, JC,P or JC,P = 3.9 Hz); 118.12 (d, CCH3 or CCH2,
3JC,P or JC,P = 5.0 Hz); 126.75 and 127.12 (both s, CCH3);
129.25 (d, mꢀCH, 3JC,P = 6.1 Hz); 129.62 (s, pꢀCH); 131.89 (d,
2
3
oꢀCH, JC,P = 17.8 Hz); 132.27 (d, CCH3, JC,P = 1.5 Hz);
139.35 (d, ipsoꢀC, 1JC,P = 18.0 Hz). 31P—{1H} NMR (C5D5N),
δ: –18.9. MS, m/z (Irel (%)): 501 (5.2) [M – Cl]+, 516 (100)
[M + O – Cl]+.
This study was financially supported by the Russian
Foundation for Basic Research (Project No. 04ꢀ03ꢀ
32288a).
19. H. G. Alt and M. Jung, J. Organomet. Chem., 1998, 568, 127.
20. T. Koch, E. HeyꢀHawkins, M. GalanꢀFereres, and M. S.
Eisen, Polyhedron, 2002, 21, 2445.
21. B. E. Bosch, G. Erker, R. Fröhlich, and O. Meyer, Organoꢀ
metallics, 1997, 16, 5449.
22. R. M. Bellabarba, G. P. Clancy, P. T. Gomes, A. M. Martins,
L. H. Rees, and M. L. H. Green, J. Organomet. Chem., 2001,
640, 93.
23. S. Döhring, V. V. Kotov, G. Erker, G. Kehr, K. Bergander,
O. Kataeva, and R. Fröhlich, Europ. J. Inorg. Chem.,
2003, 1599.
24. B. Bosch, G. Erker, and R. Fröhlich, Inorg. Chim. Acta,
1998, 270, 446.
25. W. L. F. Armarego, Purification of Laboratory Chemicals,
Pergamon Press, 4 ed., Oxford, 1996, 529.
26. S. Döhring and G. Erker, Synthesis, 2001, 43.
27. D. P. Krut´ko, M. V. Borzov, E. N. Veksler, R. S. Kirsanov,
and A. V. Churakov, Europ. J. Inorg. Chem., 1999, 1973.
References
1. C. Qian, Z. Xie, and Y. Huang, J. Organomet. Chem., 1987,
323, 285.
2. Y. Qian, J. Guo, J. Huang, and Q. Yang, Polyhedron, 1997,
16, 195.
3. C. Qian, J. Guo, C. Ye, J. Sun, and P. Zeng, J. Chem. Soc.,
Dalton Trans., 1993, 3441.
4. K.ꢀH. Thiele, C. Schließburg, and B. Neümueller, Z. anorg.
allg. Chem., 1995, 621, 1106.
5. G. Paolucci, G. Pojana, J. Zanon, V. Lucchini, and
E. Avtomonov, Organometallics, 1997, 16, 5312.
6. G. Paolucci, F. Ossola, M. Bettinelli, R. Sessoli,
F. Benetollo, and G. Bombieri, Organometallics, 1994,
13, 1746.
7.G. Paolucci, R. D. Fischer, F. Benetollo, R. Seraglia, and
G. Bombieri, J. Organometal. Chem., 1991, 412, 327.
Received January 31, 2007