Synthesis and transformations of metallacycles 29. Direct alumination of olefins, conjugated dienes, and acetylenes with alkylhaloalanes catalyzed by Zr and Ti complexes

Article abstract of DOI:10.1023/A:1025697110484

Catalytic methods were developed for the synthesis of acyclic 1,2- and 1,4-dialuminum compounds by the reactions of olefins, dienes, or acetylenes with R₂AlCl (R = Et, Et₂N, (cyclo-C₆H ₁₁)₂N, Buⁿ

Full text of DOI:10.1023/A:1025697110484

Russian Chemical Bulletin, International Edition, Vol. 52, No. 7, pp. 1573—1583, July, 2003
1573
Synthesis and transformations of metallacycles
29.* Direct alumination of olefins,
conjugated dienes, and acetylenes with alkylhaloalanes
catalyzed by Zr and Ti complexes
U. M. Dzhemilev, A. G. Ibragimov, L. G. Yakovleva, L. O. Khafizova,ꢀ A. L. Borisova, and L. R. Yakupova
Institute of Petrochemistry and Catalysis,
Bashkortostan Republic Academy of Sciences and Ufa Research Center of the Russian Academy of Sciences,
141 prosp. Oktyabrya, 450075 Ufa, Russian Federation.
Fax: +7 (347 2) 31 2750. Eꢀmail: ink@anrb.ru
Catalytic methods were developed for the synthesis of acyclic 1,2ꢀ and 1,4ꢀdialuminum
compounds by the reactions of olefins, dienes, or acetylenes with R2AlCl (R = Et, Et2N,
(cycloꢀC6H11)2N, BunO, or nꢀC6H13O) in the presence of Tiꢀ or Zrꢀcontaining complex
catalysts and magnesium metal as an acceptor of chloride ions.
Key words: organoaluminum compounds, titaniumꢀ and zirconiumꢀcontaining catalysts,
metallacycles, olefins, dienes, acetylenes, [60]fullerene, alumination.
Cyclic organoaluminum compounds (OAC) containꢀ
ing simultaneously two Al atoms at positions 1,1, 1,4, or
1,5 of the carbon chain are generally prepared2,3 by therꢀ
mal hydroalumination of acetylenes and 1,3ꢀ or 1,4ꢀdienes
with diisobutylaluminum hydride (DIBAH).
[Ti], respectively) as catalysts, which are most active in
cycloalumination of olefins and acetylenes with alkyl deꢀ
rivatives of Mg and Al giving rise to the corresponding
threeꢀ and fiveꢀmembered metallacycles of mainꢀgroup
metals.4,5
These reactions are characterized by rather low selecꢀ
tivity and are very sensitive to the structure of the starting
acetylene or diene as well as to the nature of the funcꢀ
tional groups involved in the starting unsaturated comꢀ
pound. As a consequence, this method shows little promꢀ
ise from the preparative standpoint.
With the aim of developing an efficient procedure for
the synthesis of difficultly accessible 1,2ꢀ or 1,4ꢀdialuꢀ
minum compounds, we studied the reactions of αꢀolefins,
acetylenes, 1,3ꢀdienes, and [60]fullerene with R2AlCl in
the presence of catalysts based on Ti or Zr salts and comꢀ
plexes.
We succeeded in performing the reactions shown in
Scheme 1 under catalytic conditions starting from αꢀoleꢀ
fins, 1,3ꢀdienes, or acetylenes and Et2AlCl under the conꢀ
ditions developed earlier4,5 for the synthesis of aluminaꢀ
cyclopropanes and aluminacyclopentanes. These reactions
require the use of an acceptor of chloride ions, viz., magꢀ
nesium metal, which simultaneously reduces Ti and Zr
complexes.
We studied the reactions of styrene and its derivatives,
1,2ꢀ and 1,3ꢀdienes, [60]fullerene, and monoꢀ and disubꢀ
stituted acetylenes.
When choosing the procedure for the synthesis of
1,2ꢀ and 1,4ꢀdialuminum compounds, we started from
the assumption that cycloalumination of olefins and acetyꢀ
lenes4,5 with alkylhaloalanes in the presence of Ti or Zr
complexes proceeds through the intermediate formation
of titaniumꢀ or zirconiumꢀcontaining threeꢀ and fiveꢀ
membered metallacycles, which can be transmetallated
under the reaction conditions with the starting alkylꢀ
haloalanes to give the corresponding 1,2ꢀdialuminioꢀ
ethanes, 1,2ꢀdialuminioethenes, 1,4ꢀdialuminiobutanes,
and 1,4ꢀdialuminiobutaꢀ1,3ꢀdienes (Scheme 1).
Results and Discussion
The reaction of styrene with Et2AlCl in the presence of
Mg and Cp2TiCl2 (the molar ratio styrene : Al : Mg : Ti =
10 : 22 : 12 : 0.5) in THF (∼20 °C, 8 h) afforded a mixture
of OAC 5—7 in ∼85% yield. These compounds were idenꢀ
tified based on the results of analysis of deuterolysis prodꢀ
ucts 8, 9, and 10 obtained in a ratio of ∼6 : 1 : 3 (Scheme 2).
In the reactions in benzene or toluene, the yields of
OAC 5—7 decreased to 5—8%. The reactions did not
proceed in aliphatic solvents (hexane, cyclohexane) virꢀ
tually at all. In the reactions with the use of Ti(OPri)4,
Ti(OBun)4, or TiCl4 as the catalyst, the total yield of OAC
5—7 decreased to 50, 45, or 25%, respectively, the ratio
In the aboveꢀmentioned reactions, we used the
Cp2ZrCl2 and Cp2TiCl2 complexes (hereinafter, [Zr] and
* For Part 28, see Ref. 1.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1490—1499, July, 2003.
1066ꢀ5285/03/5207ꢀ1573 $25.00 © 2003 Plenum Publishing Corporation

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Dzhemilev et al.
Scheme 1
Scheme 2
8 : 9 : 10 being ∼5 : 2 : 4. In the presence of the catalyst
Cp2ZrCl2 or ZrCl4, the yield of OAC 6 increased to
35—40% with a simultaneous decrease in the yield of
1,2ꢀbis(diethylaluminio)ꢀ1ꢀphenylethane (5) to 20—25%.
Based on our earlier results4—6 and the data published
in the literature,7,8 the most probable scheme can be proꢀ
posed for the formation of 1,2ꢀ and 1,4ꢀdialuminum comꢀ
pounds 5 and 6 from styrene in the presence of Cp2TiCl2.
In this process, powdered magnesium (activated with
the starting Et2AlCl) reduces Cp2TiCl2 to "Cp2Ti."
Titanacene, which is generated in situ, coordinates a styꢀ
rene molecule to form titanacyclopropane intermediꢀ
ate 11, whose transmetallation with Et2AlCl affords comꢀ
pound 5. Under the reaction conditions, the second styꢀ
rene molecule adds at the Ti—C bond complex 11, which
facilitates the formation of 1,1ꢀdicyclopentadienylꢀ2,5ꢀ
diphenyltitanacyclopentane (12). Transmetallation of the
latter with the starting Et2AlCl gives rise to minor prodꢀ
uct 6 (Scheme 3).
Hydroalumination product 7 is formed by hydroꢀ
metallation of a styrene molecule with Ti hydride comꢀ
plexes, which are generated9 upon dehydrogenation of
THF molecules with lowꢀvalence titanium complexes acꢀ
cording to the scheme reported earlier.10
Alumination of substituted styrenes (αꢀphenylstyrene
and oꢀ, pꢀ, and αꢀmethylstyrenes) with Et2AlCl in the

Alumination of olefins, dienes, and acetylenes
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 7, July, 2003
1575
Scheme 3
presence of Cp2TiCl2 and an activated magnesium powder
under the chosen optimum conditions gave rise to 1ꢀarylꢀ
substituted 1,2ꢀdialuminioethanes 13—16 (55—60%) and
hydroalumination byꢀproducts (25—30%) (Scheme 4).
Deuterolysis of OAC 13—16 afforded 1,2ꢀdideuterioꢀ
ethanes 17—20, respectively. In these experiments, 1,4ꢀdiꢀ
aluminioꢀ1,4ꢀdiarylbutanes were generated virtually not
all. Conceivably, in the step of formation of the titanaꢀ
cyclopropane intermediates of type 11, the bulky aryl subꢀ
stituents hinder the addition of a new arylethylene molꢀ
Scheme 4

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Dzhemilev et al.
ecule at the Ti—C bond to form 2,5ꢀdiaryltitanacycloꢀ
pentanes, which are precursors of 1,4ꢀdialuminioꢀ1,4ꢀ
diarylbutanes.
We failed to carry out Cp2TiCl2ꢀcatalyzed alumination
of disubstituted olefins, for example, of cyclohexene,
cyclooctene, or 2ꢀoctene. Apparently, the aboveꢀmenꢀ
tioned olefins form unstable titanacyclopropane intermeꢀ
diates, which cannot be transmetallated with the starting
Et2AlCl.
Of the 1,3ꢀdienes under study, viz., 1,4ꢀdiphenylbutaꢀ
1,3ꢀdiene (DPB) butadiene, isoprene, piperylene, and,
2,3ꢀdimethylbutaꢀ1,3ꢀdiene, we succeeded in performing
dialumination only of DPB.
Apparently, the fact that DPB molecule contains the
phenyl substituents, which are capable of coordinating to
the central atom of the catalyst, facilitates stabilization
of titanacyclopropane intermediates, which react with
Et2AlCl to give the corresponding dialuminum comꢀ
pounds 24 (∼60%) (Scheme 7).
To elucidate the possibility of the use of monoꢀ
haloalanes other than Et2AlCl, bis(dialkylamino)ꢀ and
dialkoxychloroalanes were subjected to Cp2TiCl2ꢀcataꢀ
lyzed alumination. The reactions were carried out in the
presence of 5 mol.% of Cp2TiCl2 in THF at 20—21 °C for
8 h to prepare Nꢀ and Oꢀcontaining 1,2ꢀdialuminioꢀ1ꢀ
phenylethanes 21a—d in 50—60% yields and hydroꢀ
alumination products in 30—35% yields (Scheme 5).
Scheme 5
Scheme 7
21: R = BunO (a), nꢀC6H13O (b), Et2N (c), (cycloꢀC6H11)2N (d)
Alumination of styrene with the use of halogenꢀconꢀ
taining amides and aluminum alkoxides produced virꢀ
tually no regioisomeric 1,4ꢀdialuminioꢀ1,4ꢀdiphenylꢀ
butanes. Apparently, the starting aluminum amides and
alkoxides containing the N and O heteroatoms with the
lone electron pair form complexes with titanacycloꢀ
propane intermediate 11 thus hindering the incorporation
of a new styrene molecule at the Ti—C bond and the
formation of 1,4ꢀdialuminum compounds.
Hydrocarbons with cumulated double bonds (for exꢀ
ample, allenes) react with Et2AlCl in THF in the presꢀ
ence of 5 mol.% of Cp2TiCl2 as the catalyst and Mg to
produce unsaturated 1,2ꢀ and 1,4ꢀdialuminum comꢀ
pounds 26 and 27 in a ratio of ∼5 : 4 in a total yield of
75—80% 12 (Scheme 8).
Unlike arylolefins, aliphatic αꢀolefins were subjected
to hydroalumination with Et2AlCl in the presence of the
[Cp2TiCl2 + Mg] catalyst to give diethylalkylalanes 22.10
In the presence of the Cp2ZrCl2 catalyst, these reactions
11
afforded 2,3ꢀdialkylꢀ1,4ꢀdialuminiobutanes 23
with
high selectivity (Scheme 6).
Scheme 8
Scheme 6
R = Alk, Ph
In deuterolysis products of the reaction mixture, we
found 1,2ꢀ and 1,4ꢀdideuterated as well as monodeuteꢀ
rated olefins (10—15%), which indicates that under the
R = Alk

Alumination of olefins, dienes, and acetylenes
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 7, July, 2003
1577
Scheme 9
m = 60—120, n = 1—6
reaction conditions used the process was accompanied by
the side hydroalumination reaction.10
The formation of compounds 32b,c and 33b,c can be
accounted for by the most probable scheme involving the
generation of "Cp2Ti" from Cp2TiCl2 under the reacꢀ
tion conditions in the presence of activated magnesium
(Scheme 11). The "Cp2Ti" compound is coordinatively
unsaturated, which facilitates the incorporation of a molꢀ
ecule of dialkylꢀsubstituted acetylene into the coordinaꢀ
tion sphere of the titanium atom to give the titanacycloꢀ
propene intermediate.14—17 Transmetallation of the latter
with the starting Et2AlCl affords the target product 31.
Unlike the bulky phenyl substituent, the alkyl substituꢀ
ents (Prn, Bun) do not hinder the addition of a new molꢀ
ecule of dialkylꢀsubstituted acetylene at the Ti—C bond
to form titanacyclopentadiene 36. The latter is transꢀ
metallated with the starting Et2AlCl to give 1,4ꢀdialuꢀ
miniobutaꢀ1,3ꢀdiene 32. Under the reaction conditions,
titanacyclopentadiene 36 can involve one more molecule
of dialkylꢀsubstituted acetylene to yield hexasubstituted
benzene 33 with elimination of reactive "Cp2Ti."
With the aim of searching for the starting OAC, which
are less pyrophoric than Et2AlCl, to perform alumination
of disubstituted acetylenes as well as for the purpose of
synthesizing new types of Nꢀ and Oꢀcontaining 1,2ꢀdiꢀ
aluminioethenes, we studied the reactions of diphenylꢀ
acetylene with bis(diethylamino)aluminum chloride and
di(nꢀbutoxy)aluminum chloride18,19 in the presence of
Cp2TiCl2 and magnesium metal (THF as the solvent, 8 h,
∼20 °C, the molar ratio R2AlCl : PhC≡CPh : Cp2TiCl2 =
25 : 10 : 0.5). Alumination of diphenylacetylene with the
aboveꢀmentioned aluminum compounds afforded Nꢀ and
The electron density distribution in the [60]fullerene
molecule imparts properties13 typical of olefins. This gave
promise that C60 could be successfully subjected to
Cp2TiCl2ꢀcatalyzed dialumination with Et2AlCl. Actuꢀ
ally, the reaction of [60]fullerene with an excess of Et2AlCl
(the molar ratio C60 : Al = 1 : (60—120), 5 mol.% of
Cp2TiCl2, a toluene—THF mixture as the solvent) in the
presence of Mg as the acceptor of chloride ions afforded a
mixture of bis(diethylaluminio)fullerenes (28) in 70—85%
yields. Hydrolysis and deuterolysis of the reaction mixꢀ
ture revealed polyhydrofullerenes C60H2n (29) and C60D2n
(30) (n = 1—6) (Scheme 9).
To examine the possibility of alumination of acetyꢀ
lenic hydrocarbons and to prepare previously unknown
unsaturated 1,2ꢀdialuminum compounds, we carried out
the Cp2TiCl2ꢀcatalyzed reactions of Et2AlCl with acetyꢀ
lenes. Using the reaction of diphenylacetylene with
Et2AlCl as an example, it was shown that the reaction in
the presence of activated Mg and Cp2TiCl2 (the molar
ratio PhC≡CPh : Al : Mg : Ti = 10 : 20 : 12 : 0.5) in THF
(8 h, ∼20 °C) produced 1,2ꢀbis(diethylaluminio)ꢀ1,2ꢀdiꢀ
phenylethene (31a) in ∼70% yield. Alumination involving
dialkylꢀsubstituted acetylenes (octꢀ4ꢀyne, decꢀ5ꢀyne) proꢀ
ceeded less selectively to give 1,2ꢀdialkylꢀ1,2ꢀbis(diethylꢀ
aluminio)ethenes 31b,c, 1,2,3,4ꢀtetraalkylꢀ1,4ꢀbis(diꢀ
ethylaluminio)butaꢀ1,3ꢀdienes 32b,c, and hexasubstituted
benzenes 33b,c in a ratio of ∼6 : 1 : 3 in a total yield of
70—85% (Scheme 10).

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Dzhemilev et al.
Scheme 10
R = Ph (a), Prn (b), Bun (c)
Scheme 11
R = Prn, Bun
Oꢀcontaining dialuminioethenes 37 and 38 in 65—70%
yields (Scheme 12).
The results of our study demonstrated that 1,2ꢀdiꢀ
aluminioethenes are formed by transmetallation of titanaꢀ
cyclopropene intermediates, which are generated in situ,
with R2AlCl.14—17 We attempted to add an ethylene molꢀ
ecule at the active Ti—C bond of titanacyclopropenes
with the aim of expanding the threeꢀmembered metallaꢀ
cycle and preparing in situ titanacyclopentene intermediꢀ
ates 39 under the reaction conditions. Transmetallation

Alumination of olefins, dienes, and acetylenes
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 7, July, 2003
1579
Scheme 12
of the latter with R2AlCl could afford previously unknown
substituted 1,4ꢀdialuminiobutꢀ1ꢀenes 40 (Scheme 13). We
chose ethylene because of its high coordinating ability
and the fact that it can be easily generated20 from 1,2ꢀdiꢀ
chloroethane and dosed in an equimolar amount with
respect to the starting acetylene.
We studied the reaction of Et2AlCl with PhC≡CPh in
the presence of an excess of Mg and catalytic amounts
(5 mol.%) of Cp2TiCl2 as the model process. 1,2ꢀDichloꢀ
roethane was supplied to the reaction zone in THF in a
mixture with an equimolar amount of acetylene during 6 h.
Activated magnesium served as the acceptor of chloride
ions thus facilitating the transformation of dichloroethane
into ethylene. Under these conditions, 1,4ꢀbis(diethylꢀ
aluminio)ꢀ1,2ꢀdiphenylbutꢀ1ꢀene (41) and 1,2ꢀbis(diꢀ
ethylaluminio)ꢀ1,2ꢀdiphenylethylene (31a) were prepared
in ∼60 and ∼10% yields, respectively (Scheme 14).
These results demonstrated that the controlled incorꢀ
poration of ethylene at the Ti—C bond in the step of
formation of titanacyclopropene intermediates provides a
simple route for the synthesis of a new class of unsaturꢀ
ated aliphatic OAC, viz., 1,2ꢀdialkyl(phenyl)ꢀ1,4ꢀdiꢀ
aluminiobutꢀ1ꢀenes, from disubstituted acetylenes and
dialkylhaloalanes.
Scheme 13

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Russ.Chem.Bull., Int.Ed., Vol. 52, No. 7, July, 2003
Dzhemilev et al.
Scheme 14
Mg (powder) (12 mmol), and THF (10 mL). The reaction soluꢀ
tion was warmed to 21—22 °C and stirred for 8 h. Then the
reaction mixture was treated with a 10% DCl solution in D2O.
The products were extracted with Et2O or hexane and isolated
by distillation.
Reaction of [60]fullerene with Et2AlCl—Mg—[Ti, Zr] (genꢀ
eral procedure). A solution of fullerene (0.025 mmol) in toluene
(30 mL) was placed in a glass reactor under dry argon and the
reaction mixture was stirred until C60 was completely dissolved.
Then Cp2TiCl2 (0.0025 mmol) and Et2AlCl (0.75 mmol) were
added. The reaction mixture was stirred for 12 h, treated with
5% HCl or DCl, and passed through a column (silica gel L,
40/100 µm). The products were isolated by successive elution
with toluene and MeOH.
1,2ꢀBis(diethylaluminio)ꢀ1ꢀphenylethane (5). 13C NMR, δ:
1.1 (t, C(7), C(9)); 8.7 (t, C(2)); 9.5 (q, C(8), C(10)); 18.3
(d, C(1)); 126.2 (d, C(6)); 128.0 (d, C(5)); 128.5 (d, C(4));
137.0 (s, C(3)).
1,2ꢀBis(diethylaluminio)ꢀoꢀtolylethane (13). 13C NMR, δ: 0.9
(br.t, C(10), C(12)); 8.9 (q, C(11), C(13)); 9.9 (br.t, C(2)); 18.2
(br.d, C(1)); 21.8 (q, C(9)); 126.5 (d, C(6)); 126.7 (d, C(7));
128.3 (d, C(5)); 128.9 (d, C(8)); 138.1 (s, C(4)); 143.3 (s, C(3)).
1,2ꢀBis(diethylaluminio)ꢀpꢀtolylethane (14). 13C NMR, δ: 1.6
(br.t, C(8), C(10)); 9.1 (q, C(9), C(11)); 9.8 (br.t, C(2)); 18.5
(br.d, C(1)); 20.9 (q, C(7)); 128.0 (q, C(5)); 129.8 (d, C(4));
133.4 (s, C(6)); 138.8 (s, C(3)).
1,2ꢀBis(diethylaluminio)ꢀ2ꢀphenylpropane (15). 13C NMR,
δ: 0.9 (br.t, C(8), C(10)); 9.0 (q, C(9), C(11)); 11.3 (br.t, C(2));
21.0 (q, C(7)); 23.2 (s, C(1)); 126.6 (d, C(6)); 127.3 (d, C(4));
128.3 (d, C(5)); 137.3 (s, C(3)).
Experimental
The reactions with organometallic compounds were carried
out under dry argon. The solvents were dried according to stanꢀ
dard procedures and distilled immediately before use. The startꢀ
ing catalysts Cp2ZrCl2 and Cp2TiCl2 were prepared according
to a known procedure.21 Commercially available 86% Et2AlCl
was purchased from the Redkinskii pilotꢀproduction plant
(Russia). The deuterolysis products were analyzed by GLC on a
Chromꢀ5 chromatograph (1200×3ꢀmm column with 5% SEꢀ30
or 15% PEGꢀ6000 on Chromaton NꢀAW, He as the carrier gas).
The IR spectra were measured on an IRꢀ75 spectrometer (films).
The mass spectra were obtained on an MXꢀ1306 mass spectromꢀ
eter (70 eV, 200 °C). The 1H and 13C NMR spectra were reꢀ
corded on JEOL FXꢀ90Q (90 and 22.5 MHz) and Bruker
AMꢀ300 (300 and 75 MHz) spectrometers in CDCl3 with Me4Si
as the internal standard. The atomic numbering scheme used for
the description of the 13C NMR spectra is shown in Scheme 15.
The 13C NMR spectra of OAC were recorded on a JEOL FXꢀ90Q
spectrometer (22.5 MHz) with broadꢀband and offꢀresonance
proton decoupling. Dilute solutions of OAC in THF with the
addition of C6D12 for internal stabilization of the magnetic field
were used. Solutions of OAC were placed in sealed tubes under
dry argon. The yields of OAC were determined by GLC of
hydrolysis products. The starting aluminum amides and alkoxides
were prepared according to known procedures.18,19 Compounds
8, 9, 18, 25, 29, 30, 34a,b, 35b, and 42 were identified by
comparing them with authentic samples.6,22—25
1,2ꢀBis(diethylaluminio)ꢀ1,1ꢀdiphenylethane (16). 13C NMR,
δ: 1.3 (br.t, C(7), C(9)); 9.1 (q, C(8), C(10)); 14.7 (br.t, C(2));
45.6 (br.s, C(1)); 126.9 (d, C(6)); 127.3 (d, C(4)); 128.2
(d, C(5)); 145.2 (s, C(3)).
oꢀ(1,2ꢀDideuterioethyl)toluene (17). B.p. 151—152 °C,
n20D 1.5046. IR, ν/cm–1: 685, 745, 880, 1010, 1060, 1310, 1370,
1
1420, 1580, 2170, 2870, 3010, 3050. H NMR, δ: 1.14 (d, 2 H,
CH2D, JC,D = 7.2 Hz); 2.24 (s, 3 H, Tol); 2.65 (t, 1 H, CHD,
JC,D = 7.2 Hz); 7.02—7.24 (m, 5 H, CH arom.). 13C NMR, δ:
15.8 (t, C(9), JC,D = 19.5 Hz); 21.6 (q, C(7)); 31.2 (d, C(8),
JC,D = 19.5 Hz); 126.5 (d, C(4)); 127.3 (d, C(5)); 128.9 (d, C(6));
129.2 (d, C(3)); 136.7 (s, C(2)); 142.5 (s, C(1)).
(1,2ꢀDideuterioisopropyl)benzene (19). B.p. 64—65 °C
(20 Torr), n20 1.4926. IR, ν/cm–1: 700, 745, 880, 1010, 1450,
D
1490, 1590, 1610, 2165 (νC,D), 2950, 3010, 3050. 1H NMR, δ:
0.97 (m, 5 H, CDH2, Me); 6.79—7.19 (m, 5 H, Ph). 13C NMR,
δ: 23.8 (t, C(6), JC,D = 18.8 Hz); 24.1 (q, C(7)); 34.1 (s, C(5),
JC,D = 18.8 Hz); 125.6 (d, C(4)); 127.5 (d, C(2)); 128.3 (d, C(3));
141.3 (s, C(1)).
Reactions of olefins with Et2AlCl—Mg—[Ti, Zr] (general proꢀ
cedure). A magnesium powder (12 mmol), Cp2TiCl2 (Cp2ZrCl2)
(0.5 mmol), THF (10 mL), olefin (10 mmol), and Et2AlCl
(22 mmol) were placed in a glass reactor under a dry argon
atmosphere at –5 °C. The reaction solution was warmed to
21—22 °C and stirred for 8 h. The reaction mixture was treated
with a 10% DCl solution in D2O. The products were extracted
with Et2O or hexane and isolated by distillation.
Reactions of acetylenes with Et2AlCl—Mg—[Ti, Zr] (genꢀ
eral procedure). Under the conditions used in the reactions of
olefins, acetylene (10 mmol) and Et2AlCl (22 mmol) were
added to a mixture of Cp2TiCl2 (Cp2ZrCl2) (0.5 mmol),
1,2ꢀDideuterioꢀ1,1ꢀdiphenylethane (20). B.p. 139—140 °C
(10 Torr), n20 1.5756. IR, ν/cm–1: 700, 745, 880, 1010, 1450,
D
1490, 1590, 2165 (νC,D), 2950, 3000. 13C NMR, δ: 21.0 (t, C(2),
JC,D = 19.1 Hz); 28.9 (s, C(1), JC,D = 19.1 Hz); 125.9 (d, C(6));
128.6 (d, C(4)); 129.0 (d, C(5)); 145.9 (s, C(3)).
1,2ꢀBis(nꢀbutoxyaluminio)ꢀ1ꢀphenylethane (21a). 13C NMR,
δ: 8.9 (br.t, C(2)); 13.9 (q, C(10), C(14)); 18.2 (br.d, C(1));
19.1 (t, C(9), C(13)); 34.8 (t, C(8), C(12)); 64.8 (t, C(7),
C(11)); 126.4 (d, C(6)); 127.0 (d, C(4)); 128.7 (d, C(5));
137.1 (s, C(3)).
1,2ꢀBis(nꢀhexyloxyaluminio)ꢀ1ꢀphenylethane
(21b).
13C NMR, δ: 8.9 (br.t, C(2)); 14.1 (q, C(12), C(18)); 18.9

Alumination of olefins, dienes, and acetylenes
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 7, July, 2003
1581
Scheme 15

1582
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 7, July, 2003
Dzhemilev et al.
(br.d, C(1)); 22.9 (t, C(11), C(17)); 25.3 (t, C(9), C(15));
31.8 (t, C(10), C(16)); 32.7 (t, C(8), C(14)); 64.9 (t, C(7),
C(13)); 125.9 (d, C(6)); 126.3 (d, C(4)); 128.7 (d, C(5));
137.1 (s, C(3)).
This study was financially supported by the Russian
Foundation for Basic Research (Project Nos. 02ꢀ03ꢀ
97903a and 02ꢀ03ꢀ97904a).
1,2ꢀBis[(diethylamino)aluminio]ꢀ1ꢀphenylethane (21c).
13C NMR, δ: 9.3 (br.t, C(2)); 15.0 (q, C(8), C(10)); 18.4 (br.d,
C(1)); 43.8 (t, C(7), C(9)); 125.9 (d, C(6)); 127.0 (d, C(4));
128.5 (d, C(5)); 137.2 (s, C(3)).
1,2ꢀBis[(dicyclohexylamino)aluminio]ꢀ1ꢀphenylethane (21d).
13C NMR, δ: 9.5 (br.t, C(2)); 19.0 (br.d, C(1)); 25.6 (t, C(9),
C(13)); 26.9 (t, C(10), C(14)); 38.3 (t, C(8), C(12)); 54.3 (d,
C(7), C(11)); 126.0 (d, C(6)); 127.3 (d, C(4)); 128.8 (d, C(5));
137.1 (s, C(3)).
References
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3,4ꢀBis(diethylaluminio)ꢀ1,4ꢀdiphenylbutꢀ1ꢀene
(24).
13C NMR, δ: 0.9 (br.t, C(13), C(15)); 8.9 (q, C(14), C(16));
18.4 (br.d, C(1)); 24.1 (br.d, C(2)); 125.8 (d, C(12)); 126.2
(d, C(8)); 128.4 (d, C(7), C(11)); 128.2 (d, C(10)); 128.8
(d, C(6)); 128.9 (d, C(4)); 130.3 (d, C(3)); 137.7 (s, C(5));
140.5 (s, C(9)).
1,2ꢀDideuterio[60]fullerene (30). MS of negative ions
(325 °C, Ee = 0 eV), m/z (Irel (%)): 720 [C60] (100); 724 [C60D2]
(8); 728 [C60D4] (14); 732 [C60D6] (28); 736 [C60D8] (16); 740
[C60D10] (12); 744 [C60D12] (24).
1,2ꢀBis(diethylaluminio)ꢀ1,2ꢀdiphenylethene
(31a).
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(d, C(4)); 128.7 (d, C(5)); 137.9 (s, C(3)).
Hexa(nꢀpropyl)benzene (33b). B.p. 160 °C (1 Torr). IR,
ν/cm–1: 710, 880, 1080, 1370, 1450, 1605, 2850, 2880, 2915,
2940. 1H NMR, δ: 0.99 (t, 18 H, Me, J = 7.0 Hz); 1.25—1.70
(m, 12 H, CH2); 2.30—2.53 (m, 12 H, CH2). 13C NMR,
δ: 13.8 (q, C(9)); 22.7 (t, C(8)); 29.1 (t, C(7)); 139.5
(s, C(1)—C(6)).
Hexa(nꢀbutyl)benzene (33c). B.p. 185 °C (1 Torr). 1H NMR,
δ: 1.08 (t, 18 H, Me, J = 7.0 Hz); 1.23—1.75 (m, 24 H, CH2);
2.39—2.57 (m, 12 H, CH2—Ph). 13C NMR, δ: 14.1 (q, C(10));
22.4 (t, C(9)); 32.5 (t, C(8)); 28.9 (t, C(7)); 139.5 (s,
C(1)—C(6)).
cisꢀ5,6ꢀDideuteriodecꢀ5ꢀene (34c). B.p. 173 °C, n20D 1.4276.
1H NMR, δ: 0.81 (t, 6 H, Me, J = 7.0 Hz); 1.25—1.40 (m, 8 H,
CH2); 1.98—2.09 (m, 4 H, CH2C=). 13C NMR, δ: 14.1 (q, C(1));
22.5 (t, C(2)); 26.9 (t, C(4)); 32.1 (t, C(3)); 129.6 (s, C(5),
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1
B.p. 153 °C (8 Torr), n25 1.4486. H NMR, δ: 0.90 (m, 12 H,
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1,2ꢀBis[(diethylamino)aluminio]ꢀ1,2ꢀdiphenylethene (37).
13C NMR, δ:* 13.0 (q, C(8)); 41.9 (d, C(7)); 125.5 (d, C(6));
126.6 (d, C(4)); 128.5 (d, C(5)); 137.7 (s, C(3)).
1,2ꢀBis[di(nꢀbutoxy)aluminio]ꢀ1,2ꢀdiphenylethene (38).
13C NMR, δ:* 13.2 (q, C(10)); 22.8 (t, C(9)); 34.2 (t, C(8));
64.6 (t, C(7)); 126.1 (d, C(6)); 127.8 (d, C(4)); 128.3 (d, C(5));
137.9 (s, C(3)).
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Alumination of olefins, dienes, and acetylenes
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Received October 23, 2002;
in revised form February 11, 2003