Synthesis and structure of novel chiral amido-imine complexes of aluminum, gallium, and indium

Article abstract of DOI:10.1007/s11172-009-0314-x

The reactions of 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-BIAN, 1) with tri-iso-butylaluminum, triethylgallium or trimethylindium give the novel amido-imine complexes (Buⁱ - dpp-BIAN)AlBui2 (4), (Et - dpp-BIAN)GaEt₂ (5)

Full text of DOI:10.1007/s11172-009-0314-x

Russian Chemical Bulletin, International Edition, Vol. 58, No. 11, pp. 2250—2257, November, 2009
2250
Synthesis and structure of novel chiral amidoꢀimine complexes
of aluminum, gallium, and indium
A. N. Tishkina,a A. N. Lukoyanov,a A. G. Morozov,a G. K. Fukin,a K. A. Lyssenko,b and I. L. Fedushkina
aA. G. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences,
49 ul. Tropinina, 603950 Nizhnii Novgorod, Russian Federation.
Fax: +7 (831) 462 7497. Eꢀmail: igorfed@iomc.ras.ru
bA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5085
The reactions of 1,2ꢀbis[(2,6ꢀdiisopropylphenyl)imino]acenaphthene (dppꢀBIAN, 1) with
triꢀisoꢀbutylaluminum, triethylgallium or trimethylindium give the novel amidoꢀimine comꢀ
plexes (Bui—dppꢀBIAN)AlBui (4), (Et—dppꢀBIAN)GaEt2 (5), and (Me—dppꢀBIAN)InMe2
2
(6), respectively. The reaction of (dppꢀBIAN)AlI(Et2O) (7) with allyl bromide affords analoꢀ
gous chiral amidoꢀimine derivative (All—dppꢀBIAN)AlBrI (8). Hydrolysis of 8 affords the
aminoꢀimino compound (All—dppꢀBIAN)H (9). The new compounds 4—6, 8, and 9 have
1
been characterized by H NMR and IR spectroscopy. The molecular structures of 5, 6, and 9
were determined by single crystal Xꢀray analysis.
Key words: aluminum, gallium, indium, diimines, chiral ligands, Xꢀray diffraction analysis.
The progress in metallorganic and coordination chemꢀ
istry is largely enabled by versatility of organic ligands
used for the synthesis of metallocomplexes. Over the last
years there has been much research activity focused on
metal diimine complexes and, in particular, the derivaꢀ
tives of acenaphtheneꢀ1,2ꢀdiimines (BIAN), which
exhibit rather interesting chemical properties. The transiꢀ
tion metal complexes with BIAN ligands catalyze alkyne
hydrogenation,1 C—C bond generating reactions,2 cycloꢀ
isomerization,3 and are especially effective in polymerꢀ
ization of olefins4 and acrylic monomers.5
Scheme 1
During recent years, we have synthesized the comꢀ
plexes of Group 1, 2, 13, 14, and 15 metals with BIAN
ligands. Magnesium and aluminum complexes with 1,2ꢀbisꢀ
[(2,6ꢀdiisopropylphenyl)imino]acenaphthene (1, dppꢀBIAN)
are highly reactive towards a wide variety of organic speꢀ
cies,6 i.e., terminal alkynes, ketones, nitriles, haloꢀsubstiꢀ
tuted hydrocarbons; they also display good activity as cataꢀ
lysts of ring opening polymerization of lactide.7
Lithium complexes containing chiral amidoꢀimine
ligand are obtained by reacting dppꢀBIAN with butylꢀ
lithium (Scheme 1).8 The reactions involve the addition
of BunLi to one of the two C=N double bonds of a ligand,
where an nꢀbutyl radical adds to the imine carbon and a
lithium atom — to the nitrogen, yielding the lithium salt
of unsymmetrical chelating amidoꢀimine ligand.
Ar = 2,6ꢀPri2C6H3
germanium(II)8 and zinc(II).9 The analogous alkaline
earth metal complexes are also known. In particular,
(dppꢀBIAN)Mg(thf)3 interacts with ethyl halides in
hexane to yield amidoꢀimine complex [(Et—dppꢀBIAN)ꢀ
An anionic amidoꢀimine ligand [Bun—dppꢀBIAN]–
can be transferred from lithium to other metals, e.g.,
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2183—2189, November, 2009.
1066ꢀ5285/09/5811ꢀ2250 © 2009 Springer Science+Business Media, Inc.

Amidoꢀimine metal complexes
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 11, November, 2009 2251
MgX(thf)n].6g The same products are formed in the reacꢀ
tions of ligand 1 with Grignard reagents.
Employment of such chelating systems give rise to
new synthetic routes offering an access to metallorganic
reagents for synthetic applications. For example, chiral
aluminum complex (iminoꢀamido)AlMe2 synthesized by
the reaction between αꢀdiimine Ar—N=C(Me)—C(Me)=
N—Ar (Ar = 2,6ꢀPri2C6H3) and Me3Al (1 : 1) or methylꢀ
alumoxane (1 : 3)10 was found to catalyze ethylene polyꢀ
merization. This makes the chemistry of complexes with
chiral ligands attractive from a practical perspective. Here
we describe synthesis and structure of the novel chiral
amidoꢀimine complexes of Group 13 metals.
C(13)
C(1)
N(1)
C(2)
C(39)
Ga
N(2)
C(41)
Fig. 1. Molecular structure of complex 5. Thermal ellipsoids
50%. Hydrogen atoms are omitted.
Results and Discussion
Synthesis and identification of compounds. New cheꢀ
late amidoꢀimine complexes (Bui—dppꢀBIAN)AlBui2 (4),
(Et—dppꢀBIAN)GaEt2 (5), and (Me—dppꢀBIAN)InMe2
(6) were prepared by reacting diimine 1 with triisobutylꢀ
aluminum, triethylgallium, and trimethylindium, respecꢀ
tively (Scheme 2).
C(13)
C(2)
N(2)
C(1)
C(38)
N(1)
Scheme 2
In
C(39)
Fig. 2. Molecular structure of complex 6. Thermal ellipsoids
50%. Hydrogen atoms are omitted.
Ar = 2,6ꢀPri2C6H3
M = Al, R = Bui (4); M = Ga, R = Et (5); M = In, R = Me (6)
The molecule of diimine dppꢀBIAN6d lies on a crysꢀ
tallographic twofold rotation axis passing through the
C—C bond linking to sixꢀmembered rings of a naphthaꢀ
lene moiety. The distances C(1)—N(1) and C(2)—N(2)
(1.282(4) Å) match with the double C=N bond, and
C(1)—C(2) distance (1.534(6) Å) is close to the value of a
single C—C bond.
Attachment of alkyl group to the imine carbon of
diimine 1 generates a chiral center at C(1) in molecules 5
and 6 and their symmetry is thus distorted. Unlike chiral
amidoꢀimine complexes of zinc9 and magnesium,6g with a
unit cell containing both isomers (R and S), compounds 5
and 6 crystallize as a conglomerate (a mechanical mixture
of enantiomers).11 Figures 1 and 2 show S isomer of 5 and
R isomer of 6, respectively.
It should be noted that the reactions occur only in
nonꢀcoordinating solvents, such as toluene or hexane.
Coordinating solvents (diethyl ether or THF) are involved
in the formation of R3M←OEt2 adducts, which hampers
the addition of metal alkyls to diimine 1. Substitution of a
coordinating solvent with toluene does not afford adduct
dissociation leading to R3M and dppꢀBIAN addition prodꢀ
uct. The above data suggest that the alkyl addition over
C=N bond begins with the coordination of dppꢀBIAN
ligand nitrogens by a Group 13 metal. Complexes 4, 5,
and 6 were synthesized in toluene and then isolated by
recrystallization from hexane as red colored prisms in 92,
87, and 83% yield, respectively. They were characterized
by IR and NMR, including 1H,1HꢀCOSY technique. The
structures of complexes 5 and 6 were determined by Xꢀray
diffraction and are shown in Figs 1 and 2, respectively.
Details of crystal data, data collection and structure reꢀ
finement are listed in Table 1. Selected bond lengths and
bond angles for structures 5 and 6, as well as the correꢀ
sponding values for dppꢀBIAN, are collected in Table 2.
It is noteworthy that crystal 6 exhibits lamellar racemic
twinning11b as indicated by Flack parameter (0.466(7)),12
whereas in crystal 5 only one enantiomer is present (Flack
parameter is 0.000(1)).
Nonꢀsymmetry of structures 5 and 6 is manifested in
different C—N bond distances in diimine fragments of

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Tishkina et al.
Table 1. Crystallographic data and Xꢀray diffraction experiment parameters for structures 5, 6, and 9
Parameter
5
6
9
Molecular formula
Molecular weight
Т/К
C
42H55GaN2
657.60
100(2)
C39H49InN2
660.62
C39H46N2
542.78
100(2)
100(2)
Crystal system
Space group
a/Å
b/Å
c/Å
Monoclinic
P21
Monoclinic
P21
Monoclinic
P21/c
10.1514(5)
16.6995(8)
10.8457(5)
98.8030(10)
1816.94(15)
2 (1)
9.8767(3)
16.0203(5)
10.8136(4)
96.0516(6)
1701.48(10)
2 (1)
18.8454(7)
17.0502(6)
20.2102(8)
99.3680(10)
6407.3(4)
8 (1)
β/deg
V/Å3
Z (Z´)
d/g cm–3
μ/mm–1
F(000)
1.202
0.788
704
1.289
0.723
692
1.125
0.064
2352
θ
max/deg
29.00
29.00
26.00
Number of measured reflections
17434
17172
38230
Number of independent
9368 (0.0350)
8767 (0.0244)
12584 (0.0363)
reflections (Rint
GOF(F2)
)
0.991
0.975
1.030
R1/wR2 (I > 2σ(I))
R1/wR2 (based on all reflections)
Residual electron
density/e•Å–3, ρmax/ρ
0.0396/0.0831
0.0495/0.0879
0.436/–0.354
0.0243/0.0571
0.0263/0.0585
0.593/–0.746
0.0437/0.1049
0.0678/0.1131
0.305/–0.366
min
Table 2. Selected bond lengths (d) and bond angles (ω) in compounds 1,6d 5, 6, and 9
Parameter
1
5
6
9
Bond
d/Å
M—N(1)
M—N(2)
—
—
1.919(1)
2.139(1)
1.465(3)
1.279(3)
1.554(3)
1.563(3)
1.994(3)b
1.983(3)d
2.123(1)
2.323(1)
1.457(3)
1.283(2)
1.551(2)
1.555(2)
2.170(2)c
2.158(2)e
—
—
C(1)—N(1)
C(2)—N(2)
C(1)—C(2)
C(1)—C(13)
M—R1
1.282(4)
1.282(4)
1.534(6)
—
1.489(2)/1.492(2)a
1.272(1)/1.271(1)a
1.554(2)/1.545(2)a
1.542(2)/1.543(2)a
—
—
—
M—R2
—
Angle
ω/deg
N(1)—M—N(2)
N(1)—M—R1
N(1)—M—R2
N(2)—M—R1
N(2)—M—R2
R1—M—R2
—
—
—
—
—
—
82.14(8)
117.6(1)b
109.0(1)d
105.0(1)
115.1(2)
121.3(2)
76.62(6)
116.7(1)c
119.2(1)e
103.4(1)
108.7(1)
120.1(1)
—
—
—
—
—
—
a Values for the second molecule.
b Ga—C(39).
c In—C(38).
d Ga—C(41).
e In—C(39).
molecules. The C(2)—N(2) bonds in 5 (1.279(3) Å) and 6
(1.283(2) Å) are double and are essentially shorter than
C(1)—N(1) (1.465(3) and 1.457(3) Å, respectively). The
C(1)—C(2) distances in 5 (1.554(3) Å) and 6 (1.551(2) Å)
are comparable with a single bond distance C(1)—C(2) in
the free ligand dppꢀBIAN (1.534(6) Å). In structures 5
and 6, a fiveꢀmembered ring MN2C(1)C(2) adopts a disꢀ
torted envelope conformation with the N(1) atom disꢀ
placed ∼0.59 Å out of the ring plane.
Both molecules 5 and 6 have distorted tetrahedral
coordination around metal centers linked to two alkyl
carbons and two nitrogens of the chelating amidoꢀimine

Amidoꢀimine metal complexes
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 11, November, 2009 2253
a
Projection of isobutyl
gꢀgroup along the
CH2—CHMe2 bond
7.5
a
6.5
5.5
4.5
3.5
2.5
1.5
0.5
e
δ
Fig. 3. Structure of complex (Bui—dppꢀBIAN)AlBui (4) from
2
1
b
1H NMR and H,1HꢀCOSY data.
g(Ha)
g(Hb)
ligand (see Figs 1 and 2). Amido and imino nitrogens
differ in their M—N bond lengths (M = metal). The
amido bond M—N(1) (5: Ga—N(1), 1.9190(19) Å;
6: In—N(1), 2.1228(17) Å) is substantially shorter comꢀ
pared to coordination bond M—N(2) (5: Ga—N(2),
2.1389(17) Å; 6: In—N(2), 2.3229(16) Å).
b
c
d
f
2.0
3.6
1.0
1.0
3.2
1.9
2.8
1.0
5.0
1.1
4.0
4.6
4.4
δ
Although compound 4 was not characterized by Xꢀray
diffraction, its structure shown in Fig. 3 was proved absoꢀ
lutely by 1H NMR data.
c
e(2 H), f(3 H), g(Hc), g(3 H)
e
e
The isobutyl group attached to dppꢀBIAN (gꢀgroup,
f
1
see Fig. 3) gives a complex signal in the H NMR specꢀ
d
d
a b
c
c
a
b
trum (Fig. 4). Two methylene protons (Ha and Hb) are
nonequivalent due to bonding to the nonsymmetrical carꢀ
bon atom of the fiveꢀmembered ligand ring. As a result,
they are found at δ 3.31—2.60 as two signals showing large
spinꢀspin splitting (doublet (Ha) at δ 3.28, J = 13.6 Hz
and double doublet (Hb) at δ 2.66, J = 13.6 and 8.8 Hz).
This set of signals can be interpreted as follows: the douꢀ
blet is due to the Ha proton which in the projection of
gꢀgroup (see Fig. 3) makes an angle of ∼90° with the
methyne proton Hc and, hence, does not interact with it
producing only the doublet (resulting from coupling with
Hb proton). The Hb proton in the projection is rotated
150° with respect to Hc proton and gives a double doublet
(coupling with Ha and Hc).
g
f
2.9 3.1 3.03.2 3.2 3.3 6.1 3.3
9.5
3.0
2.0
3.0
3.0
1.8 1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0 –0.2 δ
Fig. 4. 1H NMR spectrum of compound (Bui—dppꢀBIAN)ꢀ
AlBui (4) (C6D6, 200 MHz) (a) and assignment of signals from
2
aliphatic protons (b and c). Proton labeling is shown in Fig. 3.
Since the addition of alkyl group renders structures
4—6 chiral by generating a nonsymmetric carbon atom,
all aromatic and methine protons, and also all the eight
methyl groups are nonequivalent (see Fig. 4, a). Four
methine protons appear as four septets at δ 4.9—3.0 (see
Fig. 4, b), and eight methyl groups — as eight doublets in
the 1.8 to –0.4 region (see Fig. 4, c).
In the similar manner with the magnesium comꢀ
plexes,6g Group 13 metal complexes with nonsymmetrical
amidoꢀimine ligands can be obtained by reactions of
dppꢀBIAN dianion derivatives with alkyl halides. Such
reaction between (dppꢀBIAN)AlI(Et2O) (7) and allyl
bromide (AllBr) leads to amidoꢀimine complex (All—
dppꢀBIAN)AlBrI (8) (Scheme 3). Complex 8 was isoꢀ
lated from ether as orange crystals in 55% yield and charꢀ
acterized by IR and NMR (including 1H,1HꢀCOSY).
Compound 8 was not examined by Xꢀray diffraction; its
structure shown in Scheme 3 was tentatively identified
based on the 1H NMR data. The hydrolysis of complex 8
yielded (78%) aminoꢀimine 9 (see Scheme 3), which was
isolated from hexane as yellow crystals and characterized
by NMR.
In the field of aliphatic protons the 1H NMR spectrum
of 9 (Fig. 5) shows half of signals as compared to the
spectrum of complex 8.
Two signals from the methine protons of isopropyl
groups appear as partially overlapping septets at δ 3.46
and 3.33. Four doublets due to methyl moities of isoꢀ
propyl groups instead of the eight expected are found at

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Russ.Chem.Bull., Int.Ed., Vol. 58, No. 11, November, 2009
Tishkina et al.
Scheme 3
Ar = 2,6ꢀPri2C6H3
C(13)
C(1)
C(2)
N(2)
N(1)
C(16)
H
5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 δ, м.д.
5.5
Fig. 5. 1H NMR spectrum of compound (All—dppꢀBIAN)H (9)
(C6D6, 200 MHz). The δ field containing signals from aromatic
protons is omitted.
Fig. 6. Molecular structure of compound 9. Thermal ellipsoids
50%. Hydrogen atoms are omitted except one bound to N(1).
δ 1.5—1.1. The allylic methylene protons in the αꢀposiꢀ
tion to the chiral center give a double doublet (δ 3.64,
J = 13.3 and 7.0 Hz), the protons of the allylic =CH2
group at a double bond appear as coupled double doublets
(δ 5.13, J = 17.1 and 2.0 Hz; δ 4.79, J = 10.0 and 2.0 Hz),
the methine proton of CH2CHCH2 fragment — as a
complex signal (doublet of triplet of doublets) with three
couplings (δ 5.62, J = 17.1, 7.0 and 10.0 Hz). The proton
bonded to N atom produces a singlet at δ 4.29.
ring: it is oriented either towards the geometrical center of
the naphthalene moiety (and thus configured over the
acenaphthene plane) or outward from this centroid and
away from the aminoꢀimine. Bond lengths in all molꢀ
ecules differ inconsiderably, so we will discuss the data
of one molecule. Nonsymmetry of the structure 9 (see
Fig. 6) is evident in different C—N bond lengths. The
C(2)—N(2) (1.272(1) Å) is a double bond and is substanꢀ
tially shorter compared to a single C(1)—N(1) bond
(1.489(2) Å). The N(1) nitrogen in 9 has the trigonalꢀ
pyramidal coordination. In contrast to complexes 5 and
6, compound 9 crystallizes to produce a unit cell containꢀ
ing both R and S isomers.
In summary, we have synthesized and characterized
four novel chiral amidoꢀimine complexes of aluminum,
gallium, and indium (compounds 4—6 and 8). The reacꢀ
tion between Group 13 metal alkyls and diimine 1 was
demonstrated to lead to a single product of 1,2ꢀaddition
to the ligand C=N double bond regardless of the initial
reactant ratio. As indicated by Xꢀray diffraction data, galꢀ
lium and indium chiral amidoꢀimine complexes (5 and 6,
respectively) unlike analogous complexes of zinc and
magnesium, crystallize as a conglomerate (mechanical
mixture of enantiomers).
1
The lacking of a half of signals in the H NMR specꢀ
trum of 9 is attributable to their strong broadening resultꢀ
ant from a hindered rotation of the aniline fragment about
N(1)—C(1) bond. The detailed examination of the
1H NMR spectrum reveals an upward baseline drift at
δ 4.5—2.5 and especially at δ 2.0—0.0. As the C(1)—N(1)
and N(1)—C(16)ipso bonds are single and N(1) atom, in
contrast with the amido nitrogen N(1) in complex 8, does
not close a chelate ring, there is a possibility for the inverꢀ
sion of its pyramidal geometry.
Crystal structure of complex 9 was determined from
Xꢀray diffraction analysis and is shown in Figure 6.
The unit cell of aminoꢀimine 9 incorporates four pairs
of nonequivalent molecules. The key difference is in the
attachment mode of the allyl group on a fiveꢀmembered

Amidoꢀimine metal complexes
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 11, November, 2009 2255
(40 mL) was added Et3Ga (0.16 g, 1.0 mmol). The reaction
mixture was heated for 1 h at 90 °C. On heating the solution
changed color from a yellow to redꢀbrown. Then toluene
was replaced by hexane. Crystallization from hexane yielded
compound 5 as redꢀbrown crystals (0.57 g, 87%). M.p. 173 °C.
IR, ν/cm–1: 1937 w, 1901 w, 1872 w, 1843 w, 1807 w, 1783 w,
1709 w, 1687 w, 1626 s, 1587 s, 1535 w, 1490 m, 1365 s, 1308 s,
1287 m, 1253 s, 1204 s, 1189 s, 1167 s, 1136 m, 1102 s, 1078 m,
1046 s, 1021 s, 1005 s, 969 m, 956 m, 937 s, 924 m, 905 w, 880 m,
860 m, 835 m, 822 w, 803 s, 783 s, 762 s, 752 s, 700 w, 647 m, 633 m,
611 m, 595 m, 579 m, 537 s, 513 m, 500 m, 467 m, 450 m, 422 m.
1H NMR (400 MHz, THFꢀd8, 20 °C, a—g labeling of functional
groups is as shown in Fig. 3 for complex 4), δ: 8.03 (d, 1 H,
naphthalene moiety, J = 8.3 Hz); 8.01 (d, 1 H, naphthalene
Experimental
All the compounds mentioned above except 1 and 9 are airꢀ
and moistureꢀsensitive, thus all manipulations on their synthesis,
isolation and identification were performed in vacuo using
standard Schlenk techniques. Diimine dppꢀBIAN was obtained
via condensation of acenaphthenequinone with 2,6ꢀdiisoꢀ
propylaniline in acetonitrile by the known procedure.13 The
compound dppꢀBIANAlI(Et2O) was synthesized as described
previously.14 Melting points were determined in vacuumꢀsealed
capillary tubes. Diethyl ether, hexane, and toluene were dried
and stored over sodium/benzophenone, and withdrawn by
vacuum condensation immediately before use. IR spectra were
measured from compound suspensions in the Vaseline oil on a
FSMꢀ1201 spectrometer. 1H and 13C NMR spectra were
recorded on Bruker ARX 200, Bruker DPX 200, and Bruker
ARX 400 spectrometers.
moiety, J = 8.3 Hz); 7.50—7.45 (м, 3 H, C6H3Pri ); 7.39 (dd,
2
1 H, naphthalene moiety, J = 7.3 Hz, J = 8.3 Hz); 7.32 (dd, 1 H,
naphthalene moiety, J = 7.3 Hz, J = 8.3 Hz); 7.21 (dd, 1 H,
C6H3Pri2, J = 7.5 Hz, J = 1.5 Hz); 7.05 (dd, 1 H, C6H3Pri2,
J = 7.5, J = 7.8); 6.84 (dd, 1 H, C6H3Pri2, J = 7.8 Hz, J = 1.5 Hz);
6.40 (d, 1 H, naphthalene moiety, J = 7.3 Hz); 6.15 (d, 1 H,
naphthalene moiety, J = 7.3 Hz); 4.58 (sept, 1 H, aꢀgroup CHMe2,
J = 7.0 Hz); 3.43 (sept, 1 H, bꢀgroup CHMe2, J = 6.8 Hz);
3.13 (sept, 1 H, cꢀgroup CHMe2, J = 6.8 Hz); 2.84 (sept, 1 H,
dꢀgroup CHMe2, J = 6.8 Hz); 2.73 (м, 1 H, eꢀgroup CHaHbMe);
2.41 (m, 1 H, gꢀgroup CHaHbMe); 1.45 (d, 3 H, aꢀgroup
CH(CH3)(Me), J = 7.0 Hz); 1.43 (d, 3 H, bꢀgroup CH(CH3)(Me),
J = 6.8 Hz); 1.33 (t, 3 H, fꢀgroup GaCH2CH3, J = 8.0 Hz);
1.27 (d, 3 H, aꢀgroup CH(Me)(CH3), J = 7.0 Hz); 1.24 (d, 3 H,
cꢀgroup CH(CH3)(Me), J = 6.8 Hz); 1.19 (d, 3 H, bꢀgroup
CH(Me)(CH3), J = 6.8 Hz); 1.00 (м, 2 H, fꢀgroup GaCH2Me);
0.91 (d, 3 H, dꢀgroup CH(CH3)(Me), J = 6.8 Hz); 0.88 (t,
3 H, gꢀgroup GaCH2CH3, J = 8.0 Hz); 0.60 (d, 3 H, cꢀgroup
CH(Me)(CH3), J = 6.8 Hz); 0.47 (m, 2 H, gꢀgroup GaCH2Me);
0.11 (t, 3 H, eꢀgroup CH2CH3, J = 7.5 Hz); –0.27 (d, 3 H,
dꢀgroup CH(Me)(CH3), J = 6.8 Hz). 13C NMR (400 MHz,
THFꢀd8, 20 °C), δ: 191.9, 150.5, 149.1, 146.1, 141.1, 140.9,
140.7, 139.7, 131.8, 130.9, 128.7, 128.3, 127.3, 127.1, 125.1,
124.7, 124.3, 80.6, 66.9, 66.0, 40.6, 28.7, 28.1, 28.0. 27.2, 26.4,
25.6, 25.1, 24.3, 23.9, 23.7, 20.8, 10.9, 9.9, 9.6, 8.6, 3.7.
[(2,6ꢀDiisopropylphenyl){2ꢀ(2,6ꢀdiisopropylphenylimino)ꢀ
1ꢀisobutylꢀ1,2ꢀdihydroacenaphthylenꢀ1ꢀyl}amino]diisobutylꢀ
aluminum (4). To the solution of dppꢀBIAN (0.50 g, 1.0 mmol)
in toluene (40 mL) was added Bui Al (0.20 g, 1.0 mmol). On
3
addtion the solution changed color from a yellow to brown. The
solution was heated for 1 h at 90 °C. Then toluene was replaced
by hexane. Hexane solution was concentrated to yield compound
4 as red crystals (0.64 g, 92%), m.p. 162 °C. Found (%): C, 82.45;
H, 9.63. C48H67AlN2 (M = 699.05 g mol–1). Calculated (%):
C, 82.47; H, 9.66. IR, ν/cm–1: 1613 w, 1591 m, 1545 w, 1512 m,
1315 s, 1255 m, 1209 w, 1134 w, 1110 w, 1001 m, 927 m, 809 m,
764 s, 730 m, 687 m, 561 m, 427 w. 1H NMR (200 MHz, C6D6,
20 °C, for a—g labeling of functional groups see Fig. 3), δ: 7.48
(dd, 1 H, naphthalene moiety, J = 7.5 Hz, J = 1.8 Hz);7.45—7.25
(m, 6 H, 2 C6H3Pri ); 7.12 (dd, 1 H, naphthalene moiety,
2
J = 7.5 Hz, J = 1.8 Hz); 6.96 (dd, 1 H, naphthalene moiety, J =
= 7.0 Hz, J = 8.0 Hz); 6.80 (dd, 1 H, naphthalene moiety,
J = 7.3 Hz, J = 8.0 Hz); 6.48 (d, 1 H, naphthalene moiety, J =
= 7.3 Hz); 6.32 (d, 1 H, naphthalene moiety, J = 7.0 Hz);
4.90 (sept, 1 H, aꢀgroup CHMe2, J = 6.8 Hz); 3.64 (sept, 1 H,
bꢀgroup CHMe2, J = 6.8 Hz); 3.38 (sept, 1 H, cꢀgroup CHMe2,
J = 6.8 Hz); 3.29 (d, 1 H, gꢀgroup CHaHbCHcMe2, J = 13.6 Hz);
3.07 (sept, 1 H, dꢀgroup CHMe2, J = 6.8 Hz); 2.65 (dd, 1 H,
gꢀgroup CHaHbCHcMe2, J = 13.6 Hz, J = 8.8 Hz); 2.55 (m,
1 H, eꢀgroup AlCH2CHMe2, J = 6.6 Hz, J = 6.5 Hz, J = 6.3 Hz);
2.26 (sept, 1 H, fꢀgroup AlCH2CHMe2, J = 7.0 Hz, J = 6.6 Hz);
1.71 (d, 3 H, aꢀgroup CH(CH3)Me, J = 6.8 Hz); 1.66 (d, 3 H,
aꢀgroup CH(Me)(CH3), J = 6.8 Hz); 1.59 (d, 3 H, bꢀgroup
CH(CH3)(Me), J = 6.8 Hz); 1.49 (d, 3 H, eꢀgroup AlCH2CHꢀ
(CH3)(Me), J = 6.3 Hz); 1.43 (d, 3 H, cꢀgroup CH(CH3)(Me),
J = 6.8 Hz); 1.38 (d, 3 H, eꢀgroup AlCH2CH(Me)(CH3),
J = 6.6 Hz); 1.28 (d, 3 H, dꢀgroup AlCH2CH(CH3)(Me),
J = 6.6 Hz); 1.25 (d, 3 H, cꢀgroup CH(Me)(CH3), J = 6.8 Hz);
1.13 (d, 3 H, fꢀgroup AlCH2CH(CH3)(Me), J = 6.6 Hz);
1.06—0.82 (м, 6 H, gꢀgroup CHaHbCHc(Me)2, gꢀgroup
CHaHbCHc(CH3)(Me), eꢀgroup AlCH2CH(Me)(Me)); 0.94
(d, 3 H, fꢀgroup AlCH2CH(Me)(CH3), J = 6.6 Hz); 0.62 (d,
3 H, cꢀgroup CH(Me)(CH3), J = 6.8 Hz); 0.45 (d, 2 H, fꢀgroup
AlCH2CH(Me)(Me), J = 7.0 Hz); –0.04 (d, 3 H, dꢀgroup
CH(Me)(CH3), J = 6.8 Hz); –0.37 (d, 3 H, gꢀgroup CHaHbꢀ
CHc(Me)(CH3), J = 5.8 Hz).
[(2,6ꢀDiisopropylphenyl){2ꢀ(2,6ꢀdiisopropylphenylimino)ꢀ
1ꢀmethylꢀ1,2ꢀdihydroacenaphthylenꢀ1ꢀyl}amino]dimethylindium
(6). To the cool solution of dppꢀBIAN (0.50 g, 1.0 mmol) in
toluene (30 mL) was added Me3In (0.16 g, 1.0 mmol). The
reaction mixture was heated for 1 h at 90 °C. On heating the
solution changed color from a yellow to redꢀbrown. Then toluene
was replaced by hexane. Compound 6 was crystallized from
hexane as red rhombs. Yield 0.55 g (83%), m.p. 202 °C. IR,
ν/cm–1: 1634 s, 1618 m, 1587 m, 1542 w, 1512 w, 1491 m,
1428 m, 1366 m, 1347 m, 1313 m, 1271 w, 1252 m, 1204 m,
1194 m, 1188 w, 1175 w, 1154 m, 1106 m, 1076 m, 1055 w,
1046 m, 1015 m, 991 w, 980 w, 970 w, 961 w, 936 w, 849 m,
832 m, 801 m, 785 m, 771 m, 757 m, 696 w, 677 m, 663 w,
627 w, 612 m, 596 w, 577 w, 545 m, 496 m, 481 m, 465 w, 453 w,
422 m. 1H NMR (200 MHz, C6D6, 20 °C, a—g labeling of
functional groups is as shown in Fig. 3 for complex 4), δ:
7.35 (dd, 1 H, naphthalene moiety, J = 7.5 Hz, J = 1.8 Hz);
7.31—7.16 (m, 6 H, 2 C6H3Pri ); 7.04 (dd, 1 H, naphthalene
2
moiety, J = 7.5 Hz, J = 1.8); 6.97 (dd, 1 H, naphthalene moiety,
J = 7.0 Hz, J = 8.3 Hz); 6.79 (dd, 1 H, naphthalene moiety, J =
= 7.5 Hz, J = 7.8 Hz); 6.43 (d, 2 H, naphthalene moiety,
J = 7.0 Hz); 4.74 (sept, 1 H, aꢀgroup CHMe2, J = 7.0 Hz); 3.47
[(2,6ꢀDiisopropylphenyl){2ꢀ(2,6ꢀdiisopropylphenylimino)ꢀ
1ꢀethylꢀ1,2ꢀdihydroacenaphthylenꢀ1ꢀyl}amino]diethylgallium (5).
To the solution of dppꢀBIAN (0.50 g, 1.0 mmol) in toluene

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Russ.Chem.Bull., Int.Ed., Vol. 58, No. 11, November, 2009
Tishkina et al.
(sept, 1 H, bꢀgroup CHMe2, J = 6.8 Hz); 3.22 (sept, 1 H,
cꢀgroup CHMe2, J = 6.5 Hz); 2.98 (sept, 1 H, dꢀgroup CHMe2,
J = 6.8 Hz); 1.97 (s, 3 H, eꢀgroup Me); 1.57 (d, 3 H, aꢀgroup
CH(CH3)(Me), J = 7.0 Hz); 1.34 (d, 3 H, aꢀgroup CH(Me)ꢀ
(CH3), J = 7.0 Hz); 1.29 (d, 3 H, bꢀgroup CH(CH3)(Me),
J = 6.8 Hz); 1.20 (d, 3 H, bꢀgroup CH(Me)(CH3), J = 6.8 Hz);
1.07 (d, 3 H, dꢀgroup CH(CH3)(Me), J = 6.8 Hz); 1.02 (d, 3 H,
cꢀgroup CH(CH3)(Me), J = 6.5 Hz); 0.72 (d, 3 H, cꢀgroup
CH(Me)(CH3), J = 6.5 Hz); 0.45 (s, 3 H, fꢀgroup InMe); –0.01
(d, 3 H, dꢀgroup CH(Me)(CH3), J = 6.8 Hz); –0.04 (s, 3 H,
gꢀgroup InMe).
CH(Me)(CH3), J = 6.8 Hz); 1.16 (d, 6 H, CH(CH3)(CH3),
J = 6.8 Hz).
Xꢀray diffraction analysis of compounds 5, 6, and 9. Diffracꢀ
tion data for structures 5 and 6 were collected with a Bruker
SMART APEX II CCD diffractometer (ω—ϕꢀscans, MoꢀKα
radiation, λ = 0.71072 Å, graphite monochromator) at 100 K.
Diffraction data for structure 9 were collected with a Bruker
AXS SMART APEX diffractometer (ω—ϕꢀscans, MoꢀKα radiꢀ
ation, λ = 0.71073 Å, graphite monochromator) at 100 K. The
structures were solved by the direct method using SHELXTL
program15 and refined using the fullꢀmatrix leastꢀsquares on F2.
All nonꢀhydrogen atoms were refined anisotropically. The hydroꢀ
gen atoms were included in idealized positions (Uiso = 0.08 Å3).
SADABS program16 was used to apply absorption correction.
The analysis of difference Fourier syntheses indicated that in
crystal 5 one methyl group is disordered over two positions with
equal occupancies. Ga—C and C—C distances in the disordered
group were refined using free variables.
[(1ꢀAllylꢀ2ꢀ(2,6ꢀdiisopropylphenylimino)ꢀ1,2ꢀdihydroaceꢀ
naphthylenꢀ1ꢀyl){2,6ꢀdiisopropylphenyl}amino]aluminum bromoꢀ
iodide (8). Ether solution containing AlI3 (0.14 g, 0.33 mmol)
(or I2 (0.13 g, 0.5 mmol)) and dppꢀBIAN (0.50 g, 1.0 mmol) was
added to fine powdered aluminum foil. Reaction mixture was
stirred for 12 h until its color turned to stable rich blue. Then the
solution was decantated to remove excess metal.14 Thus formed
ether solution of dppꢀBIANAlI(Et2O) was treated with allyl
bromide (0.14 g, 1.0 mmol); on addtion it changed color from a
blue to buff. The solution was concentrated to yield compound 8
(0.43 g, 55%) as orange crystals. M.p. 193 °C. Found (%):
C, 60.37; H, 5.84. C39H45AlBrIN2 (M = 775.58 g mol–1). Calꢀ
culated (%): C, 60.34; H, 5.80. 1H NMR (200 MHz, C6D6,
This work was financially supported by the Russian
Foundation for Basic Research (Project No. 07ꢀ03ꢀ00545).
References
20 °C), δ: 7.42—7.19 (m, 6 H, 2 C6H3Pri and 1 H, naphthalene
2
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moiety); 7.15 (dd, 1 H, naphthalene moiety, J = 7.0 Hz, J =
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N,N´ꢀ(1ꢀAllylacenaphthylenꢀ1(1H)ꢀylꢀ2(1H)ꢀilidene)bisꢀ
(2,6ꢀdiisopropylbenzenamine) (9). To ether solution of
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C, 85.67; H, 8.64. C39H46N2 (M = 542.78 g mol–1). Calculꢀ
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2
naphthalene moiety); 6.98—6.87 (m, 2 H, naphthalene moiety);
6.74 (d, 1 H, C6H3Pri , J = 7.0 Hz); 5.62 (dtd, 1 H, CH2CHCH2,
2
J = 17.1 Hz, J = 7.0 Hz, J = 10.0 Hz); 5.13 (dd, 1 H,
CH2CHCH2, J = 17.1 Hz, J = 2.0 Hz); 4.79 (dd, 1 H,
CH2CHCH2, J = 10.0 Hz, J = 2.0 Hz); 4.29 (s, 1 H, NH); 3.64
(dd, 2 H, CH2CHCH2, J = 13.3 Hz, J = 7.0 Hz); 3.46 (sept,
1 H, CHMe2, J = 6.8 Hz); 3.33 (sept, 1 H, CHMe2, J = 6.8 Hz);
1.42 (d, 3 H, CH(CH3)(Me), J = 6.8 Hz); 1.36 (d, 3 H,

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Received January 12, 2009;
in revised form October 16, 2009