B. Wrackmeyer, E. V. Klimkina, W. Milius
FULL PAPER
phase was carefully decanted and volatile materials were evapo-
rated. The remaining oil was washed with pentane, dissolved in
toluene (20 mL) and pyridine (1.0 mL, 12.4 mmol) was then added.
After stirring the mixture for 2 h, insoluble materials were sepa-
rated by centrifugation, and the clear liquid was collected. Volatile
materials were removed in vacuo to leave an oil that was washed
with pentane and evaporated again to give an orange-yellow resi-
due (720 mg) containing about 90% of 1a together with 5a and
1
13
ferrocene ( H and C NMR). Washing with hexane dissolved most
of the ferrocene and 5a to give 1a (552 mg, Ͼ95%; see Figure 1).
1
Data for 1a: M.p. 230–240 °C. H NMR (399.8 MHz, CD
2
Cl
2
,
2
,5
2
3 °C): δ = –0.58 (s, 12 H, CH
3
Al), 3.91 (m, 4 H, H ), 4.22 (m, 4
), 7.96 (m, py-H ), 8.66 (m, py-H ) ppm.
H NMR (250.1 MHz, CD Cl , –40 °C): δ = –0.62 (s, 12 H,
Al), 3.90 (m, 4 H, H ), 4.21 (m, 4 H, H ), 7.52 (m, py-H
3
,4
H, H ), 7.53 (m, py-H
β
γ
α
1
2
2
2
,5
3,4
CH
.95 (m, py-H
toluene, 23 °C): δ = –0.07 (s, 12 H, CH
3
β
),
1
7
γ α 8
), 8.59 (m, py-H ) ppm. H NMR (399.8 MHz, [D ]
Al), 4.40 (m, 4 H, H ,5),
), 6.73 (m, py-H ), 8.32 (m, py-
) ppm. H NMR (399.8 MHz, [D ]toluene, 80 °C): δ = –0.18 (s,
2
3
3
,4
4
H
.75 (m, 4 H, H ), 6.37 (m, py-H
β
γ
1
α
8
2
,5
3,4
12 H, CH
3
Al), 4.26 (m, 4 H, H ), 4.60 (m, 4 H, H ), 6.56 (m,
), 8.39 (m, py-H
) ppm. Data for 5a: 1
2 3
Cl , 23 °C): δ = –0.57 (s, 6 H, CH Al), 4.01
py-H ), 6.91 (m, py-H
β
γ
α
H
NMR (399.8 MHz, CD
(
2
m, 2 H, H ), 4.08 (s, 5 H, Cp), 4.30 (m, 2 H, H3,4), 7.53 (m, py-
2,5
1
H
β
), 7.96 (m, py-H
γ
), 8.66 (m, py-H
α
) ppm. H NMR (400.1 MHz,
2
,5
[
4
D
8
]toluene, 23 °C): δ = –0.18 (s, 6 H, CH
3
Al), 4.24 (m, 2 H, H ),
.25 (s, 5 H, Cp), 4.45 (m, 2 H, H ), 6.47 (m, py-H ), 6.81 (m,
) ppm. H NMR (399.8 MHz, [D ]toluene,
Al), 4.15 (m, 2 H, H ), 4.17 (s, 5
H, Cp), 4.39 (m, 2 H, H ), 6.57 (m, py-H ), 6.91 (m, py-H ), 8.39
m, py-H ) ppm.
3
,4
β
1
py-H
γ
), 8.33 (m, py-H
α
8
Figure 6. Two different views (see the axes systems) of the arrange-
ments of the enantiomers A and B of 4 in the crystal lattice (the
2 2
CD Cl molecules are not shown).
2,5
8
0 °C): δ = –0.27 (s, 6 H, CH
3
3,4
β
γ
(
α
1
4
b
(Alkyl
.63 mmol) was taken up in hexane (40 mL); the suspension was
AlCl (1.0 in hexane, 9.3 mL, 9.3 mmol)
was added dropwise. The reaction mixture was stirred at 20 °C for
h, cooled to –20 °C and pyridine (1.50 mL; 18.54 mmol) was
2
= Et): Freshly prepared fcLi (tmeda) (1454 mg,
2 2
were used throughout. The deuterated solvent CD Cl was distilled
cooled to –10 °C and Et
2
from CaH under an atmosphere of argon. All other solvents were
2
distilled from Na metal under an atmosphere of argon. Starting
3
materials such as BuLi (1.6 in hexane), aluminum trichloride (an-
added. The mixture was kept stirring at room temperature for 20 h.
After centrifugation, the supernatant liquid phase was carefully de-
canted and volatile materials were evaporated. The resulting oil was
dissolved in toluene (30 mL), and from the clear liquid phase after
centrifugation and evaporation an oily residue was left. This was
washed with pentane to leave an orange-red residue (955 mg) con-
taining about 90% of 1b (together with 2b, 4, 5b and ferrocene,
hydrous, powder 99.999% metal basis), Me
anes), MeAlCl (1.0 solution in hexanes), EtAlCl
in toluene) (all from Aldrich), Et AlCl (1.0 in hexane) (Acros),
pyridine (anhydrous, 99.8%) (Aldrich) were commercial products
2
AlCl (1.0 in hex-
2
2
(1.8 solution
2
and used as received. The compound fcLi
2
(tmeda)[ was prepared
20]
by literature procedures. NMR measurements: Bruker ARX 250:
1
H, C, Al NMR; Varian INOVA 400: 1H, C, Al NMR;
13
27
13
27
1
13
1
about 10%; H and
399.8 MHz, CD Cl , 23 °C): δ = 0.16 (q, J = 8.2 Hz, 8 H, CH
.11 (t, J = 8.2 Hz, 12 H, CH
C
NMR). Data for 1b:
H
NMR
Al),
), 3.95 (m, 4 H, H ), 4.26 (m, 4 H,
1
chemical shifts are given with respect to SiMe
5
5
D
4
[δ H(CHDCl
2
) =
=
(
1
2
2
2
1
13
.33 ppm, δ H(C
6
D
5
CD
CD ) = 20.4 ppm]; external 1.1 Al(NO
O [δ Al = 0 for δ( Al) = 26.056890 MHz]. The melting points
2
H)
=
2.08 ppm; δ C(CD
2
Cl
2
)
)
2,5
3
13
3.8 ppm, δ C(C
6
D
5
3
3
3
in
3,4
1
H
), 7.58 (m, py-H
β
γ α
), 8.01 (m, py-H ), 8.66 (m, py-H ) ppm. H
27
27
2
NMR (399.8 MHz, [D
8
]toluene, 23 °C): δ = 0.59 (q, J = 8.2 Hz, 8
(uncorrected) were determined by using a Büchi 510 melting point
2,5
H, CH Al), 1.48 (t, J = 7.2 Hz, 12 H, CH
2
3
), 4.38 (m, 4 H, H ),
), 6.77 (m, py-H ), 8.33 (m, py-
) ppm. H NMR (399.8 MHz, [D ]toluene, 90 °C): δ = 0.49 (q,
Al), 1.39 (t, J = 8.2 Hz, 12 H, CH ), 4.24 (m,
H, H ), 4.58 (m, 4 H, H3,4), 6.56 (m, py-H
), 6.95 (m, py-H ),
) ppm. Data for 5b: H NMR (399.8 MHz, CD Cl
3 °C): δ = 0.18 (q, J = 8.2 Hz, 4 H, CH Al), 1.12 (t, J = 8.2 Hz,
), 4.05 (m, 2 H, H ), 4.10 (s, 5 H, Cp), 4.32 (m, 2 H,
apparatus. Owing to the extreme sensitivity of the new compounds
to air and moisture, a notorious property of organoaluminum com-
pounds, elemental analysis did not give reliable results. Attempts to
measure mass spectra (MS, EI, 70 eV) did not reveal the respective
3,4
4
H
.74 (m, 4 H, H ), 6.40 (m, py-H
β
γ
1
α
8
J = 8.2 Hz, 8 H, CH
2
3
2,5
4
8
2
6
β
γ
molecular ions. Instead, the pattern of diferrocene (CpFeC
was observed.
5
H
4
)
2
1
.44 (m, py-H
α
2
2
,
2
2
,5
H, CH
3
1,1Ј-Bis(dialkylalanyl)ferrocene Dipyridine Adducts 1
3
,4
1
H
β γ α
), 7.65 (m, py-H ), 8.06 (m, py-H ), 8.62 (m, py-H ) ppm. H
1a
(Alkyl Me): Freshly prepared fcLi (tmeda) (1092 mg,
=
2
NMR (399.8 MHz, [D ]toluene, 23 °C): δ = 0.42 (q, J = 8.2 Hz, 4
8
3
.48 mmol) was taken up in toluene (30 mL); the suspension was
AlCl (1.0 in heptane, 7.0 mL,
.0 mmol) was added dropwise. The reaction mixture was stirred
at –15 °C for 1 h and pyridine (1.0 mL, 12.4 mmol) was added at
°C. Then, the mixture was allowed to reach ambient temperature
whilst stirring for 20 h. After centrifugation, the supernatant liquid
H, CH Al), 1.36 (t, J = 8.2 Hz, 6 H, CH ), 4.19 (s, 5 H, Cp), 4.21
2
3
2
,5
3,4
cooled to –15 °C and Me
7
2
(m, 2 H, H ), 4.42 (m, 2 H, H ), 6.54 (m, py-H ), 6.92 (m, py-
β
H ), 8.29 (d, py-H ) ppm.
γ
α
0
1,1Ј-Bis(diethylalanyl)ferrocene Dipyridine Adduct 1b and 1-Diethyl-
alanyl-1Ј-chloro(ethyl)alanylferrocene Dipyridine Adduct 2b: Freshly
3160
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© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2009, 3155–3162