B. Wrackmeyer et al. / Inorganica Chimica Acta 362 (2009) 3941–3948
3947
g -
5-C5H5)Fe(g5
Table 2
4.9. Tri(ferrocenyl)aluminum THF adduct [{(
C5H4)}3Al(py)] (7(py)) and lithium-tetra(ferrocenyl)alanate [{(g5
C5H5)Fe(
5-C5H4)}4Al]Li (9)
Selected bond lengths (pm) and angles (°)a of the ferrocenes 7(py) (Fig. 3), and
-
[Fc3Si(py)]+b.
g
7(py)
[Fc3Si(py)]+
A mixture of freshly prepared FcLi (624 mg, 3.25 mmol) and
pure, degassed AlCl3 (85 mg, 0.64 mmol) was prepared in a
Schlenk-tube, cooled to ꢀ78 °C, and THF (20 mL) was added. After
stirring for 1 h at ꢀ78 °C and for 20 h at ambient temperature,
volatile materials were removed in vacuo, and toluene-[d8]
(4 mL) was added. Insoluble materials were separated by centrifu-
gation, and the clear liquid was collected to give a mixture con-
taining 7(THF) and some 9(ꢁ THF), along with a small amount
of ferrocene. Pyridine (0.50 mL; 6.18 mmol) was added to this
mixture at 0 °C. The solution was stirred for 1 h and analysed by
NMR spectroscopy to contain 7(py) (ꢂ80%) and 9(x py) (ꢂ10%),
a small amount of ferrocene and several unidentified side prod-
ucts (1H and 13C NMR).
Al–C(1)
Al–C(11)
Al–C(21)
Al–N
C(1)–Al–C(11)
C(1)–Al–C(21)
C(11)–Al–C(21)
C(1)–Al–N
C(11)–Al–N
C(21)–Al–N
C5 (Fe(1))/Al (b1)
197.1(5)
198.2(5)
197.7(5)
200.0(4)
111.3(2)
115.5(2)
113.0(2)
Si(1)–C(1)
Si(1)–C(11)
Si(1)–C(21)
Si(1)–N(31)
C(1)–Si(1)–C(11)
C(1)–Si(1)–C(21)
C(11)–Si(1)–C(21)
C(1)–Si(1)–N(31)
C(11)–Si(1)–N(31)
C(21)–Si(1)–N(31)
183.2(6)
183.3(6)
184.3(6)
185.8(5)
114.9(3)
115.0(3)
107.8(3)
106.8(2)
104.3(2)
107.2(2)
107.21(19)
101.73(18)
106.78(18)
13.9 (bent away
from Fe)
10.5 (towards Fe) C5 (Fe(2))/Si(1) (b2) 7.4 (towards Fe)
6.7 (bent away
from Fe)
C5 (Fe(2))/Al (b2)
C5 (Fe(3))/Al (b3)
C5/C5 (twist) (
C5/C5 (twist) (
C5/C5 (twist) (
s
s
s
1) Fe(1) 5.8
2) Fe(2) 9.0
3) Fe(3) 6.3
4.10. Lithium-tetra(ferrocenyl)alanate [{(g g
5-C5H5)Fe( 5-C5H4)}4Al]Li
(9)
a
See Refs. [18,19] for the definition of the angles b, and s.
Ref. [15].
b
A mixture of freshly prepared FcLi (147 mg, 0.77 mmol) and
freshly prepared 7(THF) (380 mg, 0.65 mmol) was placed into a
Schlenk-tube, cooled to ꢀ78 °C, and THF (5.5 mL) was added.
The mixture was warmed to RT, stirred for 30 min, and volatile
materials were removed in vacuo. The remaining solid was dis-
solved in toluene-[d8] (0.5 mL), a layer of brown-black oil was
formed at the bottom. Then pyridine (finally 1 mL) was added
in several portions. The reaction mixture contained 9(x py)
(about 80%), 7(py) (about 5%) together with ferrocene and
(Fc)2.
clear liquid was evaporated to give 883 mg of 7(THF) together with
FcH.
7(THF): 1H NMR (399.8 MHz; toluene-[d8]; 25 °C): d = 1.11 (m,
THF-Hb), 3.68 (m, THF-H ), 4.17 (s, 15H, Cp), 4.32 (m, 6H, H2,5),
a
4.44 (m, 6H, H3,4).
4.7. Tri(ferrocenyl)aluminum pyridine adduct [{(g -
5-C5H5)Fe(g5
C5H4)}3Al(py)] (7(py))
9(x py) (x ꢂ 100): 1H NMR (399.8 MHz; toluene-[d8]; 25 °C):
d = 4.24 (s, 20H, Cp), 4.41 (m, 8H, H2,5), 4.72 (m, 8H, H3,4), 6.97
(m, py-Hb), 7.34 (m, py-H ), 8.53 (m, py-H ).
Pyridine (0.2 mL, 2.5 mmol) was added to a reaction mixture
containing 7(THF)/FcH (440 mg) in toluene, at ꢀ30 °C. The solu-
tion was stirred for 1 h, insoluble materials were separated by
centrifugation, and the clear liquid was evaporated. The orange-
brown oil thus obtained was washed with hexane (10 mL), the
residue after removing of the hexane was dried in a vacuum to
give 393 mg of a mixture containing 7(py) (about 80%) together
with FcH. Single orange crystals of 7(py) for X-ray analysis were
grown from a toluene-[d8] solution after 2 weeks at ꢀ30 °C; m.p.
220–230 °C.
c
a
9(x py) (x ꢂ 10) in THF: 1H NMR (399.8 MHz; toluene-[d8];
25 °C): d = 1.55 (m, THF-Hb), 3.45 (m, THF-H ), 3.79 (s, 20H, Cp),
a
4.02 (m, 8H, H2,5), 4.22 (m, 8H, H3,4), 6.99 (m, py-Hb), 7.37 (m,
py-H ), 8.37 (m, py-H ).
c
a
Table 3
7(py): 1H NMR (399.8 MHz; toluene-[d8]; 25 °C): d = 4.05 (s,
15H, Cp), 4.40 (m, 6H, H2,5), 4.47 (m, 6H, H3,4), 6.44 (m, 2H, py-
Crystallographic data of the ferrocene 7(py).
7(py)
Hb), 6.79 (m, 1H, py-H ), 8.78 (m, 2H, py-H ).
c
a
Formula
Crystal
C35H32AlFe3N
red-orange prism
0.22 ꢁ 0.18 ꢁ 0.16
monoclinic
4.8. Tri(ferrocenyl)aluminum pyridine adduct [{(
C5H4)}3Al(py)] (7(py)) and chloro(di(ferrocenyl))aluminum pyridine
adduct [{(
5-C5H5)Fe( 5-C5H4)}2AlCl(py)] (8)
g -
5-C5H5)Fe(g5
Dimensions (mm)
Crystal system
Space group
Lattice parameters
a (pm)
b (pm)
c (pm)
b (°)
Z
C2/c
g
g
2085.4(4)
1354.1(3)
2136.8(4)
105.29(3)
8
Freshly prepared FcLi (650 mg, 3.39 mmol) in toluene (40 mL)
as a suspension was cooled to ꢀ20 °C, and pure, degassed AlCl3
(151 mg, 1.13 mmol) was added in one portion. The mixture
was kept stirring for 20 h at room temperature, cooled to 0 °C,
and pyridine (0.18 mL, 2.22 mmol) was added. This solution
was stirred for 1 h, insoluble materials were separated by centri-
fugation, and the clear liquid was evaporated. The orange-brown
oil was washed with hexane (2 ꢁ 10 mL), dried in a vacuum to
give 572 mg of a mixture containing 7(py) (about 60%) and 8
(about 40%) together with a small amount of ferrocene (1H and
13C NMR).
Absorption coefficient
Diffractometer
l
(mmꢀ1
)
1.531
STOE IPDS I (Mo Ka, k = 71.937 pm),
graphite monochromator
1.8–25.9
19 367
5514
None
361
0.0962/0.0472
0.610/ꢀ0.295
Measuring range (#, °)
Reflections collected
Independent reflections [I P 2
Absorption correctiona
Refined parameters
wR2/R1 [I P 2
Maximum/minimum residual electron
density (e pmꢀ3 10ꢀ6
r
(I)]
r(I)]
8: 1H NMR (399.8 MHz; toluene-[d8]; 25 °C): d = 4.17 (s, 10H,
Cp), 4.31 (m, 4H, H2,5), 4.42 (m, 4H, H3,4), 6.44 (m, py-Hb), 6.79
(m, py-H ), 8.78 (m, py-H ).
)
a
Absorption corrections did not improve the parameter set.
c
a