On the chemistry of gallium: Part 19. Synthesis and crystal structure analysis of novel complexes containing Ga-FeCp(CO)2-fragments

Article abstract of DOI:10.1016/S0022-328X(01)00656-8

The gallium subhalides Ga₂Cl₄·2dioxane and sonochemically prepared GaI were reacted with the carbonyl ferrate K[Cp(CO)₂Fe] and the iron carbonyl dimer [Cp(CO)₂Fe]₂, respectively. In all the reactions

Full text of DOI:10.1016/S0022-328X(01)00656-8

Journal of Organometallic Chemistry 626 (2001) 82–91
www.elsevier.nl/locate/jorganchem
ꢀ
On the chemistry of gallium
Part 19. Synthesis and crystal structure analysis of novel
complexes containing Ga–FeCp(CO) -fragments
2
Gerald Linti *, Guangming Li, Heinz Pritzkow
Anorganisch-Chemisches Institut, Uni6ersit a¨ t Heidelberg, Im Neuenheimer Feld 270, D-69120 Heidelberg, Germany
Received 19 October 2000; received in revised form 21 November 2000; accepted 21 December 2000
Abstract
The gallium subhalides Ga Cl ·2dioxane and sonochemically prepared GaI were reacted with the carbonyl ferrate
2
4
K[Cp(CO) Fe] and the iron carbonyl dimer [Cp(CO) Fe] , respectively. In all the reactions performed, the gallium(I) and
2
2
2
gallium(II) compounds disproportionated into elemental gallium and gallium(III) compounds. Several novel complexes containing
Ga–FeCp(CO) fragments were isolated and characterized spectroscopically and by X-ray crystal structure analysis. These are
2
−
+
compounds of the types Cp(CO) FeGaX (B) [B=THF, dioxane, I [FeCp(C H )] ; X=Cl, I] and [Cp(CO) Fe] GaCl(B)
2
2
7
8
2
2
[
B=THF, 0.5 KCl]. In addition, the cage compounds [Cp(CO) FeGa] (m -O) (m-OH) I and [Cp(CO) FeGa] FeK (OEt ) (m -
2
6
3
4
2 2
2
4
2
2 4
3
O) (m-Br) (m -Br) were isolated. In all these complexes the gallium atoms are surrounded tetrahedrally by substituents. GaꢀFe
bond lengths are in the range of 231–239 pm. © 2001 Elsevier Science B.V. All rights reserved.
2
4
3
4
Keywords: Gallium; Iron; Galliumꢀiron bond; Crystal structure analysis
the reactions of the gallium halides ‘‘GaI’’ [13] and
1. Introduction
Ga X ·2dioxane (X=Cl, Br) with K[FeCp(CO) ] and
2
4
2
[
FeCp(CO)2]2.
Complexes of transition metals with ligands having a
Group 13 element atom as a ligating atom have gained
interest during the past years [2–6]. This is mainly due
to the use of such complexes as single-source precursor
molecules in MOCVD [3]. On the other hand, the
alleged analogy between CO and RE-fragments [E=
Group 13 element] in their coordination properties has
been discussed controversially [7–9]. Some of the struc-
turally characterized complexes with GaꢀFe bonds are
summarized in Table 1. Most of these compounds have
been prepared starting from gallium(III) halide deriva-
tives. However, having in mind the great variety of
gallium cluster compounds [1,10–12] available from
gallium subhalides by reaction with bulky alkalimetal
silanides, reactions between carbonylmetalates and gal-
lium subhalides seem rewarding. Herein, we report on
2. Synthesis and reactions
In order to obtain compounds with GaꢀFe bonds,
gallium halides may be treated with metal-bases like
carbonyl ferrates. An alternative method to salt elimi-
nation reactions is a metathesis between compounds
with GaꢀGa and FeꢀFe bonds: if Ga Cl ·2dioxane is
reacted with one equivalent of [FeCp(CO) ] in boiling
toluene, yellow crystals of 1a and 1b are obtained in
good yields by crystallization from a THF–ether mix-
ture and toluene, respectively. Obviously, Ga Cl ·
2
4
2 2
2
4
2
dioxane serves as a source for GaCl (donor) radicals,
2
which can combine with the 17 valence electron frag-
ment FeCp(CO) to form 1. 1a and 1b are similar to
2
[
Cp(CO) FeGaCl (NMe )] [14], which was prepared
2 2 3
from GaCl (NMe)3 and K[FeCp(CO) ] in THF at
ꢀ
3
2
For Part 18, see Ref. [1].
Corresponding author. Tel.: +49-6221-548529; Fax: +49-6221-
−
78°C. A similar reaction using [Ru (CO) ] afforded
3 12
*
the RuGa3 complex [(CO) Ru{GaCl(THF) }{GaCl -
5
0
46617.
3
2
2
E-mail address: gerald.linti@urz.uni-heidelberg.de (G. Linti).
(THF)} ] [15].
2
022-328X/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(01)00656-8

G. Linti et al. / Journal of Organometallic Chemistry 626 (2001) 82–91
83
Table 1
Some structurally characterized compounds with GaꢀFe bonds
Complexes
d(GaꢀFe) (pm)
w˜ (CꢀO) (cm−1)
References
[
[
[
[
[
[
[
[
[
[
[
[
[
(CO) Fe–GaAr*]
222.48
225.6
227.71
233.7
233.78
236.18
237.5
238.18
240.6, 241.6
241.58
242.72
243.6–245.6
251.0
2032(s), 1959(s), 1941(vs), 1929 (vs)
2038, 1985, 1959
2037(s), 1966(s), 1942(vs)
2001(s), 1993(vs), 1976(vs), 1923 (vs), 1986(vs)
2011(vs), 1928(vs), 1881(vs)
1989(vs), 1934(vs)
[32]
[7]
4
(CO) Fe–GaPh*]
4
(CO) Fe–GaCp*]
[33]
[34]
[3,35]
[14]
[36]
[27]
[22]
[37]
[13,38]
[17]
[39]
4
Cp(CO) FeGaS]2
2
(CO) Fe–GaCl (tmeda)]
4
2
Cp(CO) Fe–GaCl(NMe )]
2
3
N
Cp(CO) Fe–Ga(R )(BH )]
1975(vs), 1920 (vs)
1964(s), 1921(s)
2
4
Fe (CO) {m-GaSi(SiMe ) } ]
2
6
3 3 3
t
{Cp(CO) Fe} Ga( Bu)]
1978(vw, sh), 1967(vs), 1927(vs), 1915(vw)
1952(vs), 1874(vs, sh), 1851(vs), 1827(vs, sh)
–
1987(m), 1965(s), 1929(s)
–
2
2
2
−
(CO) Fe–Ga(Me)–Fe(CO) ]
4
4
1
Cp(CO) Fe–Ga(h -C H Me) (NC H )]
2
5
4
2
5
5
{Cp(CO) Fe} Ga]
2
3
1
(CO) Fe–Ga(h -C H )(THF)]
4
2
3
2
ent temperatures affords 1a and b (Eq. (3)), too. In
addition, orange red crystals of 5 are isolated. During
this reaction the deposition of elemental gallium is
observed which indicates a disproportionation reaction.
If four equivalents of K[FeCp(CO) ] are used in a
2
similar reaction (Eq. (4)) no iron substituted digallane
is isolated, either. The same kind of redox dispropor-
tionation takes place and well-shaped orange crystals of
(
1)
6
are isolated.
(3)
There is some resemblance of the reaction according
to Eq. (1) to the reaction between InCl and
FeCp(CO) ] [16]. Here, an oxidative addition of the
[
2
2
FeꢀFe bond to the indium(I) fragment takes place to
form 2.
The analogous reaction (Eq. (2)) between Green’s
‘
‘GaI’’ and [FeCp(CO) ] in toluene does not allow the
2 2
isolation of [Cp(CO) Fe] GaI although GaI insertion
2
2
(4)
reactions into metal–halide bonds have been described
13]. This is understandable, because ‘‘GaI’’ consists
[
+
2−
predominantly of (Ga ) [Ga I ]
[1]. Instead, the
2
2 6
+
sandwich
[
cation
[CpFe(toluene)]
as
the
−
CpFe(CO) GaI ] salt, 3, is isolated in minor yield. In
2
3
addition a [FeCp(CO) ] substituted hexanuclear gallium
2
oxo/hydroxo cage 4 is formed in this reaction by partial
oxidative hydrolysis.
(5)
(
2)
Both
5
and
6
are Lewis-base adducts to
A salt elimination reaction between Ga Cl ·2dioxane
2
4
[Cp(CO) Fe] GaCl, which is known as dimer 7 [17]. In
6, the Lewis-base is a K(OEt ) Cl unit, which links two
2 2
2
2
and two equivalents of K[FeCp(CO) ] in THF at ambi-
2

8
4
G. Linti et al. / Journal of Organometallic Chemistry 626 (2001) 82–91
Table 2
Selected spectroscopic data for the complexes 1a, b, 5, 6 and 8
IR ( w˜ CꢀO (cm−1)) MSa
NMR (THF-d8)
+
’
+
’
’
1
13
1
1
1
5
6
8
a
1990.4s, 1935.4s
1989.6s, 1933.8s
1992.1s, 1982.1s,
316 (13) M , 290 (27) [M–CO]
l H (ppm)=4.96 (s, 5H, C H ); l C{ H} (ppm)=83.5
5
5
(
C H ), 215.1 (CO)
5 5
+
1
13
1
b
318 (24) [(C H ) Fe(CO) GaCl ] , 290 (31)
l
H (ppm)=4.96 (s, 5H, C H ); l C{ H}
5 5
5
5 2
2
2
’
+
[
(C H ) Fe(CO) GaCl −CO]
(ppm)=83.5 (C H ), 215.1 (CO)
5
5 2
2
2
5 5
+
’
+
’
1
13
1
458 (2) [M] , 430 (22) [M−CO]
l H (ppm)=4.87 (s, 10H, C H ); l C{ H}
5 5
1
971.4s, 1935.7s
(ppm)=83.7 (C H ), 217.3 (CO)
5 5
+
’
1
13
1
2003.7s, 1933.7s
458 (7) [[(C H ) Fe(CO) ] GaCl] , 430 (55)
l H (ppm)=4.86 (s, 10H, C H ); l C{ H}
5 5
5
5 2
2 2
+
’
[
[(C H ) Fe(CO) ] GaCl−CO]
406 (2) [GaBr C H Fe(CO) ] , 378 (10)
(ppm)=83.7 (C H ), 217.3 (CO)
5
5 2
2 2
5 5
+
’
1
13
1
1997.5s, 1946.6s
l H (ppm)=5.10 (s, 5H, C H ); l C{ H} (ppm)=84.1
5 5
2
5
5
2
+
’
[
GaBr C H Fe(CO) −CO]
(C H )
5 5
2
5
5
2
a
Most intense m/z from the isotopic pattern.
[
Cp(CO) Fe] GaCl molecules, forming a unique bicyclic
tions. The molecule of 1a (Fig. 1) exhibits a gallium
atom that is tetrahedrally coordinated by an iron, two
chlorine atoms and one oxygen atom. The iron atom is
further coordinated by a Cp-ring and two CO ligands.
2
2
KGa Cl ring.
2
3
The analogous reaction (Eq. (5)) between Ga Br ·
2
4
2
dioxane and two equivalents of K[FeCp(CO) ] did not
2
afford a bromine-analog to 1 or 5. After work-up and
crystallization from diethylether the only GaꢀFe com-
pound isolated is the unexpected cage compound 8.
The bonding parameters of the Cp(CO) Fe fragment
are in the normal range. The GaꢀFe bond length is
2
2
31.7 pm. This is 5 pm shorter than the GaꢀFe bond
length in the related complex Cp(CO) FeGaCl (NMe )
2
2
3
[14] (compare Table 1). This shortening of the GaꢀFe
bond is caused by the replacement of the coordinated
amine by a more electron withdrawing THF molecule.
The dependence of the GaꢀFe bond length on the
electronegativity of the substituents at the gallium cen-
ter has already been proven in compounds of the type
3
. Spectroscopic characterization
The IR spectra (KBr pellet) of compounds 1a, b, 5, 6
and
8
show the typical absorption bands for
Cp(CO) Fe fragments (Table 2). The high-energy car-
2
bonyl vibrations in the GaꢀFe compounds are observed
Cp(CO) FeGaX (NR ) [3]. For X=halide, the GaꢀFe
2 2 3
at higher wave numbers than in K[FeCp(CO) ] [18], but
bond is up to 10 pm shorter than for X=alkyl. Obvi-
ously, the GaꢀFe bond resembles somewhat the GaꢀSi
bond, the length of which varies in compounds of the
type (Me Si) SiGaX (THF) with the electronegativity
2
they are in a similar region than that of [CpFe(CO)2]2
[
19]. From a simple viewpoint this is in unison with the
less ionic character of the GaꢀFe bond compared to the
KꢀFe interactions.
3
3
2
of X [20]. (Me Si) SiGaCl (THF) in particular has very
3
3
2
Because of their low solubility in less polar solvents,
the NMR spectra of 1a, b, 5 and 6 were recorded in
THF. Consequently, the H- and C-NMR spectra of
similar GaꢀCl and GaꢀO bond lengths if compared to
1a. The bond angles at the gallium center in both
compounds are quite similar, too.
1
13
1a and b, 5 and 6 are not distinguishable due to
(
1
b crystallizes in the triclinic space group P1, too.
The molecule of 1b resides on a center of symmetry
Fig. 2). Thus, dioxane molecule links two
Cp(CO) FeGaCl units. The GaꢀFe and GaꢀCl bonds,
dioxane–THF and KCl–THF exchange, respectively.
The mass spectra (EI) of 1a and b show the donor
(
a
+
’
and its fragmentation. The
free [Cp(CO) FeGaCl ]
2
2
2
2
spectrum of 1b shows fragmentation of a dimer in
low intensity, too. The mass spectra for 5 and 6 are
very similar, exhibiting the fragmentation of
as well as the bond angles at the gallium center resem-
ble those of 1a. The main difference is the GaꢀO
distance, being 10 pm longer in 1b than in 1a, which
demonstrates the different donor properties of THF
and dioxane.
[
Cp(CO) Fe] GaCl. The cage compound 8 is degraded
2
2
to Cp(CO) FeGaBr , the radical cation of which is
2
2
observed as the highest mass peak.
3
crystallizes in the triclinic space group P1 with
(
1
Z=4. Due to the extremely thin crystal plates the data
set obtained is a very crude one. Therefore, the struc-
tural parameters are not to be discussed in detail. 3
4. Crystal structure analysis
1
a crystallizes in the triclinic crystal system, space
group P1 (Table 3). Both independent molecules in the
asymmetric unit are identical within the standard devia-
(
1
In spite of the nearly monoclinic cell dimensions, structure solu-
tion and refinement was only possible in P1.
(

G. Linti et al. / Journal of Organometallic Chemistry 626 (2001) 82–91
85
(
Fig. 3) is an ion pair of a CpFe(toluene) sandwich
bridging ClꢀGa distances in Ga Cl [21]. The GaꢀFe
2
6
−
cation. The anion is [Cp(CO) FeGaI ] . The Ga–Fe
bond length is 236 pm. This is longer than in 1a and b,
distances are longer than in 1a, yet similar to the ones
2
3
t
in sterically strained (Cp(CO) Fe) Ga Bu [22].
2
2
but in the typical range for Cp(CO) FeGaX (donor)
6 crystallizes in the monoclinic crystal system, space
group C2/c. In analogy to 5, it may be viewed upon as
a Lewis-base adduct of [Cp(CO) Fe] GaCl (Fig. 5).
2
2
compounds.
, the THF adduct of [Cp(CO) Fe] GaCl, crystallizes
5
2
2
2
2
in the monoclinic space group P2 /n (Fig. 4). The
This subunit consists of Ga(1), Fe(1), Fe(2) and Cl(2).
The GaꢀFe and GaꢀCl bonds are similar to those in 5.
The same is true for the Fe(1)ꢀGa(1)ꢀFe(2) (130.9°),
Fe(1)ꢀGa(1)ꢀCl(2) (109.5°) and Fe(2)ꢀGa(1)ꢀCl(2)
(106.6°) angle. The Lewis-base is a K(OEt ) Cl unit,
which coordinates via its chlorine atom [Cl(1)] to
Ga(1). This Ga(1)ꢀCl(1) contact is 25 pm longer than
the Ga(1)ꢀCl(2) distance. In addition, Cl(2) coordinates
to the potassium center. Thus, a four-membered, flat
1
central gallium atom is coordinated tetrahedrally by
two iron atoms, one chlorine atom and one oxygen
atom. The bond angles deviate markedly from the
tetrahedral angle; i.e. the Fe(1)ꢀGa(1)ꢀFe(2) angle is
2
2
very wide, due to the steric demand of the Cp(CO) Fe
2
groups. In contrast, the O(5)ꢀGa(1)ꢀCl(1) angle is near
90°. This deformation of the coordination sphere
around the gallium atom results in long GaꢀO and Cl
bonds. Compared to 1a, the GaꢀTHF distance is
butterfly-type GaCl K ring results [torsion angle
2
lengthened by 23 pm. The Ga(1)ꢀCl(1) bond [dGaCl
=
Cl(1)Ga(1)Cl(2)K(1)=11°]. Cl(1) does not coordinate
2
29.0(2) pm] is out of the typical range for terminal
to only one GaFe Cl unit; together with a second one,
2
GaꢀCl bonds [dGaCl5222 pm], and is as long as the
a bicyclo[2.2.0]hexane type structure results. One of the
Table 3
Crystal data and data collection parameters
1
a
1b
3
5
6
8
4
Formula
C11H13Cl Fe- C18H18Cl Fe - C19
H
I Fe -
C18H18ClFe2- C36H40Cl Fe -
C44H60Br Fe - C42
H
I Fe -
2
4
2
18 3
2
3
4
8
5
32 2
6
GaO3
389.7
0.35×0.35
×0.2
Ga O
723.2
0.4×0.3
×0.25
Triclinic
GaO2
840.5
0.15×0.1
×0.005
Triclinic
GaO5
531.2
0.4×0.2
×0.2
Monoclinic
Ga KO ·(C H10O) Ga K O
Ga O ·(C H10O)
2
6
2
10
4
4
2
14
6 18 4
M
1141.0 (1215.1)
0.25×0.25
×0.15
Monoclinic
C2/c
2088.5
0.20×0.15
×0.10
1832.0 (1906.1)
0.18×0.12
×0.02
Crystal size
3
(
mm )
Crystal system
Space group
a (pm)
b (pm)
c (pm)
h (°)
i (°)
k (°)
V (nm )
Triclinic
Monoclinic
Monoclinic
P1
(
P1
(
P1
(
P2 /n
P2 /n
P2 /n
1
1
1
1090.8(2
1163.5(2)
1226.2(3)
97.20(3)
104.22(3)
93.23(3)
1.4905(5)
4
678.1(14)
725.5(15)
1375.7(3)
104.8(3)
94.02(3)
107.99(3)
0.6141(2)
1
1194.1(2)
1024.7(2)
2421.7(5)
89.93(3)
89.96(3)
86.74(3)
2.958(1)
4
795.4(2)
1784.0(4)
1390.8(3)
90
96.64(3)
90
1.9603(7)
4
1.800
2.987
1064
2003.3(4)
1172.7(2)
2111.1(4)
90
1288.3(3)
2607.9(5)
2164.0(4)
90
1248.3(1)
1188.2(1)
1959.9(1)
90
91.55(1)
90
2.906(1)
2
2.16
116.99(3)
90
104.23(3)
90
3
4.419(1)
4
7.05(1)
4
Z
€calc. (kg m−3)
1.737
3.134
776
1.956
3.795
356
1.887
5.011
1560
1.715
2.807
2288
1.968
7.205
4032
−
1
v (mm
F(000)
)
5.31
1808
Index range
qmax (°)
9h9k9l
50
9h9k9l
52
9h9k9l
52
hk9l
50
9hkl
50
9h9k9l
52
9hkl
51
2
T (K)
190
190
190
190
223
190
190
Reflections
collected
5259
4759
21120
3978
3894
49965
5613
Reflections
unique
5240
3991
325
2198
2062
145
10760
6593
3431
3010
245
3894
3349
256
13097
8187
5326
3913
Reflections
observed (4|)
Parameters
Weighting
scheme x/ya
525
0.1/0
702
0.0481/0
353
0.0442/19.08
0.1149/5.2444 0.111/0
0.0606/10.8833 0.0572/0
Goodness-of-fit 1.084
1.098
2.919
1.080
1.268
0.868
1.040
on F2
R(4|)
wR2
0.067
0.205
0.061
0.156
1.40
0.171
0.492
8.1
0.052
0.140
2.53
0.035
0.105
0.73
0.042
0.098
0.76
0.041
0.100
1.65
Large res. peak 1.26
−
3
(
A
,
)
a
w−1=| F +(xP) +yP; P=(F +2F )/3.
2
2
2
2
2
o
o
c

8
6
G. Linti et al. / Journal of Organometallic Chemistry 626 (2001) 82–91
1
46.1°. This may be caused by two short KꢀH contacts
(
dKꢀH=304 pm) to methylene groups of the coordi-
nated ether molecules. Quantum chemical calculations
on the RI-DFT level with a def-SVP base and the BP86
functional [23] have been performed on
a
[
H GaCl] K(H O) Cl model, 9. The results of the calcu-
2
2
2
2
lation (Fig. 6) reveal a bicyclic structure similar to 6.
Especially the trend of the bond lengths, short and long
GaCl contacts is confirmed. The main difference be-
tween 6 and 9 is the bond angle at Cl(1). In 9, this angle
is found to be 113°, far from linear. This is probably
due to the substitution of the bulky Cp(CO) Fe groups
2
by hydrogen.
8
, the disproportionation product of the reaction
between Ga Br ·2dioxane and K[Cp(CO) Fe], crystal-
2
4
2
lizes in the monoclinic space group P2 /n. The com-
1
Fig. 1. View of a molecule of 1a. Selected bond lengths (pm) and
angles (°): Ga(1)ꢀFe(1) 231.7(1), Ga(1)ꢀCl(1) 222.0(2), Ga(1)ꢀCl(2)
22.0(2), Ga(1)ꢀO(1) 199.7(5); Cl(1)ꢀGa(1)ꢀCl(2) 104.51(9),
plicated cage compound may be described as being
built by two Cp(CO) FeGa(Br)-O-Ga(Br)Fe(CO) Cp
2
2
2
molecules which are linked together by two K(OEt ) Br
2
2
O(1)ꢀGa(1)ꢀCl(1) 95.0(2), O(1)ꢀGa(1)ꢀCl(2) 97.7(2), O(1)ꢀGa(1)ꢀ
Fe(1) 115.7(1), Cl(1)ꢀGa(1)ꢀFe(1) 115.71(7), Cl(2)ꢀGa(1)ꢀFe(1)
units and a FeBr2 unit (Fig. 7). This iron atom is
coordinated octahedrally by four bromine atoms and
the oxygen atoms of the digalloxane mentioned above.
Each of the four bromine atoms coordinates to a
1
19.44(7).
most striking features of this heterocycle is a T-shaped
gallium atom, which is tetracoordinated by
a
Ga ClK unit with a Ga(1)ꢀCl1ꢀGa(1)c angle of
2
Cp(CO) Fe group, an oxygen atom and two bromine
175.5° at the triple coordinated chlorine atom. The
2
potassium center K(1) is penta-coordinated by three
chlorine atoms and two oxygen atoms of two di-
ethylether molecules. The K(1)ꢀO(5) [O(5)c] distance
is 261.8 pm, which is normal for KꢀO distances. The
three KꢀCl contacts are nearly equal and in the typical
range.
The trigonal bipyramidal coordination polyhedron at
the potassium center is severely distorted, i.e. the
Cl(2)ꢀK(1)ꢀCl(1)c angle is not linear but equals
atoms. Both of the bromine atoms at a gallium center
coordinate a potassium atom. The latter is hexacoor-
dinated by four bromine atoms and two ether
molecules. The KꢀBr and FeꢀBr distances are in the
expected range. The terminal GaꢀFe bonds
[dGaFe(aver.)=233 pm] are short. This is consistent with
the structural discussion for 1a and b. The GaꢀO
distance [dGaO=186.0(3)−186.5(3) pm] is longer than
in an other organometallic digalloxane; in [(CO) Mn-
5
Fig. 2. View of a molecule of 1b. Selected bond lengths (pm) and angles (°): Ga(1)ꢀFe(1) 231.64(9), Ga(1)ꢀCl(1) 222.8(1), Ga(1)ꢀCl(2) 220.2(1),
Ga(1)ꢀO(3) 209.6(2); Cl(1)ꢀGa(1)ꢀCl(2) 105.62(5), O(3)ꢀGa(1)ꢀCl(1) 95.02(7), O(3)ꢀGa(1)ꢀCl(2) 96.09(8), O(3)ꢀGa(1)ꢀFe(1) 112.03(8),
Cl(1)ꢀGa(1)ꢀFe(1) 122.05(4), Cl(2)ꢀGa(1)ꢀFe(1) 120.19(4).

G. Linti et al. / Journal of Organometallic Chemistry 626 (2001) 82–91
87
Fig. 3. View of the independent ion pairs 3. Hydrogen atoms have been omitted for clarity. Selected bond lengths (pm): GaꢀFe 236.1(7), GaꢀI
2
62.9(5)ꢀ264.6(5).
i
2
Ga(C H Pr )] O the GaꢀO distance is 179 pm [24]. This
5. Conclusions
6
3 2
is not unexpected, because the oxo bridges in 8
O(9),O(10)] are triple coordinated. Consequently, the
GaꢀO(9,10)ꢀGa angles are less wide (132°) than in the
monomeric digalloxane [GaOGa=150.2(15)°].
[
The reaction of [Cp(CO)
2
Fe]
2
as well as of
K[Cp(CO)
Fe] with gallium subhalides results in dis-
Fe-
2
proportionation reactions, yielding various Cp(CO)
2
By the reaction of ‘‘GaI’’ with [Cp(CO) Fe] 3 was
obtained as well as the gallium oxo-/hydroxo cage
compound 4 (Fig. 8). It crystallizes monoclinic, space
substituted gallium halide derivatives. The structural
variety possible is documented with bicyclic 6 and the
novel cage compounds 4 and 8. Especially, the use of
2
2
group P2 /n. The core of centrosymmetric 4 consists of
Ga X ·2donor as a source for the GaX (donor) group
2 4 2
1
six gallium and six oxygen atoms. Each of the tetraco-
will be explored further. The reaction with other
ordinated gallium atoms bears a Cp(CO) Fe group with
metal–metal bonded complexes is to be examined, but
2
a relatively short GaꢀFe distance. Ga(1) and Ga(2) are
connected to three oxygen atoms. Therefore, their
GaꢀFe bond [dGaFe=233.5 pm] is a bit shorter than
that of Ga(3) [dGaFe=234.4 pm], having only two
oxygen neighbors. Additionally, Ga(3) is bonded to an
iodine atom. All GaꢀO distances are similar
(
dGaO(aver.)=191 pm), unless the oxo atoms O(1) and
O(2) bridge three gallium atoms and the hydroxo group
O(2) only two. The GaꢀO cage may be roughly de-
scribed as a distorted hexagonal prism, because no
bonding interaction between Ga(3) and O(2)c
[
Ga(3)c and O(2)] occurs. 4 represents a new type of
GaꢀO cages. Taking into account the empirical formula
R Ga O (OH) I , the compounds Mes Ga O (OH)
6
6
4
2 2
6
6
4
4
[
25] and Mes Ga O F [26] seem to be closely related,
6 6 4 4
but there is a striking difference. In both compounds,
OH groups and fluorine atoms are m -bridging, while
3
the iodine atoms in 4 are terminal and the hydroxo
groups are of m -type. The consequence is a more open,
Fig. 4. View of a molecule of 5. Hydrogen atoms have been omitted
for clarity. Selected bond lengths (pm) and angles (°): Ga(1)ꢀFe(1)
2
less symmetric cage for 4 compared to the mesityl
2
39.2(1), Ga(1)ꢀFe(2) 238.8(1), Ga(1)ꢀCl(1) 229.0(2), Ga(1)ꢀO(5)
22.9(5); Fe(1)ꢀGa(1)ꢀFe(2) 129.51(4), Fe(1)ꢀGa(1)ꢀCl(1) 110.72(6),
compounds. Other GaꢀO cages are of adamantine type
2
t
1
[
27,28] or are higher nuclear cages like Ga Bu O -
2
12 10
Fe(2)ꢀGa(1)ꢀCl(1) 108.53(6), Fe(1)ꢀGa(1)ꢀO(5) 106.7(1), Fe(2)ꢀ
Ga(1)ꢀO(5) 101.9(2), O(5)ꢀGa(1)ꢀCl(1) 92.6(1).
(
OH) [29].
4

8
8
G. Linti et al. / Journal of Organometallic Chemistry 626 (2001) 82–91
Fig. 5. View of a molecule of 6. Hydrogen atoms have been omitted
for clarity. Selected bond lengths (pm) and angles (°): Ga(1)ꢀFe(1)
2
2
37.70(8), Ga(1)ꢀFe(2) 237.7(1), Ga(1)ꢀCl(1) 258.19(6), Ga(1)ꢀCl(2)
33.5(1), K(1)ꢀCl(1) 306.1(2), K(1)ꢀCl(2) 304.9(1), K(1)ꢀO(5) 261.8;
Fe(1)ꢀGa(1)ꢀFe(2) 130.94(3), Cl(1)ꢀGa(1)ꢀCl(2) 95.26(4), Ga(1)ꢀ
Cl(1)ꢀGa(1)c 175.51(6), Ga(1)ꢀCl(1)ꢀK(1) 92.25(3).
Fig. 7. View of a molecule of 8. Hydrogen atoms and diethylether
carbon atoms have been omitted for clarity. Selected bond lengths
(
1
2
pm) and angles (°): Ga(1,2)ꢀO(10) 186.5(3), Ga(3,4)ꢀO(9) 186.0(3),
86.5(3), GaꢀFe 232.8(1)ꢀ233.1(1), Ga(1)ꢀBr(3) 250.4(1), Ga(1)ꢀBr(6)
43.2(1); FeꢀBr(1–4) 277.7(1)ꢀ280.9(1), K(1)ꢀBr(3,4) 328.9(2),
K(1)ꢀBr(6) 325.4(2); FeꢀO(9,10) 194.9(3).
Fig. 6. View of the calculated structure 9. Selected bond lengths (pm)
and angles (°): Ga(1)ꢀCl(1) 247.7, Ga(2)ꢀCl(1) 243.5, Cl(1)ꢀK 322.9,
Cl(2)ꢀK 309.5, Cl(3)ꢀK 327.6, Ga(1)ꢀCl(2) 227.8, Ga(2)ꢀCl(3) 230.3;
Ga(1)ꢀCl(1)ꢀGa(2) 112.8.
particularly the investigation of oxidative additions of
GaꢀGa bonds to unsaturated transition metal centers is
a promising project.
6. Experimental
All procedures were performed under purified nitro-
gen or in vacuum using Schlenk techniques. NMR:
Bruker ACP 200 and 250; MS were record on an Atlas
CH7 or Varian MAT 711 machine. IR spectra were
recorded from KBr pellets on a Bruker IFS 113v ma-
chine. Elemental analyses were done in the microanalyt-
ical laboratory of the Institute of Inorganic Chemistry
of University Karlsruhe. X-ray crystallographic analy-
Fig. 8. View of a molecule of 4. Carbon bonded hydrogen atoms have
been omitted for clarity. Selected bond lengths (pm): Ga(1)ꢀFe(1)
233.2(1), Ga(2)ꢀFe(2) 233.8(1), Ga(3)ꢀFe(3) 234.4(1), Ga(1)ꢀO(1)
192.0(5), Ga(1)ꢀO(3)c 190.8(4), Ga(2)ꢀO(1) 191.5(4), Ga(2)ꢀO(3)c
193.1(4), Ga(2)ꢀO(2) 191.9(4), Ga(1)ꢀO(2)c 193.6(5), Ga(3)ꢀI(1)
270.7(1).

G. Linti et al. / Journal of Organometallic Chemistry 626 (2001) 82–91
89
ses: suitable single crystal were mounted with a perfluo-
6.2. Synthesis of [CpFe(C )][Cp(CO)
[Cp(CO) FeGa] (OH) I (4)
2 2
H
7
8
2
FeGaI
3
] (3) and
rated polyether oil on the top of a glass fiber and
cooled immediately on the goniometer head. Data col-
lections were performed with graphite monochromated
2
O
6
4
Solid [CpFe(CO) ] (0.35 g, 1.00 mmol) was added to
2 2
a suspension of freshly prepared ‘‘GaI’’ (1.00 mmol) in
MoK radiation on Stoe IPDS (3, 8), Stoe STADI4 (1a,
a
2
0 ml toluene at ambient temperature. The mixture was
b, 5, 6) and Bruker AXS (4) diffractometers using
commercial software. Structures were solved and
refined using the Bruker AXS SHELXTL (PC) package.
All non-hydrogen atoms were refined anisotropically.
All hydrogen atoms bonded to carbon atoms were
included as riding model with fixed isotropic Us in the
final refinement. OH atoms were taken from a differ-
ence Fourier map and refined isotropically. ‘‘GaI’’ [13],
Ga Cl ·2dioxane and Ga Br ·2dioxan [30], [CpFe(CO) ]
heated to reflux for 3 h. The color of the mixture turned
reddish brown and some dark gray precipitate formed
during the reaction. After filtration and removal of all
volatiles in vacuo, the residue was extracted consecu-
tively with 15 ml of ether and 15 ml of THF. Colorless
crystals of 4 were obtained by cooling the ether solution
to −4°C; yield: 0.22 g 4 (36% with respect to iron).
Very thin yellow plates of 3 crystallized from the con-
2
4
2
4
2 2
centrated THF solution at −30°C; yield: 0.21 g 3 (25%
[
18] and K[CpFe(CO) ] [31] were prepared as described
1
2
with respect to iron). — 3: H-NMR (THF-d ): l=
8
in the literature. Other chemicals were used as pur-
chased.
7
.10 (m, 5H, C H ), 4.85 (s, 10H, C H ), 2.27 (s, 3H,
6 5 5 5
13
CH3).
—
C-NMR (THF-d ): l=25.3 (CH ), 85.6
8 3
−
1
(
1
C H ), 128.8 (C H ). — IR (KBr, cm ): w˜ (CꢀO)
5
5
6
5
987.3s, 1980.3s, 1937.6s, 1924.8s. — MS (70 eV, EI):
6
.1. Synthesis of (THF)GaCl [CpFe(CO) ] (1a) and
2
2
+
’
m/z (%)=550 (2) [(C H )Fe(CO) ] GaI] , 522 (100)
(
dioxane){GaCl [CpFe(CO) ]} (1b)
5
5
2 2
2
2
2
+
’
[(C H )Fe(CO) ] GaI−CO] , 494 (95) [[(C H ) Fe-
5 5 2 2 5 5 2
[
(
2
(
+
+
CO) ] GaI−2CO] , 373 (52) [(C H )Fe(CO) GaI] ,
2 2 5 5 2
A mixture of [CpFe(CO) ] (0.35 g, 1.00 mmol) and
+
+
2
2
’
42 (10) [(C H ) Fe ] , 213 (1) [C H FeC H ] , 186
5 5 2 2 5 5 7 8
Ga Cl ·2dioxan (0.46 g, 1.00 mmol) was heated to
+
+
2
4
’
35) [(C H ) Fe] , 121 (43) [C H Fe] . — Anal.
5
5 2
5
5
reflux in 30 ml of toluene for 2 h. The color of the
mixture turned yellow and a gray precipitate formed at
the end of the reaction. After filtration a yellow com-
pound crystallized from the yellow toluene solution
upon cooling to −4°C. The yellow crystalline com-
pound was redissolved in 15 ml of a 5:1 mixture of
ether and THF (5:1). Yellow single crystals of 1a were
obtained by over-laying the mixture of ether and THF
with pentane at ambient temperature, yield: 0.62 g, 1a
Found: C, 27.40; H, 2.28. Calc. for C H I Fe GaO
19
18 3
2
2
1
(
(
1
(
840.5): C, 27.15; H, 2.16. — 4: NMR (THF-d ): l H
8
−1
ppm)=5.18 (s, C H ). — IR (KBr, cm ): w˜ (CꢀO)
5
5
992.9s, 1938.3s. — MS (70 eV, EI): m/z (%)=522
+
’
,
26)
[(C H )Fe(CO) ] GaI−CO]
494
(29)
5
5
2 2
+
’
{[(C H )Fe(CO) ] GaI−2CO} , 373 (11) [(C H )Fe-
(CO) GaI] , 317 (13) [(C H )Fe(CO) GaI−2CO] ,
248 (8) [(C H )FeI] , 186 (39) [(C H ) Fe] , 121 (26)
5
5
2 2
5
5
+
+
2
5
5
2
+
’
+
’
5
’
5
5
5 2
+
[C H Fe] . — Anal. Found: C, 28.85; H, 2.64. Calc.
5
5
(
1
80% with respect to iron). Single crystals of 1b (0.07 g,
8%) were isolated by cooling the toluene solution
for C42
2.22.
H32Fe Ga I O18·C H10O (1906.1): C, 28.99; H,
6 6 2 4
1
to −20°C — 1a: H-NMR (THF-d ): l=4.96 (s,
C H ).
2
1
8
1
3
6.3. Synthesis of GaCl[CpFe(CO) ] (5)
—
C-NMR (THF-d ): l=83.5 (C H ),
2 2
5
5
8
−
5
5
1
17.3 (CO). — IR (KBr, cm ): w˜ (CꢀO) 1990.4s,
935.4s. — MS (70 eV, EI, M=GaCl C H Fe(CO) ):
A solution of K[CpFe(CO) ] (0.76 g, 3.50 mmol) in
20 ml of THF was added dropwise to a stirred solution
2
2
5
5
2
+
’
+
’
m/z (%)=318 (16) M , 290(34) [M−CO] 262 (83)
+
’ ’
+
of Ga Cl ·2dioxane (0.80 g, 1.75 mmol) in 20 ml of
2
4
[
[
[
M−2CO] , 225 (4) [M−2CO−Cl] , 186 (7)
(C H ) Fe]
C H Fe]
+
’
+
’
THF at ambient temperature. The mixture was stirred
for an additional 2 h at room temperature. The color of
the mixture turned red and a gray precipitate formed at
the end of the reaction. After filtration and removal of
all volatiles in vacuo, the residue was redissolved in 15
ml of THF. Red crystals of 5 were obtained by over-
,
156 (100) [C H FeCl]
,
121 (41)
5
5 2
5
5
+
’
.
— Anal. Found: C 34.13, H 3.23. Calc.
5
5
for C H Cl FeGaO (389.7): C, 33.90; H, 3.36;
1
1
13
2
3
1
—
—
—
1b: H-NMR (THF-d8): l=4.96 (s, C H ).
C-NMR (THF-d ): l=83.5 (C H ), 217.3 (CO).
5
5
1
3
8
5
5
−
1
IR (KBr, cm ): w˜ (CꢀO) 1989.6s, 1933.8s. — MS
laying the THF solution with pentane at −30°C; yield:
(
70 eV, EI, M=GaCl C H Fe(CO) ): m/z (%)=580
1
2
5
5
2
0
.33 g (35% with respect to iron). — 5: H-NMR
+
’
+
’
(
4) [2M−2CO] , 474 (13) [2M−GaCl−2CO] , 318
13
8 5 5 8
−1
(THF-d ): l=4.87 (s, C H ). — C-NMR (THF-d ):
+
’
+
’
+
’
(
24) M , 290 (31) [M−CO] , 262 (85) [M−2CO] ,
l=83.7 (C H ), 217.3 (CO). — IR (KBr, cm ):
w˜ (CꢀO) 1992.1s, 1982.1s, 1971.4s, 1935.7s. — MS (70
eV, EI, M=GaCl[(C H )Fe(CO) ] ): m/z (%)=458
5
5
+
+
’
25 (4) [M−2CO−Cl] , 186 (3) [(C H ) Fe] , 156
5 5 2
2
(
+
’
100) [C H FeCl] , 121 (33) [C H Fe] . — Anal.
5 5 5 5
+
5
5
2 2
+
’
+
’
+
’
Found: C, 29.47; H, 2.13. Calc. for C H Cl Fe Ga O
1
8
18
4
2
2
6
(1.6) [M] , 430 (22) [M−CO] , 402 (33) [M−2CO] ,
+
’
42 (31) [(C H ) Fe ] , 225 (25) [C H FeGaCl] ,
5 5 2 2 5 5
+
(
723.3): C, 29.89; H, 2.51.
2

9
0
G. Linti et al. / Journal of Organometallic Chemistry 626 (2001) 82–91
+
’
+
1
86 (100) [(C H ) Fe] , 121 (53) [C H Fe] . Anal.
7. Supplementary material
5
5 2
5
5
Found; C, 40.35; H, 3.27. Calc. for C H ClFe GaO
1
8
18
2
5
(
531.2): C, 40.70; H, 3.42.
For further details see Table 3, the crystallographic
data (excluding structure factors) for the structure(s)
reported in this paper have been deposited with the
Cambridge Crystallographic Data Centre as supple-
mentary publication no. CCDC-150682 (1a), 150683
6
{
.4. Synthesis of
(Et O) K(v-Cl) (v -Cl)Ga [CpFe(CO) ] } (6)
2
2
2
3
2
2 4
(
1b), 150684 (3), 150685 (4), 150686 (5), 150687 (6),
A solution of K[CpFe(CO) ] (0.43 g, 2.00 mmol) in
0 ml of THF was added dropwise to a stirred solution
150688 (8). Copies of the data can be obtained free of
charge on application to The Director, CCDC, 12
Union Road, Cambridge CB2 1EZ, UK [Fax: +44-
1223-336-033; e-mail: deposit@ccdc.cam.ac.uk or www:
http://www.ccdc.cam.ac.uk].
2
2
of Ga Cl ·2dioxane (0.22 g, 0.50 mmol) in 20 ml of
2
4
THF at −78°C. No color change was observed at
78°C. The mixture was warmed to ambient tempera-
−
ture slowly and stirred for an additional 8 h. The color
of the mixture turned yellowish brown and a gray
precipitate formed at the end of the reaction. After the
removal of all volatiles in vacuo, the residue was redis-
solved in 15 ml of ether. Well-shaped orange red crys-
tals of 6 were obtained upon cooling the solution to
Acknowledgements
We thank Ms E. M o¨ llhausen and Dr E. Baum (Uni-
versit a¨ t Karlsruhe) for their assistance in X-ray data
collection as well as Prof. Dr H. Schn o¨ ckel for diffrac-
tometer time. Financial support by the Deutsche
Forschungsgemeinschaft, the Fonds der Chemischen
Industrie and Chemetall GmbH is gratefully
acknowledged.
−
4°C, yield 0.23 g 6 (40% with respect to iron). 6:
1
13
H-NMR (THF-d ): l=4.86 (s, C H ).
—
C-NMR
8
5
5
−
1
(THF-d ): l=83.7 (C H ). — IR (KBr, cm ):
8 5 5
w˜ (CꢀO) 2003.7s, 1933.7s. — MS (70 eV, EI,): m/z
+
’
%)=458 (7.3) {[(C H )Fe(CO) ] GaCl} , 430 (55)
5 5 2 2
(
+
’
[(C H )Fe(CO) ] GaCl−CO} , 402 (50) {[(C H )Fe-
5 5 2 2 5 5
{
+
’
’
(
[
[
CO) ] GaCl−2CO} , 242 (52) [(C H ) Fe ] , 225 (64)
2
2
5
5 2
2
+
+
’
C H FeGaCl] , 186 (100) [(C H ) Fe] , 121 (88)
5 5 5 5 2
References
+
’
C H Fe] . — Anal. Found: C, 35.33; H, 2.57. Calc.
5
5
for C H Cl Fe Ga KO ·C H O (1066.8): C, 35.99; H,
2
8
20
3
4
2
8
4
10
[
1] G. Linti, M. Kehrwald, W. K o¨ stler, A. Rodig, T. Blank, N.
Wiberg, Organometallics (2000), in press.
2.81.
[
[
2] G. Linti, H. Schn o¨ ckel, Coord. Chem. Rev. 206–207 (2000) 285.
3] R.A. Fischer, J. Weiß, Angew. Chem. Int. Ed. Engl. 38 (1999)
2
830.
6
.5. Synthesis of (Et O) K (GaBr ) FeO [(CpFe(CO) ]
2 4
2
4
2
2 4
2
[
[
4] N.A. Compton, R.J. Errington, N.C. Norman, Adv. Organomet.
Chem. 31 (1990) 91.
5] K.H. Whitmire, J. Coord. Chem. Sect. B 17 (1988) 95.
(
8)
K[CpFe(CO) ] (0.43 g, 2.00 mmol) was dissolved in
0 ml of THF and added dropwise to a vigorously
[6] P. Corradini, A. Sirigu, Inorg. Chem. 6 (1967) 601.
2
[
[
[
7] C. B o¨ hme, G. Frenking, Chem. Eur. J. 5 (1999) 2184.
8] F.A. Cotton, X. Feng, Organometallics 17 (1998) 128.
9] R. K o¨ ppe, H. Schn o¨ ckel, Z. anorg. allg. Chem. 626 (2000) 1095.
2
stirred solution of Ga Br ·2dioxane (0.63 g, 1.00 mmol)
2
4
in 20 ml of THF. After warming to ambient tempera-
ture, the mixture was stirred for an additional 8 h. The
color of the mixture turned to yellowish brown and a
gray precipitate was formed. After the removal of all
volatiles in vacuo, the residue was redissolved in 15 ml
of ether. Pale yellow crystals of 8 were obtained by
[
10] G. Linti, W. K o¨ stler, Angew. Chem. 109 (1997) 2758; Angew.
Chem. Int. Ed. Engl. 36 (1997) 2644.
[11] G. Linti, A. Rodig, Angew. Chem. 112 (2000) 3076; Angew.
Chem. Int. Ed. Engl. 39 (2000) 2952.
[
12] A. Schnepf, E. Weckert, G. Linti, H. Schn o¨ ckel, Angew. Chem.
11 (1999) 3578; Angew. Chem. Int. Ed. Engl. 38 (1999) 3381.
1
[
13] M.L.H. Green, P. Mountford, G.J. Smout, S.R. Speel, Polyhe-
dron 9 (1990) 2763.
cooling the solution to −4°C for a few days; yield 0.32
1
g 8 (38% with respect to iron). 8: H-NMR (THF-d ):
[14] R.A. Fischer, A. Miehr, T. Priermeier, Chem. Ber. 128 (1995)
31.
[15] G.N. Harakas, B.R. Whittlesey, Inorg. Chem. 36 (1997) 2704.
16] N.C. Norman, L.M. Clarkson, L.J. Farrugia, Organometallics
0 (1991) 1286.
8
1
3
8
l=4.96 (s, 20H, C H ).
—
C-NMR (THF-d ): l=
5
5
8
−
1
8
1
4.1 (C H ). — IR (KBr, cm ): w˜ (CꢀO) 1997.5s,
5
5
[
946.6s. — MS (70 eV, EI): m/z (%)=476 (9)
1
+
2 2 5 5 2 2 2 5 5
[
(
(
Ga Br C H Fe(CO) ] , 448 (15) [Ga Br C H Fe-
[17] R.M. Campbell, L.M. Clarkson, W. Clegg, D.C.R. Hockless,
N.L. Pickett, N.C. Norman, Chem. Ber. 125 (1992) 55.
+
’ ’
CO) −CO] , 406 (2) [GaBr C H Fe(CO) ] , 378
2 2 5 5 2
+
+
’
[
18] B.R. King, F.G.A. Stone, Inorg. Synth. 7 (1963) 110.
[19] B.F. Hallam, P.L. Pauson, J. Chem. Soc. (1956) 3030.
20] G. Linti, R. Frey, W. K o¨ stler, H. Urban, Chem. Ber. 129 (1996)
61.
10) [GaBr C H Fe(CO) −CO] , 350 (18) [GaBr -
C H Fe(CO) −2CO] , 186 (96) [(C H ) Fe] , 200
’
50) [C H FeBr] , 121 (100) [C H Fe] . — Anal.
5 5 5 5
2
5
5
2
2
+
’
+
’
5
5
2
5
5 2
+
[
+
(
5
Found: C, 24.86; H, 2.63. Calc. for C H Br -
44
60
8
[21] A.F. Wells, Structural Inorganic Chemistry, Clarendon Press,
Oxford, 1984.
Fe Ga K O ·(2088.5): C, 25.30; H, 2.90.
5
4
2
4

G. Linti et al. / Journal of Organometallic Chemistry 626 (2001) 82–91
91
[
[
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[
[
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