Low-valent nickel and palladium complexes with 1,1′-bis(phosphanyl)- ferrocenes: Syntheses and structures of acrylic acid and ethylene complexes

Article abstract of DOI:10.1002/ejic.200601051

Thermally stable acrylic acid complexes with low-valent nickel or palladium of the type [(L)M(η²-CH₂=CH-COOH)] [1a: M = Ni, L = 1,1′-bis(diphenylphosphanyl)ferrocene (dppf), 1b: M = Ni, L = 1,1′-bis(diisopropylphosphanyl)ferrocene (d

Full text of DOI:10.1002/ejic.200601051

FULL PAPER
DOI: 10.1002/ejic.200601051
Low-Valent Nickel and Palladium Complexes with 1,1Ј-Bis(phosphanyl)-
ferrocenes: Syntheses and Structures of Acrylic Acid and Ethylene Complexes
[a]
[a]
[a]
[a]
Jens Langer, Reinald Fischer, Helmar Görls, and Dirk Walther*
Keywords: Alkene ligands / Chelates / Nickel / Palladium / P ligands
Thermally stable acrylic acid complexes with low-valent
plexes in case of 2a (L = dppf) and 2b (L = dippf) whereas the
unstable compound 2c [L = 1,1Ј-bis(di-tert-butylphosphanyl)-
ferrocene (dtbpf)] undergoes fast reductive decoupling to
2
nickel or palladium of the type [(L)M(η -CH
2
=CH-COOH)]
1a: M = Ni, L = 1,1Ј-bis(diphenylphosphanyl)ferrocene
dppf), 1b: M = Ni, L = 1,1Ј-bis(diisopropylphosphanyl)ferro-
[
(
2
form CO and the ethylene complex [(dtbpf)Ni(ethylene)]
cene (dippf), 1c: M = Pd, L = dippf] were obtained by reaction
of [Ni(cod) ] or [(L)Pd(nb)] with acrylic acid in the presence
of the phosphane ligands. X-ray diffraction analysis of 1a and
c, respectively display that only the olefin part is coordi-
(3c). The related complex [(dippf)Ni(ethylene)] (3b) was pre-
pared from nickel(0) complexes by ligand exchange reaction.
3b and 3c were characterized by elemental analyses, NMR
spectroscopy and X-ray structure analysis of single crystals.
2
1
nated. Hydrogen bonds between two carboxyl groups result
in dimers in the solid state. The isomeric nickela-cyclic car-
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
2 2
boxylates of the type [(L)Ni(CH CH COO)] are stable com- Germany, 2007)
Introduction
Recently we have described some model complexes of the
hypothetical catalytic reactions between ethylene and CO
2
to form acrylic acid or its derivatives.[ In connection with
1]
these investigations we have also tried to synthesize the
2
hitherto unknown nickel(0) complexes with η -coordinated
acrylic acid which are assumed to be model compounds of
the final intermediate of the catalytic cycle. However, such
complexes could not be obtained with N-donor ligands or
phosphanes of the type R P(CH ) PR .
2
2 n
2
In this paper we report that some 1,1Ј-bis(phosphanyl)-
ferrocenes (L) are able to form surprisingly stable com-
2
plexes of the type [(L)M(η -acrylic acid)]. Furthermore, we
have isolated the isomeric form of [(dippf)Ni(acrylic acid)],
the metallacycle [(dippf)Ni(CH CH COO)], and we also
2
2
succeeded in obtaining ethylene nickel(0) complexes with
bis(phosphanyl)ferrocene ligands which are also hitherto situ.[5,6] This is somewhat surprising since low-valent nickel
unknown. These three types of complexes may also be con- complexes with 1,1Ј-bis(phosphanyl)ferrocene ligands are
sidered as model compounds for intermediates of the metal- known to be intermediates in numerous homogeneous cata-
[
7–13]
mediated reaction between ethylene and CO2 to form lytic reactions.
acrylic acid.
sors for new catalysts and for the study, in a stoichiometric
In addition, they may serve as precur-
Generally, the low-valent nickel chemistry with 1,1Ј-bis- manner, of key steps in the catalytic reactions.
(phosphanyl)ferrocene ligands L is rather limited. To the
best of our knowledge the only isolated nickel(0) com-
[
2,3]
pounds are some carbonyl complexes
and [(dppf)-
Results and Discussion
[
4]
Ni(cod)]. The compound [(dppf) Ni] was only prepared in
2
Nickel(0) and Palladium(0) Complexes with Acrylic Acid
[
a] Institute of Inorganic and Analytical Chemistry, Friedrich-
Schiller University Jena,
The acrylic acid complexes 1a and 1b were obtained by
Lessingstraße 8, 07743 Jena, Germany
Fax: +49-3641-948102
E-mail: dirk.walther@uni-jena.de
reacting a mixture of [Ni(cod) ], dppf or dippf and acrylic
2
acid in a solution of THF at 0 °C according to Scheme 1.
Eur. J. Inorg. Chem. 2007, 2257–2264
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2257

J. Langer, R. Fischer, H. Görls, D. Walther
FULL PAPER
Figure 1. Molecular structure of 1a (H atoms except the one at O2
are omitted for clarity, cocrystallized THF not shown). Selected
bond lengths [Å] and angles [°]: Ni–C1 1.945(2), Ni–C2 1.993(3),
Ni–P1 2.1781(7), Ni–P2 2.1411(8), C1–C2 1.417(4), C2–C3
Scheme 1. Formation of nickel complexes with acrylic acid.
1
.446(4), C3–O1 1.275(4), C3–O2 1.291(4), P1–Ni–P2 109.71(3),
1
a was isolated in good yields (71%) as red crystalline
P1–Ni–C2 111.55(9), P2–Ni–C1 109.71(3), C1–Ni–C2 42.2(1), pla-
ne(P1,P2,Ni)-plane(Ni,C1,C2) 6.24.
compound. NMR spectroscopic data showed that both
phosphorus donor atoms coordinate to the nickel in a dif-
ferent chemical environment ( P{ H} NMR ([D ]THF):
6.7 and 32.6 ppm). In the H NMR spectrum ([D ]THF)
the proton signals of the olefinic CH group appeared at δ
1.95 and 2.25 ppm and the resonance of the olefinic CH
3
1
1
8
1
the resonance of the COOH proton appeared at δ =
1
were found at 32.7 (=CH ) and 42.7 (=CH) ppm and the
signal of the COOH group was observed at δ = 177.7 ppm
confirming the olefin-like coordination of the acrylic acid
ligand as well. In addition, X-ray structure of single crystals
2
8
0.35 ppm. The 13C resonances of 1b for the olefin group
2
2
=
group was found at δ = 2.98 ppm. A broad signal for the
COOH proton appeared at δ = 9.64 ppm. Furthermore, six
different signals of the cp groups integrating together to
eight protons were observed, and the 20 protons of phenyl
(not depicted) showed that 1b has essentially the same solid-
2
groups appeared between 7.28 and 7.80 ppm. The 13
state structure as 1a with the η coordination of the acrylic
acid ligand and hydrogen bonds between two acrylic acid
ligands resulting in a dimer.
C
NMR spectrum also confirmed the olefin-like coordination
of the acrylic acid with the two signals for the olefinic car-
bons at δ = 43.9 and 49.8 ppm and the signal of the COOH
group at δ = 175.9 ppm.
Reaction between acrylic acid and nickel(0) complexes in
the presence of Cy P was already investigated by Yama-
moto et al. In this case, however, no stable nickel(0) com-
plex of acrylic acid was formed, instead the interconversion
into the isomeric nickela-cyclic carboxylate [(Cy P)-
Ni(CH CH COO)] was observed. This clearly demon-
3
[
14]
Single crystals of 1a were grown from a solution of THF
and an X-ray diffraction analysis (Figure 1) showed the
nickel atom, surrounded by two phosphorus atoms and the
two carbon atoms C1 and C2 of the alkene group. Since the
angle between the P1,P2,Ni plane and the C1,C2,Ni plane
is only 6.24°, the coordination geometry around the metal
centre can be considered as essentially planar. The COOH
group is not coordinated. Complex 1a forms a dimer in the
solid state since two carboxylic groups are connected by
the typical hydrogen bond pattern of carboxylic acids. As
expected, the bond length between C1 and C2 of the olefin
group [1.417(4) Å] is slightly enlarged compared with the
uncoordinated state of acrylic acid. Other relevant bond
lengths and angles (see caption of Figure 1) are within the
normal range and need therefore no further discussion.
3
2
2
n
strates the strong influence of the supporting ligands on the
following equilibrium (Scheme 2).
Scheme 2. Equilibrium between
(Ln)Ni(CH CH COO)].
n 2
L Ni(CH =CH-COOH)) and
[
2
2
1a is surprisingly thermally stable in THF as well in the
solid state. Even heating the complex for 3 h in refluxing
The reaction between [Ni(cod) ], dippf und acrylic acid THF did not result in any reaction. This demonstrates that
2
in THF resulted in a mixture of the acrylic acid complex the isomerization into the nickela-cyclic carboxylate (see
1b as main product and traces of a second compound, sus- Scheme 2) is in this case an energetically unfavourable path-
pected to be the isomeric nickela-cyclic carboxylate [(dippf)- way.
Ni(CH CH COO)] (2b, see below) according to the signals
in the P NMR spectrum of the mother liquor.
So far, only the metal(0) acrylic acid complex
2
2
3
1
[15]
[(acrylic acid)Fe(CO) ] was described.
Furthermore, the
4
I
2
The pure complex 1b was isolated upon crystallisation dimeric Cu compound [ClCu(acrylic acid)] with η coor-
2
1
[16]
from a solution of THF or DMF in good yields. H NMR dinated acrylic acid has been prepared. In addition, Car-
spectroscopy of 1b revealed that the compound has a sim- mona has found that acrylate hydrido molybdenum(II) and
ilar structure as found for 1a: The proton signals of the tungsten(II) complexes were formed by reaction of ethylene
0
[17]
coordinated CH =CH- group at 2.57 and 2.88 are only and CO at an electron-rich Mo(0) or W fragment.
In
2
2
0
0
slightly downfield shifted compared with those of 1a, and contrast, acrylic ester complexes with Ni or Pd have been
2258
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© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2007, 2257–2264

Complexes with 1,1Ј-Bis(phosphanyl)ferrocenes
FULL PAPER
found to be stable[18,19] due to the lack of the reactive dppf, dippf, dtbpf) (2) are stable compounds, we reacted
COOH group. [(py) Ni(CH CH COO)] with these ligands in DMF at
2
2
2
To demonstrate that the ability of 1,1Ј-bis(phosphanyl)- room temperature. This pyridine complex is a labile ligand
ferrocene ligands in stabilizing acrylic acid complexes is not complex which serves as precursor for many other reac-
0
[20–22]
restricted to nickel(0) we also prepared the related Pd com- tions.
Scheme 3 displays that, depending on the bis-
plex [(dippf)Pd(acrylic acid)] 1c by reacting of [(dippf)- (phosphanyl)ferrocene ligands, different products were
Pd(nb)] (nb = norbornene) with an excess of acrylic acid in formed.
THF [Equation (1)].
[
(dippf)Pd(nb)] + HOOC–CH=CH
2
Ǟ
2
[(dippf)Pd(η -CH
2
=CH–COOH)] (1c) + nb (1)
Isolation of the orange solid and recrystallisation from
diethyl ether resulted in orange single crystals. To confirm
the structure in the solid state, the X-ray crystal structure
analysis of 1c was carried out. Figure 2 reveals the molecule
structure which shows that 1c has the same arrangement of
the ligands as the related nickel(0) acrylic acid complexes
with the olefin part of acrylic acid being coordinated at Pd0
centre and with a C=C bond lengths of 1.419(3) Å. Also,
the other bond lengths and angles lie within a typical range.
The angle between the plane (P1,P2,Pd) and the (Pd,
C1,C2) is only 2.27° which undoubtedly shows that the Pd0
centre is in a planar environment formed by the two P do-
nor atoms and the carbons C1 and C2 of the olefinic part
of the acrylic acid ligand. 1c forms also a dimer in the solid
state in which two carboxylic groups are connected by hy-
drogen bonds.
Scheme 3. Reactions of bis(phosphanyl)ferrocene ligands with a
nickela-lactone.
In contrast to the formation of the thermally unstable
complex 2a from dppf and [(py) Ni(CH CH COO)], the re-
2
2
2
action with dippf resulted in the formation of the thermally
stable nickela-cyclic carboxylate 2b which was isolated as
orange crystals in high yields (85%). 2b was fully charac-
terized by elemental analyses, IR, and NMR spectroscopy,
1
and by X-ray analysis of single crystals. In the H NMR
spectrum of 2b in [D ]THF the Ni-CH protons were ob-
8
2
served at δ = 0.96 ppm and those of the CH COO unit reso-
2
nated at δ = 1.96 ppm; each of these signals correspond to
two protons. The signals of the CH groups appeared at
3
1
2
.23–1.54 ppm, the signals of the CH groups were found at
.20–2.47 ppm and the cp protons were observed as singlets
13
at δ = 4.40 and 4.44 ppm. In addition, the C NMR spec-
Figure 2. Molecular structure of 1c (the formation of hydrogen
bonds analogously to fig. 1 is indicated by the dotted lines indicat-
trum showed the expected simple pattern of signals for the
ing the points at which the dimer is formed; H atoms except the Ni–CH
group at 12.4 and for the CH -COO- fragment at
2
2
one at O1, and cocrystallized THF have been omitted clarity). Se-
δ = 37.2 ppm, besides the resonances for the ligand carbons,
and in the P{ H} NMR spectrum in [D ]DMF the
signals appeared at δ = 36.4 and 44.7 ppm. In the IR spec-
lected bond lengths [Å] and angles [°]: Pd–C1 2.100(2), Pd–C2
.154(2), Pd–P1 2.3116(7), Pd–P2 2.3215(8), C1–C2 1.419(3), C2–
C3 1.457(3), C3–O1 1.327(3), C3–O2 1.237(3), P1–Pd–P2
31
1
31
P
7
2
–1
1
3
05.98(3), P1–Pd–C1 104.35(7), P2–Pd–C2 110.67(7), C1–Pd–C2 trum the ν(C=O) band was found at 1634 cm .
8.95(9), plane (P1,P2,Pd)-plane(Pd, C1,C2) 2.27.
Single crystals were grown from DMF at –20 °C and the
crystal structure of 2b has been solved by X-ray diffraction
analysis. Its molecule structure is displayed in Figure 3 and
shows it to be very similar to the starting complex
Nickela-Cyclic Carboxylates of the Type [(L)
NiCH CH COO] (L = dppf, dippf)
[
22]
[
(py) Ni(CH CH COO)]
and other closely related nick-
However, due to the disorder of
2
2
2
2
2
[1,21]
ela-cyclic carboxylates.
In order to proof whether the isomers of 1, the nickela- the nickela-cylopentanone unit a closer comparison with
cyclic carboxylates of the type [(L)Ni(CH CH COO)] (L: other nickela-cyclic carboxylates is not possible.
2
2
Eur. J. Inorg. Chem. 2007, 2257–2264
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
2259

J. Langer, R. Fischer, H. Görls, D. Walther
FULL PAPER
Figure 3. Molecular structure of 2b (H atoms have been omitted
for clarity).
Figure 4. Molecular structure of 4 (H atoms have been omitted for
clarity). Selected bond lengths [Å] and angles [°]: Ni–P1A 2.269(2),
Ni–P2A 2.238(2), Ni–P1B 2.243(2), Ni–P2B 2.237(2), P1A–Ni–P1B
1
20.93(4), P1A–Ni–P2A 106.28(5), P1A–Ni–P2B 115.62(4), P1B–
Ni–P2A 106.47(5), P1B–Ni–P2B 101.64(4), P2A–Ni–P2B
15.62(4).
2
a is extremely sparingly soluble in organic solvents pre-
venting complete characterization by NMR spectroscopy.
1
The compound shows the typical ν(C=O) band for a nick-
–
1
ela-cyclic carboxylate at 1642 cm in nujol suspension.
3
1
Furthermore, P NMR measurements in [D ]DMF at
7
Complexes of the Type [(L)Ni(ethylene)] [L: dtbpf, (dippf)]
25 °C gave two signals for the coordinated P atoms in a
different chemical environment at δ = 19.4 and 39.0 ppm.
In addition, in the H NMR spectrum the two resonances [(py) Ni(CH CH COO)] under similar conditions a dif-
The steric bulky ligand dtbpf yielded in the reaction with
1
2
2
2
of the coordinated CH CH COO fragment were observed ferent product compared to the dippf complex. In this case
2
2
at δ = 0.64 ppm (as a multiplet of the Ni-CH group) and reductive decoupling of the NiCH CH COO- unit was ob-
2
2
2
at δ = 1.93 ppm. The latter appears as a triplet and is as- served resulting in the formation of the nickel(0) ethylene
signed to the CH COO protons. Comparison of these data complex [(dtbpf)Ni(ethylene)] 3c and CO (Scheme 1). This
2
2
with those of the nickela-cyclic carboxylate 2b suggest that demonstrates how sensitive the reactivity can be influenced
a is also the expected nickela-cyclic carboxylate according by the steric demand of the ligands. 3c was characterized
to Scheme 3. by NMR spectroscopy in [D ]DMF and by an X-ray analy-
a is a thermally unstable compound. Even at 40 °C in sis of single crystals grown from DMF. When the nickela-
2
7
2
DMF the complex decomposes into a mixture of com- cycle 2b was heated at 80 °C, reductive decoupling was ob-
pounds. One product isolated from the reaction mixture served as well, resulting in the formation of [(dippf)Ni(ethy-
was the nickel(0) complex [(dppf) Ni] (4). This compound lene)] (3b) in good yields.
2
was already generated in situ either by reaction of NiBr2,
As expected for a symmetrical structure in solution, the
3
1
1
dppf and Zn or by reduction of [Ni(acac) ] using DIBAL-
P{ H} NMR spectrum of 3c in [D ]DMF at room tem-
2
7
H in the presence of dppf,[
5,6]
however to the best of our perature showed only one signal at δ = 65.6 ppm. In the
1
knowledge it has not been isolated so far. Complex 4 was
H NMR spectrum the ethylene protons appeared at δ =
1
13
characterized by elemental analyses, H and C NMR 1.86 ppm. The methyl protons of the tert-butyl group reso-
spectroscopy and by a single crystal structure analysis. Fig- nated at δ = 1.35 ppm and the singlets at δ = 4.06 and
ure 4 shows its molecule structure and contains the most 4.21 ppm (each integrating to four protons) were assigned
relevant bond lengths and angles in the caption.
the cp ring protons. Single crystals of 3c were grown from
The nickel centre is in the tetrahedral environment of DMF suitable for X-ray structure determination, and its
four P donor atoms with typical Ni–P bond lengths. In the molecule structure is shown in Figure 5.
dppf ligand A the two cp ligands have a synclinal staggered
The nickel(0) centre is in the distorted tetrahedral envi-
conformation with a torsion angle τ of 43.9°. This confor- ronment of the two P donor groups and the carbons of the
mation is the most common one found for dppf in its metal ethylene ligand with typical bond lengths for the Ni–P and
complexes (characteristic values: 18° Ͻ τ Ͻ 54°).[ In the Ni–C bonds. As expected, the double bond of the coordi-
other ligand B, however, the torsion angle is only 15.0° and nated ethylene ligand [C(1)–C(2) 1.399(4) Å] is significantly
23]
the cp ligands have a synperiplanar eclipsed conformation elongated compared to free ethylene.
characteristic region: 0° Ͻ τ Ͻ 18°).[ This different ar-
23]
It is noteworthy, that the hitherto unknown ethylene
(
rangement results in different bite angles (106.3° for P1A– complexes with 1,1Ј-bis(phosphanyl)ferrocene ligands can
Ni–P2A and 101.6° for P1B–Ni–P2B). also be formed by other methods. For example, the ethylene
2260
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© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2007, 2257–2264

Complexes with 1,1Ј-Bis(phosphanyl)ferrocenes
FULL PAPER
All manipulations were carried out by using modified Schlenk tech-
niques under an atmosphere of argon. Prior to use, THF, benzene
and diethyl ether were dried with potassium hydroxide and distilled
2
from sodium/benzophenone. DMF was dried with CaH .
dppf, dippf, and dtbpf were prepared in analogy to known pro-
cedures by reaction of nBuLi/tmeda with ferrocene, followed by
addition of the chlorodiphenylphoshane, chlorodiisopropylphos-
[
24–27]
[28]
phane or chlorodi-tert-butylphosphane.
2 4 7 10 3
Ni(C H H )
[Ni(cod)
2
],
2
[(py) -
COO)][ and [Pd(η -C ][29] were prepared according
22]
2
to literature procedures.
2
[
4
4
(dppf)Ni(η -CH
2
=CH-COOH)] (1a): A solution of dppf (2.67 g,
] (1.32 g,
.80 mmol). The suspension was stirred until all solids had dis-
.82 mmol) in THF (30 mL) was added to solid [Ni(cod)
2
solved. Afterwards the stirred solution was cooled to 0 °C and
acrylic acid (0.37 g, 5.13 mmol) was added, resulting in formation
of a yellow precipitate. This solid was isolated by filtration and
dried in a vacuum. Yield: 2.83 g (71%). Suitable crystals of
Figure 5. Molecular structure of 3c (H atoms have been omitted
for clarity). Selected bond lengths [Å] and angles [°]: Ni–C1
(
1a)·2THF for X-ray measurement were obtained by slowly cooling
a saturated solution in THF from room temperature to 5 °C. In a
1
.980(3), Ni–C2 1.984(3), Ni–P1 2.1893(6), Ni–P2 2.1908(6), C1–
2
similar manner, crystals of [(dppf)Ni(η -CH
2
=CH-COOH)]·
C2 1.399(4), P1–Ni–P2 111.95(3), P1–Ni–C1 103.96(9), P2–Ni–C2
1.5DMF were obtained from a solution of DMF. Those crystals
1
1
04.03(9), C1–Ni–C2 41.3(2), plane (P1,P2,Ni)-plane(Ni,C1,C2)
5.71.
2
were used for elemental analysis. C41.5H42.5FeN1.5NiO3.5P (794.8)
1
calcd. C 62.71, H 5.39, N 2.64; found C 62.11, H 5.54, N 2.53. H
NMR ([D ]THF, 25 °C): δ = 1.95 (m, 1 H, CH =), 2.25 (m, 1 H,
CH =), 2.98 (m, 1 H, CH=), 3.89 (s, 1 H, CH cp), 4.07 (s, 1 H,
8
2
complex 3b was additionally prepared by ligand displace-
ment from (cyclododeca-1,5,9-triene)nickel(0) [Equation
2
CH cp), 4.22 (s, 2 H, CH cp), 4.26 (s, 1 H, CH cp), 4.29 (s, 1 H,
(
2)].
CH cp), 4.35 (s, 2 H, CH cp), 7.28–7.80 (m, 20 H, CH ph), 9.64
1
3
1
(
=
7
(
br., 1 H, COOH). C{ H} NMR ([D
19.6 Hz, CH =). 49.8 (d, JP,C = 11.6 Hz, CH=), 71.1 (dd, JP,C
.3 Hz, JP,C = 4.1 Hz, CH cp), 72.9 (d, JP,C = 6.4 Hz, CH cp), 74.4
dd, JP,C = 20.0 Hz, JP,C = 6.0 Hz, CH cp), 75.3 (dd, JP,C = 17.5 Hz,
P,C = 13.8 Hz, CH cp), 81.9 (dd, JP,C = 40.4 Hz, JP,C = 5.1 Hz, C
cp), 82.2 (dd, JP,C = 40.4 Hz, JP,C = 5.1 Hz, C cp), 128.4 (dd, JP,C
7.5 Hz, JP,C = 2.9 Hz, CH), 128.7 (d, JP,C = 9.3 Hz, CH), 129.3
d. JP,C = 8.3 Hz, CH), 130.2 (d, JP,C = 20.1 Hz, CH), 134.0 (dd,
P,C = 12.2 Hz, JP,C = 5.9 Hz, CH), 135.5 (dd, JP,C = 49.6 Hz, JP,C
8
]THF, 25 °C): 43.9 (d, JP,C
[Ni(cdt)] + dippf + C
2
H
4
Ǟ [(dippf)Ni(C
2
H
4
)] + cdt
(2)
2
=
NMR spectroscopic data are very similar to those of the
dtbpf complex 3c, and the crystal structure of single crystals
of 3b (not depicted) is also comparable with that of the
closely related complex 3c and need therefore no further
discussion.
J
=
(
J
=
1
P,C
J J =
P,C = 37.8 Hz, C), 137.2 (d, 1
15,2 Hz, CH), 137.2 (d,
3
1
1
Conclusions
37.8 Hz, C), 175.9 (COOH). P{ H} NMR ([D ]THF, 25 °C): δ =
2
8
2
2
6.7 (d, JP,P = 21.9 Hz), 32.6 (d, JP,P = 21.9 Hz).
2
Complexes of the type [(L)M(η -CH =CH-COOH)] (1a–
c) are the first Ni- and Pd complexes with acrylic acid as [(dippf)Ni(η -CH
2
0
2
1
2
=CH-COOH)] (1b): A solution of dippf (2.21 g,
5
5
2
.28 mmol) in THF (30 mL) was added to [Ni(cod) ] (1.45 g,
.27 mmol). The mixture was stirred until all solids had dissolved
olefin-like ligand. Due to the rigidity and the bulkiness of
the ferrocenyl-bisphosphane ligands these complexes are
surprisingly stable and do not thermally interconvert into
the isomeric nickela-lactones of the type [(L)Ni(CH CH -
COO)] (2) which could be independently prepared by ligand
exchange from [(py) Ni(CH CH COO)] as thermally stable
and then cooled to 0 °C. At this temperature acrylic acid (0.38 g,
.27 mmol) was added drop wise. The resulting reaction mixture
5
2
2
was stored at 5 °C overnight. Afterwards the solvent was removed
by distillation under reduced pressure and ether was added to the
remaining residue, resulting in the formation of a yellow precipi-
tate. This solid was isolated by filtration and dried in a vacuum.
2
2
2
compounds. The nickela-lactones 2b and 2c react at heating
under reductive decoupling to yield the new ethylene com- Suitable crystals for X-ray measurement were obtained by layering
plexes of the type 3, however, the isomerization of the com- a saturated solution of 1b in DMF with ether. Yield: 1.76 g
plexes of the type 2 to form the acrylic acid complexes 1 (60.6%). C25
H
40FeNiO
2
P
2
(549.0) calcd. C 54.68, H 7.34; found C
4.36, H 7.53. H NMR ([D ]THF): δ = 0.65 (dd, J = 10.3 Hz, J
), 0.74 (m, 3 H, CH ), 0.65 (dd, J = 10.3 Hz, J
), 1.03 (dd, J = 15.6 Hz, J = 7.1 Hz, 3 H, CH ),
), 1.27–1.56 (m, 12 H,
], 1.97 [m, 2 H, CH(CH ], 2.57
), 2.88 (br., 1 H, CH=), 3.94 (s, 2 H, CH cp), 3.99
(s, 1 H, CH cp), 4.01 (s, 1 H, CH cp), 4.03 (s, 2 H, CH cp), 4.16
1
5
8
was not observed.
=
=
3.6 Hz, 3 H, CH
3.6 Hz, 3 H, CH
3
3
3
3
1
.15 (dd, J = 13.7 Hz, J = 6.9 Hz, 3 H, CH
CH ), 1.85 [m, 2 H, CH(CH
(br., 1 H, =CH
3
Experimental Section
3
3
)
2
3 2
)
General: Infrared spectra were recorded using a Perkin–Elmer 2000
2
FT-IR; 1H-NMR spectra were recorded on a Bruker 400 MHz/
2
00 MHz spectrophotometer. The mass spectra were recorded (s, 1 H, CH cp), 4.29 (s, 1 H, CH cp), 10.35 (br., 1 H, COOH).
1
3
1
using a SSQ 170, Finnigan Mat. Electro spray mass spectra were
recorded on a Finnnigan MAT, MAT 95 XL. Values for m/z are
for the most intense peak of isotope envelope.
C{ H} NMR ([D
8
]THF): δ = 17.7 (CH
3
), 17.8 (CH
), 21.2 (CH ), 22.5 (d, JP,C
P,C
P,C = 8.7 Hz, CH ), 26.3 (d, J =
3 3
), 19.2 (CH ),
2
2
19.4 (CH
= 9.2 Hz, CH
3
), 20.5 (d, JP,C = 7.3 Hz, CH
3
3
), 22.6 (d, 2
J
1
3
3
Eur. J. Inorg. Chem. 2007, 2257–2264
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
2261

J. Langer, R. Fischer, H. Görls, D. Walther
FULL PAPER
3
=
(
8.6 Hz, 2ϫCH-P), 26.7 (d, 1JP,C = 23.5 Hz, 2ϫCH-P), 32.7 (br.,
CH ), 42.7 (br., =CH), 69.3 (CH, cp), 69.4 (CH, cp), 71.0
2ϫCH, cp), 72.4 (CH, cp), 72.7 (CH, cp), 73.8 (d, JP,C = 4.0 Hz,
complex in DMF at room temp. und subsequent cooling to –20 °C.
2
Yield: 0.8 g (85%). C25
H
40
P
2
1
O
2
FeNi (549.08) calcd. C 54.69, H
]THF, 25 °C): δ = 0.96
(tdd, JH,H = 6.9 Hz, JP,H = 4.0 Hz, JP,H = 8.7 Hz, 2 H, Ni–CH ),
), 1.96 (tdd, JH,H = 7.0 Hz, JP,H = 5.1 Hz,
-COO), 2.20–2.47 (m, 4 H, CH), 4.40 (m,
7.34; found. C 54.21, H 7.39. H NMR ([D
8
1
3
3
3
CH, cp), 73.9 (d, JP,C = 4.7 Hz, CH, cp), 83.8 (dd, JP,C = 23.7 Hz,
2
3
1
3
4
J
P,C = 5.1 Hz, C-P, cp), 84.7 (d, JP,C = 25.4 Hz, C-P, cp), 177.7
1.23–1.54 (m, 24 H, CH
3
3
1
1
2
4
(br., COOH). P{ H} NMR ([D
8
]THF, 25 °C): δ = 46.9 (d, JP,P
J
P,H = 7.2 Hz, 2 H, CH
4 H, CH cp), 4.44 (m, 4 H, CH cp). C{ H} NMR ([D
5 °C): δ = 12.4 (dd, J = 31.6 Hz, J = 59.9 Hz, Ni-CH ), 19.8 (d,
J = 11.5 Hz, CH ), 20.6 (d, J = 5.7 Hz, CH ), 37.2 (dd, J = 2.7 Hz,
J = 4.6 Hz, CH -COO), 71.1 (d, J = 4.5 Hz, CH cp), 71.9 (d, J =
.9 Hz, CHЈ cp), 73.3 (d, J = 6.3 Hz, CH cp), 73.5 (d, J = 6.2 Hz,
2
15.3 Hz), 39.3 (d, 2JP,P = 15.3 Hz).
13
1
=
8
]THF,
2
2
[
(
0
(dippf)Pd(nb)]: A solution of dippf (0.36 g, 0.86 mmol) in THF
20 mL) was cooled to –30 °C and added to solid [(nb) Pd] (0.30 g,
.77 mmol) at this temperature. The stirred solution was allowed
3
3
3
2
3
to slowly warm to room temperature. Afterwards half of the solvent
was distilled of under reduced pressure. The remaining orange col-
oured solution was stored at –20 °C for several days, resulting in
the formation of orange red crystals. These crystals were separated
by filtration and dried in a vacuum. From the mother liquor a
second crop of product was obtain by further reduction of the vol-
ume and layering with diethyl ether. Yield: 120 mg (25%).
CHЈ cp), 82.2 (d, J = 10.7 Hz, C cp), 82.8 (d, J = 10.7 Hz, CЈ
cp), 185.5 (m, COO). The signals for CH groups of the isopropyl
substituents overlap with the signals of the used solvent and were
3
1
1
7
therefore not detected. P{ H} NMR ([D ]DMF, 25 °C): δ = 36.5
(
1
d, JP,P = 14.4 Hz), 44.7 (d, JP,P = 14.4 Hz). IR (nujol): ν˜ = (C=O)
634 cm–1 (s).
C
7
29
H
46
1
P
2
FePd (618.9) calcd. C 56.28, H 7.49; found C 56.12, H
2
[
(dippf)Ni(η -C
2
H
4
)] (3b): a) A suspension of [(dippf)Ni(C
2
H
4
-
2
.52. H NMR ([D
8
]THF, 25 °C): δ = 0.58 (d, JH,H = 7.6 Hz, 1
, 2ϫCHHЈ, CHHЈ
COO)] (2b) (200 mg, 0.36 mmol) in DMF (5 mL) was heated to
0 °C. The resulting clear solution was stirred at this temperature
H, CHHЈ bridge), 1.05–1.30 (m, 15 H, 4ϫCH
bridge), 1.52 (m, 2 H, 2ϫCHHЈ), 2.19 (m, JH,P = 6.0 Hz, 4 H,
CH iPr), 2.88 (s, 2 H, CH), 2.99 (d, JH,P = 6.0 Hz, 2 H, CH), 4.23
3
8
2
for additional 3 h. Upon slow cooling to room temperature orange
coloured crystals were formed overnight. These crystals were col-
lected by filtration and dried in a vacuum. A second crop of prod-
uct was obtained by storing the mother liquor at 0 °C for 3 d. Yield:
2
1
3
1
(s, 2 H, CH cp), 4.28 (s, 6 H, CH cp). C{ H} NMR ([D
8
]THF):
iPr), 20.4 (br., 4ϫCH iPr),
6.9 (t, JC,P = 6.3 Hz, 2ϫCH iPr), 27.0 (t, JC,P = 7.6 Hz, 2ϫCH
2
δ = 20.0 (t, JC,P = 5.0 Hz, 4ϫCH
2
iPr), 29.9 (t,
3
3
1
1
1
30 mg (70%). C24
H
40FeNiP
2
(505.06) calcd. C 57.07, H 7.98;
, 25 °C): δ = 1.13 (sext, J
), 2.05 (m, 4 H, CH iPr), 2.19 (br., 4 H, C ),
4
J
CP = 5.0 Hz, 2ϫCHHЈ), 43.4 (s, CHHЈ), 45.6 (s,
1
found 57.17, H 8.16. H NMR (C
6
4
6
D
6
2
ϫCH), 64.2 (pseudo-dt, 2ϫ= CH-), 69.8 (s, 4ϫCH cp), 73.7 (t,
.8 Hz, 24 H, CH
3
2 4
H
2
C,P = 3.8 Hz, 4ϫCH cp), 85.3 (t, 1
J
J
C,P = 9.5 Hz, 2ϫC cp).
13
1
.06 (br., 4 H, CH cp), 4.21 (br., 4 H, CH cp). C{ H} NMR
31
1
P{ H} NMR (81 MHz, [D
8
]THF, 25 °C): δ = 36.4 (s).
2
2
(
C
6
D
6
, 25 °C): δ = 19.9 (t, JP,C = 3.2 Hz, CH
3
), 20.1 (t, JP,C
=
=
1
2
2
3.2 Hz, CH
3
), 26.0 (t,
JP,C = 10.6 Hz, CH iPr), 34.7 (t,
J
P,C
[(dippf)Pd(η -CH
2
=CH-COOH)] (1c): Acrylic acid (0.03 mL,
2
7
8
4
2
.3 Hz, CH ), 69.3 (br., CH, cp), 72.7 (t, JP,C = 2.9 Hz, CH cp),
0
0
.44 mmol) was added to a solution of [(dippf)Pd(nb)] (40 mg,
.065 mmol) in THF (1 mL) at 0 °C with rapid stirring. The re-
1
31
1
6 6
6.4 (t, JP,C = 12.6 Hz, C cp). P{ H} NMR (C D , 25 °C): δ =
2.4 (s).
sulting mixture was warmed to room temperature and stirred for
additional 30 min. Afterwards the solvent was completely removed
by distillation under reduced pressure. The remaining orange red
sticky oil was treated with diethyl ether (2 mL) and stirred for
2
[
(dtbpf)Ni(η -C
2
H
4
)] (3c): A solution of dtbpf (0.50 g, 1.05 mmol)
Ni(C
in DMF (3 mL) was added to a suspension of green [(py)
2
2 4-
H
COO)] (0.29 g, 1.00 mmol) in DMF (3 mL) at room temperature.
The resulting orange brown solution was stirred for 2 h and after-
wards 3 mL of DMF were distilled of under reduced pressure at
room temperature. The resulting orange coloured precipitate was
collected by filtration and dried in a vacuum. Suitable crystals for
X-ray measurement were obtained from a saturated solution of the
2
0 min. The resulting suspension was filtered and the clear yellow
solution was stored at –20 °C. The isolated solid was redissolved in
a few drops of THF and that solution was kept at 5 °C for several
days. From both solutions, suitable crystals for X-ray measurement
2
were obtained; [(dippf)Pd(η -CH
2
=CH-COOH)] from ether,
2
[[(dippf)Pd(η -CH
2
=CH-COOH)]·THF from THF]. The yield was
complex in DMF at room temp. und subsequent cooling. Yield:
not determined.
1
0
.3 g (50%). C28
H
48
P
2
FeNi (561.18). H NMR ([D
7
]DMF, 25 °C):
3
δ = 1.35 (d, JH,P = 11.5 Hz, 36 H, CH
.40 (m, 4 H, CH cp), 4.45 (br., 4 H, CH cp). C{ H} NMR ([D
tBu), 36.6 (t, JC,P = 7.0 Hz, C
7.3 (t, JC,P = 6.2 Hz, C tBu), 69.6 (s, CH cp), 75.4 (s, CH cp),
7.0 (t, JC,P = 8.4 Hz, C cp). P{ H} NMR ([D
65.6 (s).
3
tBu), 1.80 (s, 4 H, CH
2
),
8
]-
4
),
[
(dppf)Ni(C -COO)] (2a): Yellow dppf (0.77 g, 1.39 mmol) was
added to a suspension of green [(py) Ni(C COO)] (0.40 g,
.38 mmol) in DMF (8 mL) at 0 °C. The solution was allowed to
2 4
H
1
3
1
4
2
2 4
H
2
THF, 25 °C): δ = 32.0 (s, CH
3
8
=
3
2
H
1
1
slowly warm to room temperature, while the starting materials dis-
solved and a yellow precipitate was formed. To remove liberated
pyridine, 2 mL of DMF was distilled of under reduced pressure
at room temperature. Afterwards the yellow solid was isolated by
1
31
1
7
]DMF, 25 °C): δ
[
(dppf)
Ni] (4):[5,6] A suspension of 2a in THF was heated to 40 °C
2
filtration, washed with diethyl ether and dried in a vacuum. Yield:
and DMF was added with rapid stirring until nearly all solids have
dissolved. The resulting solution was filtered through celite and
stored for 2 weeks at 5 °C. During this period, some precipitate
was formed and afterwards removed by decantation. The remain-
ing solution was concentrated in vacuo until all THF was removed.
1
0
.91 g (96%) yellow powder. H NMR ([D
7
]DMF, 25 °C): δ = 0.64
-COO), 4.45 (s, 4
H, CH cp), 7.45–8.00 (m, 20 H Phenyl). P{ H} NMR ([D ]DMF,
5 °C): δ = 19.4 (br), 39.0 (br). IR (nujol): ν˜ = (C=O) 1642 cm .
2 2
(m, 2 H, Ni-CH ), 1.93 (t, J = 6.9 Hz, 2 H, CH
31
1
7
–
1
2
[
1
[
(dippf)Ni(C -COO)] (2b):
.98 mmol) in DMF (4 mL) was added to a suspension of green
Ni(C COO)] (0.49 g, 1.70 mmol) in DMF (4 mL) at room occurred. These crystals were collected by filtration and dried in a
2
H
4
A
solution of dippf (0.83 g, The residual orange brown coloured solution in DMF was stored
for several weeks at –20 °C, after which orange red crystals had
(py)
2
2 4
H
temperature. The resulting solution was stirred for 1 h. Meanwhile
an orange yellow precipitate was formed. The solid was afterwards
collected by filtration and dried in a vacuum. Suitable crystals for
X-ray measurement were obtained from a saturated solution of the
vacuum. The yield was not determined. C68
calcd. C 69.72, H 5.16; found C 69.82, H 5.09. HNMR ([D
25 °C): δ = 3.97 (s, 8 H, CH cp), 4.10 (s, 8 H, CH cp), 6.84 (pt, J
= 7.4 Hz, 16 H, o-CH ph), 7.01 (pt, J = 7.2 Hz, 8 H, p-CH ph),
H
60
1
P
4
Fe
2
Ni (1171.51)
]THF,
8
2262
www.eurjic.org
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2007, 2257–2264

Complexes with 1,1Ј-Bis(phosphanyl)ferrocenes
FULL PAPER
.45–7.55 (m, 16 H, m-CH ph). 13C{ H} NMR ([D
1
]THF, 25 °C): 106.060(2)°, V = 5272.0(3) Å , T = –90 °C, Z = 8, ρcalcd.
3
=
7
8
–
3
–1
δ = 70.5 (s, 8ϫCH cp), 75.2 (s, 8ϫCH cp), 87.5 (m, 4ϫC cp),
α
1.504 gcm , µ (Mo-K ) = 13.73 cm , F(000) = 2464, 15456 reflec-
1
7
27.4 (s, 16ϫm-CH ph), 128.1 (s, 8ϫp-CH ph), 135.1 (pt, JC,P
.5 Hz, 16ϫo-CH ph), 142.0 (m, 8ϫC ph).
=
tions in h(–24/25), k(–13/9), l(–35/34), measured in the range
2.14°ՅΘՅ27.50°, completeness Θmax = 97.4%, 5901 independent
reflections, Rint = 0.1058, 4654 reflections with F
parameters, 0 restraints, R1obs = 0.0537, wR2obs = 0.1336, R1all
.0736, wR2all = 0.1471, GOOF = 1.028, largest difference peak
o o
Ͼ 4σ(F ), 300
X-ray Crystallographic Studies: The intensity data for the com-
pounds were collected on a Nonius KappaCCD diffractometer by
=
0
α
using graphite-monochromated Mo-K radiation. Data were cor-
–
3
and hole: 0.847/–0.871 e·Å .
Crystal Data for 2b:[34]
40FeNiO
low-green prism, size 0.10ϫ0.10ϫ0.02 mm , monoclinic, space
group P2 /c, a = 17.3484(9), b = 8.7957(6), c = 16.7547(8) Å, β =
96.382(4)°, V = 2540.8(2) Å , T = –90 °C, Z = 4, ρcalcd.
rected for Lorentz and polarization effects, but not for absorption
[
30,31]
–1
effects.
(
The structures were solved by direct methods
C
25
H
2 2
P , Mr = 549.07 gmol , yel-
[
32]
3
SHELXS ) and refined by full-matrix least-squares techniques
against F
2
[33]
o
(SHELXL-97 ). All hydrogen atoms were included at
1
3
calculated positions with fixed thermal parameters. All non-hydro-
gen atoms were refined anisotropically.[ XP (SIEMENS Analyti-
cal X-ray Instruments, Inc.) was used for structure representations.
=
4]
–3
–1
1.435 gcm , µ (Mo-K
tions in h(–22/22), k(–10/11), l(–21/21), measured in the range
.36°ՅΘՅ27.45°, completeness Θmax = 99.4%, 5774 independent
reflections, Rint = 0.0555, 3696 reflections with F Ͼ 4σ(F ), 288
parameters, 0 restraints, R1obs = 0.0740, wR2obs = 0.1567, R1all
.1260, wR2all = 0.1807, GOOF = 1.066, largest difference peak
α
) = 14.57 cm , F(000) = 1160, 9791 reflec-
2
[
34]
Crystal Data for 1a·1.5DMF:
C
37
H
32FeNNiO
Mr = 795.78 gmol , orange prism, size 0.12ϫ0.12ϫ0.10 mm ,
monoclinic, space group P2 /n, a = 14.5426(3), b = 13.9250(6), c =
2 2 3 7
P ·1.5C H ON,
–1
3
o
o
=
1
0
3
1
4
1
9.0968(7) Å, β = 108.237(2)°, V = 3673.0(2) Å , T = –90 °C, Z =
, ρcalcd. = 1.439 gcm , µ (Mo-K
2426 reflections in h(–18/18), k(–18/16), l(–24/24), measured in the
–
3
and hole: 1.321/–0.610 e·Å .
–
3
–1
α
) = 10.38 cm , F(000) = 1660,
Crystal Data for 3b:[34]
C
H
40FeNiP
, Mr = 505.06 gmol , orange
–1
24
2
3
¯
range 1.55°ՅΘՅ27.60°, completeness Θmax = 93%, 7921 indepen-
dent reflections, Rint = 0.0553, 4887 reflections with F Ͼ 4σ(F
41 parameters, 0 restraints, R1obs = 0.0743, wR2obs = 0.2116, R1all
prism, size 0.10ϫ0.09ϫ0.08 mm , triclinic, space group P1, a =
), 8.7665(2), b = 9.0021(2), c = 17.1663(3) Å, α = 87.0310(10), β =
o
o
3
4
82.8390(10), γ = 65.4730(10)°, V = 1222.86(4) Å , T = –90 °C, Z =
2, ρcalcd. = 1.372 gcm , µ (Mo-K ) = 15.02 cm , F(000) = 536,
α
–
3
–1
=
0.1110, wR2all = 0.2206, GOOF = 1.058, largest difference peak
–3
and hole: 0.815/–0.499 e·Å .
9447 reflections in h(–10/11), k(–11/11), l(–22/22), measured in the
range 2.74°ՅΘՅ27.43°, completeness Θmax = 99.5%, 5557 inde-
[
34]
Crystal Data for 1a·2THF:
37 2 2 4 8
C H32FeNiO P ·2C H O, Mr =
pendent reflections, Rint = 0.0345, 4870 reflections with F
o
Ͼ
–1
3
8
29.33 gmol , orange prism, size 0.18ϫ0.12ϫ0.08 mm , triclinic,
space group P1, a = 11.1233(7), b = 12.7648(6), c = 14.696(1) Å, α
87.660(4), β = 79.684(3), γ = 77.065(3)°, V = 2000.8(2) Å , T =
90 °C, Z = 2, ρcalcd. = 1.377 gcm , µ (Mo-K
4σ(F
o
), 277 parameters, 0 restraints, R1obs = 0.0343, wR2obs
=
¯
0
.0894, R1all = 0.0416, wR2all = 0.0950, GOOF = 1.016, largest
3
=
–
–
3
difference peak and hole: 0.374/–0.557 e·Å .
–3
–1
α
) = 9.55 cm , F(000)
Crystal Data for 3c:[34]
C
28
H
48FeNiP , Mr = 561.16 gmol , orange
–1
=
868, 13225 reflections in h(–14/14), k(–16/16), l(–19/18), mea-
2
3
sured in the range 1.64°ՅΘՅ27.49°, completeness Θmax = 95.6%,
782 independent reflections, Rint = 0.0588, 5591 reflections with
Ͼ 4σ(F ), 484 parameters, 0 restraints, R1obs = 0.0447, wR2obs
0.0980, R1all = 0.0746, wR2all = 0.1036, GOOF = 0.901, largest
prism, size 0.10ϫ0.08ϫ0.07 mm , orthorhombic, space group
Pbca, a = 16.0359(2), b = 11.61920(10), c = 29.9821(4) Å, V =
8
3
–3
F
o
o
5586.39(11) Å , T = –90 °C, Z = 8, ρcalcd. = 1.334 gcm , µ (Mo-
–
1
=
K
α
) = 13.22 cm , F(000) = 2400, 11956 reflections in h(–20/20),
k(–15/15), l(–38/38), measured in the range 2.88°ՅΘՅ27.48°,
completeness Θmax = 99.4%, 6363 independent reflections, Rint
.0422, 4695 reflections with F Ͼ 4σ(F ), 317 parameters, 0 re-
straints, R1obs = 0.0368, wR2obs = 0.0784, R1all = 0.0630, wR2all
–3
difference peak and hole: 0.719/–0.765 e·Å .
=
Crystal Data for 1b:[34] , Mr = 549.07 gmol–1,
C
H
40FeNiO
25
2 2
P
0
o
o
3
orange prism, size 0.12ϫ0.12ϫ0.10 mm , triclinic, space group
P1, a = 10.2600(4), b = 10.8590(4), c = 12.7729(3) Å, α = 84.885(2),
β = 73.799(2), γ = 68.3570(10)°, V = 1270.07(7) Å , T = –90 °C, Z
2, ρcalcd. = 1.436 gcm , µ (Mo-K
596 reflections in h(–12/13), k(–14/12), l(–16/14), measured in the
range 2.40°ՅΘՅ27.48°, completeness Θmax = 96.6%, 5633 inde-
=
¯
0
.0863, GOOF = 0.985, largest difference peak and hole: 0.376/
3
–
3
–0.447 e·Å .
–3
–1
=
8
α
) = 14.58 cm , F(000) = 580,
Crystal Data for 4:[34]
C H56Fe NiP , Mr = 1167.42 gmol ,
–1
68 2 4
3
orange prism, size 0.03ϫ0.03ϫ0.02 mm , triclinic, space group
P1, a = 12.9787(5), b = 13.8150(6), c = 15.2711(7) Å, α = 86.939(2),
β = 89.940(2), γ = 87.033(2)°, V = 2730.5(2) Å , T = –90 °C, Z =
α
2, ρcalcd. = 1.420 gcm , µ (Mo-K ) = 10.26 cm , F(000) = 1208,
¯
pendent reflections, Rint = 0.0549, 4352 reflections with F
o
Ͼ
3
4σ(F
o
), 304 parameters, 0 restraints, R1obs = 0.0341, wR2obs
=
–
3
–1
0
.0920, R1all = 0.0458, wR2all = 0.0949, GOOF = 1.002, largest
–3
18086 reflections in h(–16/15), k(–16/17), l(–19/19), measured in the
range 2.10°ՅΘՅ27.50°, completeness Θmax = 95.8%, 11986 inde-
difference peak and hole: 0.553/–0.532 e·Å .
[
34]
Crystal Data for 1c·THF:
6
C
25
H
40FeO
68.86 gmol , yellow prism, size 0.05ϫ0.05ϫ0.05 mm , mono-
clinic, space group P2 /n, a = 10.242(2), b = 15.994(3), c =
2 2 4 8
P Pd·C H O, Mr =
pendent reflections, Rint = 0.0487, 7647 reflections with F
o
Ͼ
–1
3
4σ(F
o
), 676 parameters, 0 restraints, R1obs = 0.0629, wR2obs
=
1
0
.1086, R1all = 0.1191, wR2all = 0.1295, GOOF = 1.045, largest
3
1
ρ
2
8.487(4) Å, β = 96.18(3)°, V = 3010.8(10) Å , T = –90 °C, Z = 4,
calcd. = 1.476 gcm , µ (Mo-K
0354 reflections in h(–10/13), k(–20/20), l(–23/23), measured in the
–3
difference peak and hole: 0.444/–0.472 e·Å .
–3
–1
α
) = 12.13 cm , F(000) = 1392,
range 1.69°ՅΘՅ27.47°, completeness Θmax = 99.6%, 6871 inde- Acknowledgments
pendent reflections, Rint = 0.0232, 6267 reflections with F
o
Ͼ
4
0
σ(F
o
), 349 parameters, 0 restraints, R1obs = 0.0291, wR2obs
=
This research was supported by a grant from the Deutsche Bundes-
stiftung Umwelt and by the Deutsche Forschungsgemeinschaft
(DFG) (SFB 436).
.0789, R1all = 0.0327, wR2all = 0.0820, GOOF = 0.983, largest
–3
difference peak and hole: 1.891/–0.850 e·Å .
Crystal Data for 1c:[34]
C
25
H
40FeO Pd, Mr = 596.76 gmol , yel-
–1
2 2
P
3
low prism, size 0.06ϫ0.04ϫ0.04 mm , monoclinic, space group
C2/c, a = 19.7868(7), b = 10.0423(4), c = 27.6093(9) Å, β =
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2263

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Received: November 9, 2006
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Published Online: February 21, 2007
2264
www.eurjic.org
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2007, 2257–2264