Novel ferrocene derivatives with PH-functionalized phosphanylalkylcyclopentadienyl ligands: Syntheses and molecular structures of rac-[Fe{(η5-C5H4) CMe2PHR}2] (R = Ph, Mes) and rac-[Fe{(η5-

Article abstract of DOI:10.1002/1099-0682(200205)2002:5<1174::AID-EJIC1174>3.0.CO;2-A

6,6-Dimethylfulvene reacts with LiPHMes (Mes = 2,4,6-Me₃C₆H₂) to give Li[(C₅H₄)CMe₂PHMes] (1). The ferrocene derivatives rac-[Fe{(η⁵-C₅H₄) CMe₂PH

Full text of DOI:10.1002/1099-0682(200205)2002:5<1174::AID-EJIC1174>3.0.CO;2-A

FULL PAPER
Novel Ferrocene Derivatives with PH-Functionalized
Phosphanylalkylcyclopentadienyl Ligands: Syntheses and Molecular Structures
of rac-[Fe{(η5-C5H4)CMe2PHR}2] (R ؍ Ph, Mes) and
rac-[Fe{(η5-C5H4)CMe2PHPh(Cp*TaCl4)}2][‡]
Thomas Höcher,[a] Steffen Blaurock,[a] and Evamarie Hey-Hawkins*[a]
Dedicated to Professor Joachim Strähle on the occasion of his 65th birthday
Keywords: Metallocenes / P ligands / Bridging ligands / Secondary phosphanes / Tantalum
6,6-Dimethylfulvene reacts with LiPHMes (Mes = 2,4,6-
Me3C6H2) to give Li[(C5H4)CMe2PHMes] (1). The ferrocene
derivatives rac-[Fe{(η5-C5H4)CMe2PHR}2] [R = Ph (2), Mes ture determinations were carried out on 2−4.
(3)] are obtained in high yield from the lithium reagents
rac-[Fe{(η5-C5H4)CMe2PHPh(Cp*TaCl4)}2] (4). Compounds
1−4 were characterized spectroscopically, and crystal struc-
Li[(C5H4)CMe2PHR] (R = Ph, Mes) and FeCl2. Compound 2
(
Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany,
reacts with [Cp*TaCl4] to give the heterotrinuclear complex 2002)
they can bridge two (different) metal centers (B) (M ϭ
metal, M1 ϭ M2 or M1 ϶ M2, L ϭ ligands, X ϭ spacer
(alkylidene, arylidene), R ϭ alkyl, aryl).
Introduction
Since the first report of a cyclopentadienyl transition
metal complex in which the cyclopentadienyl ligand bears
a donor-functionalized side chain, by Mathey et al. in
1978,[1] this area has expanded rapidly.[2] While numerous
O- and N-functionalized cyclopentadienyl ligands are
known, the number of cyclopentadienes with a P-func-
tionalized alkyl or silyl side chain is still small,[1,3] and only
recently have we reported the first such compounds in
which the P atom has a reactive PϪH bond, namely, 1-
SiMe2PHCy-2,3,4,5-Me4C5H, Li2[(C5Me4)SiMe2PR] [R ϭ
Cy, 2,4,6-Me3C6H2 (Mes)], Li[(C5H4)CMe2PHR] (R ϭ Ph,
tBu) and Li2[(C5H4)CH2CH2PPh].[4,5] The molecular struc-
tures of [Li(tmeda)]2[(C5H4)CMe2PPh][6] and [Li(tmeda)]-
[(C5H4)CMe2PR2][7] (R ϭ Ph, Me) were also reported. Such
compounds are useful precursors for mono- or dianionic
bifunctional ligands in transition metal chemistry. Thus, the
monoanionic phosphanylalkylcyclopentadienyl ligands can
act as chelating ligands towards one metal center (A) or
We have recently shown that Li2[(C5Me4)SiMe2PR]
(R
ϭ
Cy, Mes) reacts with ZrCl4 to give [{(η5-
C5Me4)2SiMe2}ZrCl2] and (PCy)4 or (PHMes)2, while
Li[(C5H4)CMe2PHR] reacts with ZrCl4 or [TiCl3(THF)3]
to yield [{(η5-C5H4)CMe2PHR}2ZrCl2] or [{(η5-
C5H4)CMe2PHR}2TiCl] (R ϭ Ph, tBu).[5] However, these
complexes slowly decompose in solution with formation of
[{(η5-C5H4)2CMe2}MCl2] (M ϭ Zr, Ti).[5] Erker et al. re-
ported that the complexes [{CyPCMe2(η5-C5H4)}M(NR2)2]
(M ϭ Ti, R ϭ Me; M ϭ Zr, R ϭ Et) are active catalysts
for the polymerization of α-olefins.[8]
We now report the synthesis of the novel stable PH-func-
tionalized
ferrocene
derivatives
rac-[Fe{(η5-C5H4)-
CMe2PHR}2] [R ϭ Ph (2), Mes (3)] and the heterotrinu-
clear complex rac-[Fe{(η5-C5H4)CMe2PHPh(Cp*TaCl4)}2]
(4) of type B.
Ferrocene derivatives usually show enhanced stability
and are generally nontoxic. Thus, their industrial applica-
tions range from additives for heating oil to reduce forma-
tion of soot, iron-containing fertilizers, UV absorbers and
protective coatings for rockets and satellites.[9]
[‡]
Parts of this work were presented as a poster at the 34th
International Conference on Coordination Chemistry,
Edinburgh, 9Ϫ14 July 2000 (abstract no. P0600) and at the
XVth International Conference on Phosphorus Chemistry,
Sendai, 29 July Ϫ 3 August 2001 (abstract no. PB065).
[a]
Institut für Anorganische Chemie der Universität,
Johannisallee 29, 04103 Leipzig, Germany
E-mail: hey@rz.uni-leipzig.de
1174
WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002 1434Ϫ1948/02/0505Ϫ1174 $ 20.00ϩ.50/0 Eur. J. Inorg. Chem. 2002, 1174Ϫ1180

Ferrocene Derivatives with PH-Functionalized Phosphanylalkylcyclopentadienyl Ligands
FULL PAPER
Results and Discussion
cemic form (R,R and S,S enantiomer) and the meso form
(S,R enantiomer). As bulky substituents are present on the
cyclopentadienyl rings, the antiperiplanar conformation is
favored (see X-ray crystal structure determinations of 2Ϫ4
below).
Syntheses of Compounds 1؊4.
As a general synthetic route to cyclopentadienes with P-
functionalized side chains, the addition of alkali metal
phosphanides to fulvenes has been employed.[3aϪ3c,4,5]
Accordingly, 6,6-dimethylfulvene reacts with LiPHMes
in Et2O at room temperature to give the highly air and
water sensitive compound Li[(C5H4)CMe2PHMes] (1)
[Equation (1)].
No meaningful 31P NMR spectra of the reaction mixture
could be obtained due to the presence of small amounts of
FeCl2. However, the 31P NMR spectra recorded for 2 at
different stages of workup always indicated the presence of
only one diastereomer. Thus, in the 31P{1H} NMR spec-
trum of crystalline 2, only one signal is observed. However,
in the 31P NMR spectrum of 3, obtained from n-hexane,
two overlapping doublets of different intensity (ca. 4:1) are
observed at δ ϭ Ϫ33.4 and Ϫ33.9 with PϪH coupling con-
stants of 219 and 213 Hz, respectively, even at elevated tem-
perature (340 K); this indicates the formation of both dia-
stereomers, one of which is preferred. Recrystallization
from toluene yields the preferred isomer (which was shown
to be the rac isomer by crystal structure determination) as
orange rod-like crystals. The meso isomer could not be ob-
tained in pure form.
(1)
1
The H NMR spectrum of 1 indicates that the methyl
groups in PϪC(Me2) are prochiral and thus diastereotopic.
Therefore, the two nonequivalent Me groups appear as two
doublets due to PϪH coupling [δ ϭ 1.43 (3JPϪH ϭ 8.8 Hz);
δ ϭ 1.41 (3JPϪH ϭ 13.0 Hz)]. However, in the 31P NMR
spectrum, the two Me groups are equivalent, and a doublet
of septets is observed. As was observed for
Li[(C5H4)CMe2PHR] (R ϭ Ph,[4] Cy[5]), the signal is shifted
to low field by ca. 110 ppm, and the PϪH coupling con-
stant increases by ca. 10Ϫ15 Hz relative to the primary
phosphane [1: δ ϭ Ϫ45.6 (1JPϪH ϭ 216 Hz); PH2Mes:[10]
δ ϭ Ϫ154.8 (1JPϪH ϭ 203 Hz)]. Similarly, the signal of the
In the proton-coupled 31P NMR spectrum of 2 and 3, a
doublet of multiplets is observed [2: δ ϭ 8.8 (1JPϪH
ϭ
207 Hz); 3: δ ϭ Ϫ32.8 (1JPϪH ϭ 214 Hz)], which are shifted
to low field by ca. 10Ϫ13 ppm relative to
Li[(C5H4)CMe2PHR] (R ϭ Ph, Mes). The complex coup-
ling pattern in 2 arises from coupling of the protons of the
1
Me and Ph groups. As was already observed for 1, the H
NMR spectra of 2 and 3 indicate that the methyl groups in
PϪC(Me2) are prochiral and thus diastereotopic. Thus, the
two nonequivalent Me groups appear as two doublets due
to PϪH coupling [2: δ ϭ 1.32 (3JPϪH ϭ 12.0 Hz), 1.38
(3JPϪH ϭ 12.4 Hz); 3: δ ϭ 1.39 (3JPϪH ϭ 13.0 Hz), 1.45
(3JPϪH ϭ 8.8 Hz)]. These signals and those of the PϪH
group are only slightly shifted relative to those of the li-
thium reagents, while a shift to high-field of ca. 1.8 ppm is
observed for the CϪH protons of the cyclopentadienyl
rings.
1
PH group is shifted to low field in the H NMR spectrum
by ca. 0.2Ϫ0.9 ppm relative to the phosphane (1: δ ϭ 4.36;
PH2Mes:[10] δ ϭ 3.53). Compared with the signals of 6,6-
dimethylfulvene (Me: δ ϭ 2.19; C5H4: δ ϭ 6.53Ϫ5.45),[11]
the corresponding signals in 1 are shifted to high field (δ ϭ
1.41, 1.43 and 5.56).
The ferrocene derivatives [Fe{(η5-C5H4)CMe2PHR}2]
[R ϭ Ph (2), Mes (3)] are obtained in high yield from the
lithium reagents Li[(C5H4)CMe2PHR] (R ϭ Ph, Mes (1)]
and FeCl2 in THF at room temperature [Equation (2)].
At room temperature, the ortho-Me groups of the mesityl
1
ring in 3 give a broad signal at δ ϭ 2.27 in the H NMR
(2)
(3)
After workup and repeated recrystallization from n-pent-
ane (2) or toluene (3), the ferrocene derivatives are obtained
as orange solids, which are air-stable, at least for a limited
period of time. Due to the presence of two chiral phos-
phanyl groups, two diastereomers can be formed: the ra-
Eur. J. Inorg. Chem. 2002, 1174Ϫ1180
1175

T. Höcher, S. Blaurock, E. Hey-Hawkins
FULL PAPER
spectrum, indicating that rotation around the PϪC(mesityl) signals are observed. From the coalescence temperature
bond is hindered. At 340 K, only one sharp signal is ob- [Tc ϭ 291(2) K] the activation enthalpy (∆G# ϭ 56 Ϯ 1 kJ/
served for the Me groups, while below 263 K two separate mol)[12] was determined by using the Eyring equa-
˚
Table 1. Selected bond lengths [A] and bond angles [°] for 2Ϫ4
[Fe{(η5-C5H4)CMe2PHPh}2] (2)
FeϪC
P(1)ϪC(6)
P(1)ϪH(1P)
2.045(5)Ϫ2.064(5)
1.891(3)
1.43(8)
P(1)ϪC(9)
P(1)ϪH(2P)
1.823(3)
1.7(2)
C(9)ϪP(1)ϪC(6)
C(6)ϪP(1)ϪH(1P)
C(6)ϪP(1)ϪH(2P)
C(14)ϪC(9)ϪP(1)
C(7)ϪC(6)ϪP(1)
103.3(1)
101(3)
119(5)
120.7(3)
109.4(3)
C(9)ϪP(1)ϪH(1P)
C(9)ϪP(1)ϪH(2P)
C(10)ϪC(9)ϪP(1)
C(1)ϪC(6)ϪP(1)
C(8)ϪC(6)ϪP(1)
116(3)
105(5)
120.8(3)
103.4(2)
110.8(3)
[Fe{(η5-C5H4)CMe2PHMes}2] (3)
FeϪC
P(1)ϪC(14)
P(1)ϪH(1P)
P(2)ϪC(23)
C(14)ϪP(1)ϪC(11)
C(11)ϪP(1)ϪH(1P)
C(26)ϪP(2)ϪH(2P)
C(15)ϪC(14)ϪP(1)
C(31)ϪC(26)ϪP(2)
C(1)ϪC(11)ϪP(1)
C(13)ϪC(11)ϪP(1)
C(25)ϪC(23)ϪP(2)
2.042(2)Ϫ2.085(2)
1.848(2)
1.25(3)
1.901(2)
107.55(9)
98(1)
P(1)ϪC(11)
P(2)ϪC(26)
P(2)ϪH(2P)
1.903(2)
1.838(2)
1.0(1)
100(1)
106.87(9)
99(8)
123.2(2)
118.8(2)
108.8(2)
110.3(1)
103.8(1)
C(14)ϪP(1)ϪH(1P)
C(26)ϪP(2)ϪC(23)
C(23)ϪP(2)ϪH(2P)
C(19)ϪC(14)ϪP(1)
C(27)ϪC(26)ϪP(2)
C(12)ϪC(11)ϪP(1)
C(6)ϪC(23)ϪP(2)
C(24)ϪC(23)ϪP(2)
111(8)
117.7(2)
122.7(2)
110.7(1)
103.3(2)
109.4(1)
[Fe{(η5-C5H4)CMe2PHPh(Cp*TaCl4)}2] (4)
TaϪC
Ta(1)ϪCl(1)
Ta(1)ϪCl(3)
Ta(2)ϪCl(5)
Ta(2)ϪCl(7)
Ta(1)ϪP(1)
P(1)ϪC(14)
P(1)ϪH(1P)
2.446(5)Ϫ2.530(4)
2.400(1)
2.404(1)
2.393(1)
2.388(1)
2.758(1)
1.829(4)
1.45(5)
1.909(5)
87.39(4)
85.32(5)
152.81(4)
71.78(4)
80.16(4)
116.9(2)
105.3(2)
96(2)
104.7(3)
106.8(3)
123.1(4)
86.34(5)
86.91(4)
151.24(4)
72.44(4)
78.80(4)
117.4(2)
100(2)
FeϪC
Ta(1)ϪCl(2)
Ta(1)ϪCl(4)
Ta(2)ϪCl(6)
Ta(2)ϪCl(8)
Ta(2)ϪP(2)
P(1)ϪC(11)
P(2)ϪC(33)
2.040(5)Ϫ2.070(4)
2.390(1)
2.402(1)
2.402(1)
2.401(1)
2.798(1)
1.899(5)
1.821(4)
1.29(4)
151.90(4)
87.39(4)
86.83(5)
78.37(4)
74.66(4)
127.9(1)
99(2)
P(2)ϪC(30)
P(2)ϪH(2P)
Cl(2)ϪTa(1)ϪCl(1)
Cl(1)ϪTa(1)ϪCl(4)
Cl(1)ϪTa(1)ϪCl(3)
Cl(2)ϪTa(1)ϪP(1)
Cl(4)ϪTa(1)ϪP(1)
C(14)ϪP(1)ϪTa(1)
C(14)ϪP(1)ϪC(11)
C(11)ϪP(1)ϪH(1P)
C(1)ϪC(11)ϪP(1)
C(12)ϪC(11)ϪP(1)
C(15)ϪC(14)ϪP(1)
Cl(7)ϪTa(2)ϪCl(8)
Cl(7)ϪTa(2)ϪCl(6)
Cl(8)ϪTa(2)ϪCl(6)
Cl(6)ϪTa(2)ϪP(2)
Cl(8)ϪTa(2)ϪP(2)
C(33)ϪP(2)ϪTa(2)
C(30)ϪP(2)ϪH(2P)
C(6)ϪC(30)ϪP(2)
C(32)ϪC(30)ϪP(2)
C(34)ϪC(33)ϪP(2)
Cl(2)ϪTa(1)ϪCl(4)
Cl(2)ϪTa(1)ϪCl(3)
Cl(4)ϪTa(1)ϪCl(3)
Cl(1)ϪTa(1)ϪP(1)
Cl(3)ϪTa(1)ϪP(1)
C(11)ϪP(1)ϪTa(1)
C(14)ϪP(1)ϪH(1P)
Ta(1)ϪP(1)ϪH(1P)
C(13)ϪC(11)ϪP(1)
C(19)ϪC(14)ϪP(1)
Cl(7)ϪTa(2)ϪCl(5)
Cl(5)ϪTa(2)ϪCl(8)
Cl(5)ϪTa(2)ϪCl(6)
Cl(5)ϪTa(2)ϪP(2)
Cl(7)ϪTa(2)ϪP(2)
Ta(2)ϪP(2)ϪH(2P)
C(30)ϪP(2)ϪTa(2)
C(33)ϪP(2)ϪH(2P)
C(31)ϪC(30)ϪP(2)
C(38)ϪC(33)ϪP(2)
C(33)ϪP(2)ϪC(30)
106(2)
112.6(4)
118.8(4)
152.66(4)
88.10(5)
85.19(5)
74.66(4)
78.01(4)
103(2)
127.3(2)
101(2)
107.9(3)
120.3(4)
103.5(2)
105.2(3)
110.0(3)
121.9(3)
1176
Eur. J. Inorg. Chem. 2002, 1174Ϫ1180

Ferrocene Derivatives with PH-Functionalized Phosphanylalkylcyclopentadienyl Ligands
FULL PAPER
tion.[13] Compound 2 reacts with [Cp*TaCl4] in toluene at be determined, the presence of the rac isomer can be de-
room temperature to give the heterotrinuclear complex rac- duced for 2, too.
[Fe{(η5-C5H4)CMe2PHPh(Cp*TaCl4)}2] (4) [Equation (3)].
The trinuclear complex 4 is unstable in solution at room
temperature. When brown crystals of 4 are dissolved in ben-
zene or toluene at room temperature, a white precipitate
forms after only a few minutes. Thus, for the NMR spectro-
scopic studies the crystals were cooled to Ϫ195 °C in an
NMR tube and the solvent ([D8]toluene or [D6]benzene)
was added at this temperature. The sample was warmed to
ca. Ϫ50 °C prior to the NMR spectroscopic studies.
At Ϫ50 °C, two doublets are observed in the 31P NMR
spectrum at δ ϭ 8.5 and 57.6 (ratio ca. 1:2), which collapse
into one broad singlet at room temperature (δ ϭ 33.7).
Recrystallization from dichloromethane and toluene yielded
small brown crystals suitable for crystal structure deter-
mination, which showed this to be the rac isomer.
Molecular Structures of 2؊4
The ferrocene derivatives crystallize in the centrosym-
metric monoclinic space group no. 14 [P21/n (2, 3) and P21/
c (4)]. For 2, two molecules are present in the unit cell, while
for 3 and 4, four molecules are present.
In all three complexes, the substituted cyclopentadienyl
rings adopt an antiperiplanar conformation, as expected for
bulky substituents (see Table 1 for bond lengths and
Figure 2. Molecular structure of rac-[Fe{(C5H4)CMe2PHMes}2]
angles). An antiperiplanar conformation was also observed
(3) showing the atom numbering scheme employed (ORTEP plot,
50% probability, SHELXTL PLUS; XP[23]); hydrogen atoms (other
than PϪH) are omitted for clarity; only the R,R isomer is shown.
for [Fe{(η5-C5H4)CH2PPh2}2].[14]
In 2, the Ph and cyclopentadienyl rings are almost copla-
nar [angle between plane of Ph ring and cyclopentadienyl
ring 6.0(3)°]. The Fe atom is located on a crystallographic
center of inversion. As the PϪH proton is disordered over
two positions (Figure 1), the configuration of the phos-
phanyl group could not be determined.
In 3 and 4, the aryl rings and the cyclopentadienyl rings
adopt an angle of 31.2(1)° and 34.1(1)° (3) or 31.4(2)° and
33.3(2)° (4). In 4, the TaϪP bond lengths of 2.758(1) and
˚
2.798(1) A are longer than those in the phosphane complex
[15]
˚
[Cp*TaCl4(PH2Ph)] [2.651(3) A].
Apparently, replace-
ment of the small H substituent by the bulky (C5H4)CMe2
substituent at the P atom weakens the TaϪP bond. In 4,
˚
the Ta atom is located 0.573(1) A above the plane formed
by the four Cl atoms. This distance is similar to that in [Cp*
˚
TaCl4(PH2Ph)] [0.602(2) A] and smaller than that observed
[15]
˚
for [Cp*TaCl4] [0.806(2) A],
due to the higher steric de-
mand of the phosphane ligands in [Cp*TaCl4(PH2Ph)] and
4. Only one other trinuclear bis(phosphanylmethyl)ferro-
cene complex, namely [Fe{(η5-C5H4)CH2PPh2[RuCl2(η6-
1,2,3,4-Me4C6)]}2], has been structurally character-
ized.[16,17]
Figure 1. Molecular structure of rac-[Fe{(C5H4)CMe2PHPh}2] (2)
showing the atom numbering scheme employed (ORTEP plot, 50%
probability, SHELXTL PLUS; XP[23]); hydrogen atoms (other than
PϪH) are omitted for clarity; the PϪH proton is disordered
˚
The FeϪC bond lengths of 2.04Ϫ2.08 A and the distance
R
˚
FeϪCpcenter of ca. 1.65Ϫ1.67 A in 2Ϫ4 are in good agree-
ment with those of related ferrocene derivatives.[14,16Ϫ19]
In 3 (Figure 2) and 4 (Figure 3), the PH protons were
We are now extending these synthetic approaches to
located in the difference Fourier synthesis and refined iso- other cyclopentadienes with P-functionalized side chains
tropically. Only the rac isomer is present in the unit cell. As and investigating their coordination properties towards
4 is derived from 2, in which the configuration could not other transition metals and main group metals.
Eur. J. Inorg. Chem. 2002, 1174Ϫ1180
1177

T. Höcher, S. Blaurock, E. Hey-Hawkins
FULL PAPER
Figure 3. Molecular structure of rac-[Fe{(C5H4)CMe2PHPh(Cp*TaCl4)}2] (4) showing the atom numbering scheme employed (ORTEP
plot, 50% probability, SHELXTL PLUS; XP[23]); hydrogen atoms (other than PϪH) are omitted for clarity; only the S,S isomer is shown
1
δ ϭ Ϫ45.6 (d of m, JPϪH ϭ 216 Hz). IR (KBr): ν˜ ϭ 2337 (νPH,
Experimental Section
m), 1463 (νCϭC m, br) cmϪ1
.
Synthesis of rac-[Fe{(η5-C5H4)CMe2PHPh}2] (2): A solution of
Li[(C5H4)CMe2PHPh] (3.5 g, 15.6 mmol) in THF (30 mL) was
slowly added to a suspension of FeCl2 (1.0 g, 7.8 mmol) in THF.
During the addition, FeCl2 slowly dissolved, and the initially pale
pink solution turned first yellow and finally red-brown. The solu-
tion was stirred for 16 h. The solvent was then evaporated under
vacuum and the brown residue treated with Et2O. The rust-brown
powder was separated from the yellow solution by filtration and
extracted repeatedly with Et2O. The Et2O fractions were combined
and the solvent was evaporated under vacuum. The yellow residue
was recrystallized repeatedly from n-hexane or n-pentane. At Ϫ20
°C orange needles of 2 were obtained. Yield: 2.2 g (59%), m.p.
97Ϫ100 °C (from n-pentane). 1H NMR (C6D6): δ ϭ 1.32 (d,
General: All experiments were carried out under purified dry argon.
Solvents were dried and freshly distilled under argon. The NMR
spectra were recorded with an AVANCE DRX 400 spectrometer
(Bruker), 1H NMR (400 MHz): internal standard solvent, external
standard TMS. 13C NMR (100.6 MHz): external standard TMS,
internal standard solvent. 31P NMR (162 MHz): external standard
85% H3PO4. The IR spectra were recorded on an FT-IR spectro-
meter PerkinϪElmer System 2000 in the range 350Ϫ4000 cmϪ1
.
MS: MAT 212 (Varian). The melting points were determined in
sealed capillaries under argon and are uncorrected. 6,6-dimethylful-
vene,[11] LiPHMes,[20] Li[(C5H4)CMe2PHPh][4] and [Cp*TaCl4][21]
were prepared according to the literature procedures. FeCl2 is com-
mercially available (Aldrich).
3
3JPϪH ϭ 12.0 Hz, 3 H, CH3 in CMe2), 1.38 (d, JPϪH ϭ 12.4 Hz,
Synthesis of Li[(C5H4)CMe2PHMes] (1): 6,6-Dimethylfulvene
(0.8 mL, 6.7 mmol) was added slowly in 0.1 mL portions to an or-
ange suspension of LiPHMes (1.1 g, 6.7 mmol) in Et2O (30 mL),
and the resulting pale yellow reaction mixture stirred for 12 h. The
resulting solid was isolated by filtration and washed twice with ca.
20 mL Et2O, then twice with ca. 20 mL n-hexane and dried under
vacuum to yield 1 as a white powder (1.4 g, 63%). M.p. 220 °C
3 H, CH3 in CMe2), 3.75Ϫ3.61 (m, 2 H, CH in C5H4), 3.95Ϫ3.91
1
(m, 2 H, CH in C5H4), 4.08 (d, JPϪH ϭ 206.7 Hz, 1 H, PH), 7.05
(m, 3 H, o- and p-CH in Ph), 7.16 (m, 2 H, m-CH in Ph). 13C
2
NMR (C6D6): δ ϭ 28.4 (d, JPϪC ϭ 16.3 Hz, 1C, CH3ϪC), 28.9
2
1
(d, JPϪC ϭ 16.0 Hz, 1C, CH3ϪC), 33.6 (d, JPϪC ϭ 12.6 Hz, 1C,
CϪCH3), 66.6 (s, 1C, C4 in C5H4), 67.1 (s, 1C, C3 in C5H4), 68.3
(d, 3JPϪC ϭ 21.0 Hz, 2C, C2, C5 in C5H4), 99.6 (d, 2JPϪC ϭ 7.2 Hz,
1C, C1 in C5H4), 126.6 (s, 1C, p-C in Ph), 129.3 (d, 3JPϪC ϭ 5.6 Hz,
2C, m-C in Ph), 135.5 (d, 1JPϪC ϭ 17.8 Hz, 1C, ipso-C in Ph), 137.0
(d, 2JPϪC ϭ 15.5 Hz, 2C, p-C in Ph). 31P NMR (C6D6): δ ϭ 8.8 (d
1
3
(dec.). H NMR ([D8]THF): δ ϭ 1.41 (d, JPϪH ϭ 13.0 Hz, 3 H,
3
CH3 in CMe2), 1.43 (d, JPϪH ϭ 8.8 Hz, 3 H, CH3 in CMe2), 2.19
(s, 3 H, p-CH3 in Mes), 2.26 (s, 6 H, o-CH3 in Mes), 4.36 (d,
1JPϪH ϭ 215.6 Hz, 1 H, PH), 5.56 (s, 4 H, CH in C5H4), 6.78 (s, 2
H, m-CH in Mes). 13C NMR ([D8]THF): δ ϭ 21.0 (s, 1C, p-CH3
1
of m, JPϪH ϭ 207 Hz). IR (KBr): ν˜ ϭ 2283 (νPH, m), 1463 and
1432 (νCϭC, Ph, m), 741 and 697 (δCϭC, Ph, st) cmϪ1. EI MS:
m/z (%) ϭ 486 (15) [Mϩ], 377 (10) [Mϩ Ϫ PHPh], 266 (100) [Mϩ
Ϫ 2 PHPh], 226 (5) [Mϩ Ϫ 2 PHPh Ϫ CMe2], and fragmentation
products thereof. C28H32FeP2 (486.3): calcd. C 69.1, H 6.6, P 12.7;
found C 68.7, H 6.3, P 12.1.
2
in Mes), 23.9 (m, 2C, o-CH3 in Mes), 30.4 (d, JPϪC ϭ 17.8 Hz,
2
1C, CH3-C), 31.5 (d, JPϪC ϭ 9.7 Hz, 1C, CH3ϪC), 37.2 (d,
3
1JPϪC ϭ 12.5 Hz, 1C, CϪCH3), 101.7 (d, JPϪC ϭ 3.5 Hz, 2C, C2,
2
C5 in C5H4), 102.7 (s, 2C, C3, C4 in C5H4), 127.1 (d, JPϪC
ϭ
3
9.6 Hz, 1C, C1 in C5H4), 129.1 (d, JPϪC ϭ 2.5 Hz, 2C, m-C in
Mes), 132.6 (d, 1JPϪC ϭ 29.1 Hz, 1C, ipso-C in Mes), 137.3 (s, 1C, Synthesis of rac-[Fe{(η5-C5H4)CMe2PHMes}2] (3): A solution of
p-C in Mes), 143.8 (s, 2C, br, o-C in Mes). 31P NMR ([D8]THF):
Li[(C5H4)CMe2PHMes] (1.6 g, 6.0 mmol) in THF (20 mL) was
1178
Eur. J. Inorg. Chem. 2002, 1174Ϫ1180

Ferrocene Derivatives with PH-Functionalized Phosphanylalkylcyclopentadienyl Ligands
FULL PAPER
Table 2. Crystal data and structure refinement for 2, 3, and 4
2
3
4
Empirical formula
Mr
C28H32FeP2
486.33
220(2)
C34H44FeP2
570.48
220(2)
C48H62Cl8FeP2Ta2
1402.27
220(2)
Temperature (K)
Crystal system
Space group
monoclinic
P21/n (no. 14)
6.1170(3)
21.2473(9)
9.6680(4)
102.292(1)
1227.74(9)
2
monoclinic
P21/n (no. 14)
8.0117(2)
17.7373(5)
20.7827(6)
93.602(1)
2947.5(1)
4
monoclinic
P21/c (no. 14)
15.2794(7)
14.8736(6)
22.925(1)
95.607(1)
5184.9(4)
4
˚
a [A]
˚
b [A]
˚
c [A]
β [°]
V [A ]
3
˚
Z
ρcalcd. [Mg mϪ3
F(000)
]
1.316
512
1.286
1216
1.796
2752
Crystal size [mm]
Abs. coeff. [mmϪ1
Θ range [°]
0.50 ϫ 0.40 ϫ 0.20
0.758
1.92 to 28.85
12421
0.40 ϫ 0.40 ϫ 0.40
0.642
1.51 to 28.81
29937
0.20 ϫ 0.10 ϫ 0.05
4.993
1.34 to 28.29
32451
]
Refl. collected
Independent reflections
Rint
Parameters
2994
0.0283
192
7185
0.0440
510
12325
0.0495
780
R [I Ͼ 2σ(I)]
wR2 (all data)
0.0673
0.1641
0.246
Ϫ0.528
0.0387
0.1212
0.571
Ϫ0.379
0.0339
0.0618
1.007
Ϫ1.424
Ϫ3
˚
(∆/ρ)min. [e A
]
]
Ϫ3
˚
(∆/ρ)max. [e A
slowly added to a suspension of FeCl2 (0.4 g, 3.0 mmol) in THF separated from the solution by filtration. Cooling to Ϫ20 °C gave
(30 mL). During the addition, FeCl2 slowly dissolved, and the ini- unconverted [Cp*TaCl4], which was also separated by filtration.
tially pale pink solution turned first yellow and finally red-brown. The solvent was evaporated under vacuum, and the resulting brown
The solution was stirred for 16 h. Then the solvent was evaporated residue was extracted with CH2Cl2. The dichloromethane solution
under vacuum, and the brown residue treated with Et2O (20 mL). was concentrated. Cooling to Ϫ20 °C gave a fine brown solid,
The insoluble rust-brown powder was separated from the orange
solution by filtration and extracted repeatedly with Et2O. The Et2O
fractions were combined and the solvent was evaporated under va-
cuum. The yellow residue was recrystallized repeatedly from n-hex-
ane, n-pentane or toluene. At Ϫ20 °C yellow platelets (from hex-
which was recrystallized repeatedly from toluene. Finally, small
brown crystals were obtained together with a brown powder. Yield:
1
0.9 g (45%), m.p. 162Ϫ167 °C (from toluene). H NMR ([D8]tol-
3
uene): δ ϭ 1.65 (d, JPϪH ϭ 12.0 Hz, 6 H, CH3 in CMe2), 2.24 (s,
30 H, CH3 in Cp*), 3.49 (m, 4 H, CH in C5H4), 3.75 (m, 2 H, CH
ane) or orange rod-like crystals (from toluene) of 3 were obtained.
in C5H4), 4.32 (m, 2 H, CH in C5H4), 6.97Ϫ7.01 (m, 10 H, CH in
1
Yield: 0.9 g (55%), m.p. 162 °C (from toluene). H NMR (C6D6): Ph). 13C NMR ([D8]toluene and C6D6): δ ϭ 13.7 (s, CH3 in Cp*),
δ ϭ 1.39 (d, 3JPϪH ϭ 13.0 Hz, 3 H, CH3 in CMe2), 1.45 (d, 3JPϪH ϭ
8.8 Hz, 3 H, CH3 in CMe2), 2.08 (s, 3 H, p-CH3 in Mes), 2.27 (br.
27.4 [br. s, C(CH3)], 27.6 (br. s, C(CH3)], 37.8 [s, C(CH3)], 54 (br.
s, ?), 67.2 (s, C3 and C4 in C5H4), 68.6 (s, C2 and C5 in C5H4),
s, 6 H, o-CH3 in Mes), 3.87Ϫ3.60 (m, 4 H, CH in C5H4), 4.4 (d, 100.4 (br., C1 in C5H4), 128.9 (s, CϪCH3 in Cp*), 129.7 (s, m-C in
1JPϪH ϭ 216.1 Hz, 1 H, PH), 6.76 (s, 2 H, m-H in Mes). 13C NMR
Ph), 133.9 (s, ipso-C in Ph), 137.3 (s, o-C in Ph); p-C in phenyl
(C6D6): δ ϭ 21.7 (s, 1C, p-CH3 in Mes), 24.8 (br. s, 2C, o-CH3 in obscured by solvent. 31P NMR ([D8]toluene): T ϭ 230 K: δ ϭ 57.6
1
1
Mes), 29.3 (br. s, 1C, CH3ϪC), 29.6 (br, 1C, CH3ϪC), 35.7 (d, (d, JPϪH ϭ 364 Hz), 8.5 (d, JPϪH ϭ 204 Hz); T ϭ 300 K: δ ϭ
1JPϪC ϭ 15.2 Hz, 1C, CϪCH3), 66.8 (s, 1C, C3 in C5H4), 67.3 (s, 33.6 (br). IR (KBr): ν˜ ϭ 2965 (CH3, m), 2286 (PH, m), 1463 and
1C, C4 in C5H4), 68.5 (d, JPϪC ϭ 12.2 Hz, 2C, C2, C5 in C5H4), 1435 (CϭC Ph, m), 742 and 697 (CϭC Ph, st) cmϪ1
.
3
2
3
127.1 (d, JPϪC ϭ 9.6 Hz, 1C, C1 in C5H4), 129.1 (d, JPϪC
ϭ
2.5 Hz, 2C, m-C in Mes), 132.6 (d, 1JPϪC ϭ 29.1 Hz, 1C, ipso-C in
Data Collection and Structural Refinement of 2, 3, and 4: Data (Mo-
Kα ϭ 0.71073 A) were collected with a Siemens CCD (SMART)
Mes), 137.3 (s, 1C, p-C im Mes), 143.8 (s, 2C, br, o-C in Mes). 31P
˚
1
NMR (C6D6): δ ϭ Ϫ32.8 (d of m, JPϪH ϭ 214 Hz). IR (KBr):
diffractometer. All observed reflections were used for refinement
(SAINT) of the unit cell parameters. Empirical absorption correc-
tion with SADABS.[22] The structures were solved by direct
methods (SHELXTL PLUS).[23] Fe, Ta, P, Cl, and C atoms were
refined anisotropically; H atoms were located by difference maps
and refined isotropically. Table 2 lists crystallographic details.
ν˜ ϭ 2345 and 2310 (νPH, m) cmϪ1. EI MS: m/z (%) ϭ 570 (10)
[Mϩ], 418 (8) [Mϩ Ϫ PHMes], 313 (5) [Mϩ Ϫ C5H4CMe2PHMes],
266 (100) [Mϩ Ϫ 2 PHMes], and fragmentation products thereof.
C34H44FeP2 (570.5): calcd. C 71.6, H 7.8, P 10.9; found C 71.1, H
8.3, P 10.3.
Synthesis of rac-[Fe{(η5-C5H4)CMe2PHPh(Cp*TaCl4)}2] (4): A so- CCDC-173678 (2), -173679 (3) and -173680 (4) contain the supple-
lution of 2 (0.7 g, 1.4 mmol) in toluene (15 mL) was added drop- mentary crystallographic data for this paper. These data can be
wise to a suspension of [Cp*TaCl4] (1.3 g, 2.8 mmol) in toluene
obtained free of charge at www.ccdc.cam.ac.uk/conts/retriev-
(30 mL). The color of the reaction mixture changed from orange ing.html [or from the Cambridge Crystallographic Data Centre, 12,
to brown. The mixture was then heated to 70 °C for 2 h, allowed Union Road, Cambridge CB2 1EZ, UK; Fax: (internat.) ϩ44-1223/
to cool, and stirred at room temperature overnight. The solid was
336-033; E-mail: deposit@ccdc.cam.ac.uk].
Eur. J. Inorg. Chem. 2002, 1174Ϫ1180
1179

T. Höcher, S. Blaurock, E. Hey-Hawkins
FULL PAPER
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We gratefully acknowledge financial support from the Deutsche
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Received October 25, 2001
[I01420]
1180
Eur. J. Inorg. Chem. 2002, 1174Ϫ1180