Phosphane coordination to rare earth metal centers: Monomeric, solvent-free complexes of type Cp′2LnX with phosphanoethyl substituted cyclopentadienyl ligands

Article abstract of DOI:10.1016/S0022-328X(00)00205-9

The reaction of phosphanoethyl substituted cyclopentadienides [C₅H₄CH₂CH₂PR₂]M, R=Me, Cy, t-Bu, Ph, M=Li, K with LnX₃ (Ln=rare earth metal, X=Cl^-, CF₃SO₃^-) afforded twofold substituted metal complexes of the type [C₅H₄CH₂CH₂PR₂] ₂LnX. Using the dianionic ligand Li₂[(C₅H₄CH₂CH₂) ₂PMe] phosphano bridged ansa metallocene derivatives [(C₅H₄CH₂CH₂)₂PMe]LnX (Ln=Y, Lu; X=Cl^-, CF₃SO₃^-) were isolated. The complexes are soluble in toluene, monomeric and free of solvent. According to X-ray studies on [C₅H₄CH₂CH₂PMe₂] ₂YCl, a distorted trigonal bipyramid with two axial phosphano groups and two equatorial cyclopentadienyl moieties is the structural motif, the third equatorial site being occupied by the halide ligand.

Full text of DOI:10.1016/S0022-328X(00)00205-9

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Journal of Organometallic Chemistry 604 (2000) 72–82
Phosphane coordination to rare earth metal centers: monomeric,
solvent-free complexes of type Cp%LnX with phosphanoethyl
2
substituted cyclopentadienyl ligands
Hans H. Karsch *, Volker W. Graf, Wolfgang Scherer
Anorganisch-Chemisches Institut der Technischen Uni6ersita¨t Mu¨nchen, Lichtenbergstraße 4, D-85747 Garching, Germany
Received 17 December 1999; received in revised form 4 March 2000
Abstract
The reaction of phosphanoethyl substituted cyclopentadienides [C5H4CH2CH2PR2]M, R=Me, Cy, t-Bu, Ph, M=Li, K with
LnX3 (Ln=rare earth metal, X=Cl−, CF3SO3−) afforded twofold substituted metal complexes of the type
[C5H4CH2CH2PR2]2LnX. Using the dianionic ligand Li2[(C5H4CH2CH2)2PMe] phosphano bridged ansa metallocene derivatives
[(C5H4CH2CH2)2PMe]LnX (Ln=Y, Lu; X=Cl−, CF3SO3−) were isolated. The complexes are soluble in toluene, monomeric and
free of solvent. According to X-ray studies on [C5H4CH2CH2PMe2]2YCl, a distorted trigonal bipyramid with two axial phosphano
groups and two equatorial cyclopentadienyl moieties is the structural motif, the third equatorial site being occupied by the halide
ligand. © 2000 Elsevier Science S.A. All rights reserved.
Keywords: Anionic phosphane ligands; Rare earth metal complexes; Cyclopentadienyl complexes
1. Introduction
lic chemistry of rare earth elements, in particular for
catalytic reactions a combination of a ‘stable’ (Cp−)
with a ‘labile’ (PR3) ligand is desired. Therefore phos-
phanoalkyl cyclopentadienide ligands seem to provide
an attractive potential in this field by a reversible
phosphane donor capacity (‘hemilabile ligand’) (Scheme
1).
The phosphane functionality should also prevent the
system from oligomerisation reactions as well as from
coordination of donor solvent molecules, as do some
cyclopentadienyl based ligands with donor functional-
ized side chains, but exhibiting a less reversible coordi-
nation to the metal center [6–8].
Because of the very weak interaction of the ‘hard’
lanthanoid cation and the ‘soft’ phosphorus atom only
a few examples of lanthanoid complexes with neutral
phosphane ligands are known so far [1]. In order to
achieve more stable complexes the concept of anionic
phosphane ligands was introduced in rare earth metal
chemistry. Complexes are known with phosphanides
[2], phosphanoalkoxides [3], amidophosphanes [4] and
phosphanomethanides [5]. Whereas cyclopentadienides
are the most important class of ligands in organometal-
By varying the organic substituents at the phospho-
rus atom the solubility and the donor strength of the
phosphane can be influenced and thus adjusted to the
respective needs. Apart from a foregoing preliminary
account from our laboratory [9], rare earth metal com-
plexes with phosphanoalkyl substituted cyclopentadi-
enides have not been described as yet. Indeed,
cyclopentadienyl ligands with a directly attached phos-
phane moiety have successfully been introduced in rare
earth metal chemistry, i.e. CpLa(C5H4PPh2)2·THF [10],
Yb(C5H4PPh2)2·THF [11], (COT)SmC5Me4PR2(THF)2
Scheme 1. Reversible coordination of phosphanoalkyl substituted
cyclopentadienyl ligands.
* Corresponding author. Tel.: +49-89-32093132; fax: +49-89-
32093132.
0022-328X/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(00)00205-9

H.H. Karsch et al. / Journal of Organometallic Chemistry 604 (2000) 72–82
73
[12], however, it is important to realize that in all these
compounds phosphorus is not coordinated to the metal
center.
There are several routes to synthesize phos-
phanoalkyl substituted cyclopentadienides [13]. Most of
these procedures are tedious and proceed in low yield.
However, mono- and dianionic phosphanoethyl substi-
tuted cyclopentadienides can be prepared by the reac-
tion of the corresponding mono- and dimetallated
phosphanes with spiro[2,4]hepta-4,6-diene [14] in satis-
fying yields [9,15–17] (Scheme 2).
Monoanionic alkali cyclopentadienides of the type
M[C5H4(CH2)2PR2] (M=Li, K) with R=Ph [15,16],
Me [9], i-Pr [15], t-Bu [15] and the dianionic derivative
Li2[(C5H4CH2CH2)2PPh] [17] are known. An X-ray
structure determination of K[C5H4(CH2)2PPh2] [16] has
been reported. The lithium cyclopentadienides
Li[C5H4(CH2)2PCy2] and Li2[(C5H4CH2CH2)2PMe]
were newly synthesized using the nucleophilic ring
opening reaction mentioned above.
Scheme 2. Synthetic route to phosphanoethyl cyclopentadienyl
lithium derivatives according to [9,15–17].
results were as follows: The yttrium complex 1, as
obtained from the reaction according Eq. (2), is a
colorless crystalline solid, monomeric and soluble in
hydrocarbons. It is isomorphous to the bromine ana-
logue [(C5H4CH2CH2PMe2)2]YBr (2), which was de-
scribed previously [9].
2. Results and discussion
2.1. Complexes of the type [(C5H4CH2CH2PMe2)2]LnX
Complexes of type Cp2LnX normally are not readily
obtained due to ligand scrambling. Furthermore, donor
solvent molecules (e.g. THF) and/or metal halides (e.g.
LiCl) are additionally coordinated or dimerisation is
observed [18]. Hence, on attempted syntheses, complex
mixtures often are encountered, and only in cases,
where crystalline products are obtained or diamagnetic
metal nuclei are involved, a structural characterization
is possible. In an attempt to get clear-cut results and to
obtain compounds Cp%2LnX free of solvent and alkali
halides, we therefore reacted the diamagnetic salts
LnX3 (Ln=Sc, Y, La, Lu; X=Cl, O3SCF3) with two
equivalents of [C5H4CH2CH2PR2]Li (R=Me, Cy, t-
Bu, Ph) in THF as solvent Eq. (1).
(2)
In the 31P{1H}-NMR spectrum of 1 a doublet at l
1
−34.65 with a JPY coupling constant of 74.0 Hz (cf.:
1
2, JPY=72.8 Hz [9]; Y[N(SiMe2CHPMe2)(SiMe2CH2-
PMe2)][N(SiMe2CH2PMe2)2], 1JPY=70.0 Hz [19]),
which is invariant with temperature (+60 to −80°C)
and solvent (C6D6 or [d8]THF), is detected. Thus the
two YꢀP bonds remain retained within this range of
temperature. The coordination of both phosphane
functionalities is also evident from the 13C{1H}-NMR
signals of the methylene and Cipso carbon atoms, which
1
each appear as a ‘pseudotriplet’ [20]. However, H- and
13C{1H}-NMR spectra, in contrast to the 31P{1H}-
NMR spectrum, are clearly temperature dependent:
whereas the methyl and methylene protons at r.t. ap-
pear as broad singlets, at −80°C these signals each
split into signals of equal intensity. As well, whereas the
ring carbon nuclei and the methyl groups each give rise
to a single broad line, at −80°C these signals are split
into two singlets for the methyl carbon atoms and four
(1)
In all cases, products with the desired composition
were obtained, but depending on the metal, the anionic
group X and the size of the phosphane substituent R,
not in all cases in a pure state and with different
coordination mode and behavior of the ligands. The

74
H.H. Karsch et al. / Journal of Organometallic Chemistry 604 (2000) 72–82
signals for the ring carbon atoms (besides the separate
signal for the Cipso ring carbon atom, vide supra). Thus
a dynamic process is evident, which is not due to a
dissociative YꢀP bond cleavage but should involve
some kind of pseudorotation, probably analogously to
Table 1
,
Selected bond distances (A) and angles (°) for 1 (left column) and 2
(right column) [9] for comparison
Bond length
YꢀX1a a
YꢀX1b a
YꢀCl
2.3917(11)
2.3953(15)
2.6248(6)
2.9417(7)
2.9754(7)
YꢀX1a a
YꢀX1b a
YꢀBr
YꢀP1
YꢀP2
2.392
2.386
2.794(1)
2.960(1)
2.933(1)
YꢀP1
YꢀP2
Fig. 1. PLATON representation of ClY(C5H4CH2CH2PMe2)2 (1).
Thermal ellipsoids are given at the 50% probability level; hydrogen
atoms are omitted for clarity.
Bond angles
X1aꢀYꢀX1b
P1ꢀYꢀP2
ClꢀYꢀX1a
ClꢀYꢀX1b
126.30(5)
153.55(2)
116.86(3)
116.84(4)
X1aꢀYꢀX1b
P1ꢀYꢀP2
BrꢀYꢀX1a
BrꢀYꢀX1b
129.9
154.8(1)
117.1
113.0
the Berry process as established for many other penta-
coordinated species [21]. Alternatively, but much less
likely, dissociation of the anionic groups (Cl, C5H4)
would occur, while the YꢀP bond remains intact.
Indeed, the solid state structure of 1 confirms a
structural geometry around the metal, which best can
be described as distorted trigonal bipyramid.
a X1a, b: center of the Cp rings.
Table 2
Crystallographic data for (C5H4CH2CH2PMe2)2YCl (1)
Crystal data
Chemical formula
C18H28ClP2Y
430.70
White
Crystals suitable for X-ray analysis of 1 were ob-
tained by slowly removing the solvent of the filtered
solution. Selected bond distances and angles are given
in Table 1 and were compared with those of 2 [9].
Crystallographic data are given in Table 2 and Fig. 1.
In line with the spectroscopic findings, 1 displays a
distorted trigonal bipyramidal geometry with the yt-
trium center coordinated by both phosphorus atoms in
axial positions. The YꢀP bond lengths of 2.9417(7) and
fw (g mol−1
)
Color
Crystal size (mm)
Crystal system
Space group
0.25×0.3×0.5
Monoclinic
P21/n
10.8217(2)
15.6988(3)
12.3731(2)
108.3363(9)
1995.31(6)
4
193
1.434
32.1
888
,
a (A)
,
b (A)
,
c (A)
i (°)
3
,
V (A )
,
2.9754(7) A are only slightly longer than in {Y[N(Si-
Z
T (K)
Me2CHPMe2)(SiMe2CH2PMe2)[N(SiMe2CH2PMe2)2]}
zcalc. (g cm−3
)
,
[19] [2.871(1), 2.896(1) and 2.903(1) A]. The YꢀCl bond
v (cm−1
F(000)
)
,
distance [2.6248(6) A] in 1 lies between that found in
,
(Me5C5)2YCl(THF) [2.576(1) A] [22] and in
[(C5H5)2YCl]2 [2.674(1) and 2.689(1) A] [22] and close
to that found in [(C5H4CH2CH2SEt)2]YCl [2.6071(6) A]
[8c]. The average YꢀCp(center) distance of 2.393 A
agrees well with that of other yttrium cyclopentadienyl
complexes [6–8,23].
Data collection
,
,
u (A)
0.71073
€-scan
4.0–26.4
913, 919,
−15–+14
,
Scan method
,
q range (°)
Data collected (h, k, l)
The influence of increasing steric bulk of the phos-
phane substituents is demonstrated by the reaction of
YCl3 with [C5H4CH2CH2PR2]Li (R=Cy, tBu) (Eq. (3)
and (4)).
Refinement
Reflections collected
Independent reflections
Observed reflections with [I\2|(I)]
Rint
15 344
4049
3849
0.035
0.029
0.081
1.05
+0.56, −0.46
a
R1
b,d
wR2
Goodness-of-fit c
−3
,
Dzmax/min (e A
)
a R1=ꢀ(ꢁꢁFoꢁ−ꢁFcꢁꢁ)/ꢀꢁFoꢁ.
b wR2=[ꢀ w(Fo2−Fc2)2/ꢀ w(Fo2)2]1/2
.
c GOF=[ꢀ w(Fo2−F2c)2/(NO−NV)]1/2
.
d w=1/[|2(F2o)+(0.0442P)2+1.90P] where P=(Fo2+2F2c)/3.
(3)

H.H. Karsch et al. / Journal of Organometallic Chemistry 604 (2000) 72–82
75
Compound 3 thus obtained forms a colorless foam
and is easily soluble in aromatic hydrocarbons. The
31P{1H}-NMR spectrum consists of a doublet at l
−2.30 with a PꢀY coupling constant of 29.4 Hz, which
positive charge at yttrium and thus also might explain
the increasing value of the PꢀY coupling constant in
going from 3 to 5.
3+
Comparable in size to Y3+ (0.90 A) is Lu
(0.86
,
1
,
is not temperature dependent. The H-NMR spectrum
A). The lutetium complex 6 obtained according to Eq.
(5) is a colorless solid, soluble in aromatic hydrocar-
bons.
is very complex, because of superpositions of the cyclo-
hexyl proton signals. For the ring protons an uncom-
pletely resolved A2B2 spin system at l 5.84 is observed.
In the 13C{1H}-NMR spectrum each a singlet is ob-
served for the methylene carbon atoms (no pseu-
dotriplet splitting as in the case of 1). This indicates a
markedly weaker coordination of the phosphane func-
tionality in 3 compared to 1 due to the sterical demand
of the cyclohexyl substituents.
The influence of the remaining anionic functionality
X (the leaving group) on the coordination of the phos-
phanoalkyl cyclopentadienyl ligand to rare earth metal
centers is evident from Eq. (4). Both 4 and 5 were
obtained as colorless solids from toluene in good yields.
(5)
The 31P{1H}-NMR spectrum consists of one singlet
at l −26.27. This signal remains unchanged over a
temperature range from r.t. to −90°C: no dynamic
behavior can be observed in solution. Similar to 1 the
13C{1H} resonances of the CH3 groups, the CpCH2
groups, the CH2P groups and the Cipso atom of 6 each
show a ‘pseudo triplet’ splitting indicating likewise a
bis-phosphane coordination [20]. In the case of 6, also
1
the H-NMR signals indicate this kind of coordination
by the triplet nature of the PCH3, PCH2 and CH2C5H4
1
resonances. No temperature dependence of the H- and
13C{1H}-NMR signals is observed, as it was the case
with 1. This might be taken as an indication of a higher
coordination number in 6 (‘pseudooctahedral’).
With scandium as the smallest rare earth metal ele-
ment a bis-substitution product was even observed
when a 3:1 stoichiometry of Li[C5H4CH2CH2PMe2] and
Sc(CF3SO3)3 was used Eq. (6).
(4)
NMR spectroscopic studies confirm both complexes
4 and 5 are monomeric and do not contain additional
solvent molecules.
The 31P{1H}-NMR spectrum of [C5H4CH2CH2-
P(tBu)2]2Y(CF3SO3) (4) consists of a doublet at l 31.94
with a PꢀY coupling constant of only 7.1 Hz, whereas
for complex [C5H4CH2CH2P(tBu)2]2YCl (5) a doublet
at l 32.56 with a PꢀY coupling constant of 48.5 Hz is
observed. Obviously the l 31P shift is not an adequate
indicator for the type of coordination of the phosphane
moiety. The small PꢀY coupling constant for 4 indi-
cates that the ‘phosphane arms’ are not effectively
(6)
Some unidentified by-products (ca. 1%) were also
found and complicate the identification and characteri-
zation of 7. However, the spectroscopic data seem to
indicate a coordination of both P-atoms to the scan-
dium center: the complex pattern of the 1H-NMR
signals is indicative for a bis-phosphane coordination.
Nevertheless the exact mode of coordination in 7 re-
mains uncertain.
1
bonded to the metal center. The H-NMR signal of the
With the large La3+ cation distinct difficulties in the
synthesis of twofold complexes occur. The reaction of
LaCl3 with two equivalents Li[C5H4CH2CH2PMe2] or
K[C5H4CH2CH2PPh2] proceeded under the formation
of a precipitate which was insoluble in THF, whereas
ring protons in compound 4 appears as an uncom-
pletely resolved A2B2 pattern, whereas for 5 a singlet is
detected. These findings indicate that complex 5 might
be involved in faster exchange processes of the anionic
groups than 4 and 3. This process would increase the

76
H.H. Karsch et al. / Journal of Organometallic Chemistry 604 (2000) 72–82
the reaction of La(CF3SO3)3 with Li[C5H4CH2-
CH2PMe2] yielded a colorless solid, which was com-
pletely soluble in toluene Eq. (7).
Li2[(C5H4CH2CH2)2PMe] is introduced into rare earth
chemistry.
The reaction of one equivalent of Li2[(C5H4CH2-
CH2)2PMe] with one equivalent of YCl3 in THF pro-
ceeded under formation of the [(C5H4CH2CH2)2P-
Me]YCl (9x) which obviously contains LiCl and THF,
from which it could not be separated because of the
insolubility of the product in toluene (Scheme 3).
Nevertheless, 31P{1H}- and 13C{1H}-NMR measure-
ments of the reaction mixture confirm the presence of
the desired product: after 12 h reaction time the
31P{1H}-NMR spectrum consists of a doublet at l
1
−21.29 with a JPY coupling constant of 84.3 Hz.
The 1H-NMR spectrum exhibits a doublet for the
methyl group at l 1.06 with a 2JHP coupling constant of
5.9 Hz. For the methylene protons very complex signals
are detected. The CH2P groups are observed at l
1.30–1.38 and the CpCH2-groups at l 2.45–2.59. The
signals are complex because of the formation of the
chelate ring. Within this ring system all protons are
diastereotopic. For the ring protons of the cyclopenta-
dienyl fragment an uncompletely resolved ABCD spin
system is observed (lA, 5.54; lB, 5.60; lC, 5.78; lD,
5.98; cf.: Fe(C5H4CH2CH2)2PPh) [17]. Since separation
and purification of 9 from the mixture was not possible,
an alternative strategy was employed. Compound 9x
was converted into the corresponding hexamethyl disy-
lazide derivative [(C5H4CH2CH2)2PMe]YN(SiMe3)2
(7)
Two signals in the 31P{1H}-NMR spectrum at l
−43.58 and −30.31, respectively, show that a mixture
of the twofold and the threefold substituted lanthanum
complexes 8 and 8a [9] was obtained. Therefore H-
NMR data could not be attributed conclusively and
1
constitutional assignments for 8 therefore are not feasi-
7
ble. According to the Li-NMR spectrum of the mix-
ture, the monotriflate compound 8 contains LiCF3SO3.
2.2. Complexes of the type [(C5H4CH2CH2)2PMe]LnX
To increase the reactivity of the biscyclopentadienyl
complexes towards substitution reactions the ligand
Scheme 3. Preparation of pure [(C5H4CH2CH2)2PMe]YCl (9).

H.H. Karsch et al. / Journal of Organometallic Chemistry 604 (2000) 72–82
77
3. Conclusions
(10), which could be separated from LiCl by extraction
with toluene. Reaction of 10 with NH4Cl in toluene
finally led to the pure chlorine compound 9 (Scheme 3).
As it was the case with product 9x, pure 9 likewise is
insoluble in toluene and the H-NMR spectra of both
materials are identical.
Using the diamagnetic rare earth metal centers Sc, Y,
La and Lu a coordination of the phosphane functional-
ity of phosphanoethyl cyclopentadienyl ligands is feasi-
ble. The strength of the metalꢀphosphorus bond
strongly may be influenced by the nature of the ligand
(monoanionic or dianionic), the phosphorus sub-
stituents and the residual anionic group X present at
the metal (Cl−, O3SCF3−). The nature of the metal-X
bond likewise is tunable by the specific phosphorus
substituents. Indeed, it is this anionic functionality,
which makes the compounds described in this paper,
valuable precursors for reactions and derivatisations in
this field of chemistry. Quite remarkably, most of the
1
The 31P{1H}-NMR spectrum of 10 consists of a
doublet at l −19.95 with a PꢀY coupling constant of
110.8 Hz. The value of the coupling constant is remark-
able high and may indicate a strengthening of the
yttrium to phosphorus bond. (Note that the spectrum
of 10 was recorded in C6D6, whereas the spectrum of 9
was recorded in C6D6+THF. It might be concluded,
that THF coordinates (reversible) to 9, while 10 is free
1
of THF). In the H-NMR spectrum of 10, two signals
compounds Cp%LnX with additional phosphanoalkyl
2
for the methyl protons of the silyl groups (l 0.14, 1.38)
are observed. Accordingly two signals are observed for
these groups in the 13C{1H}-NMR spectrum (l 5.54,
6.27). Due to this result rotation about the YꢀN bond
seems to be hindered even at r.t.
The monotriflate complex [(C5H4CH2CH2)2P-
Me]Lu(CF3SO3) (11) on the other hand is easily soluble
in aromatic hydrocarbons like toluene. It is accessible
side chains are obtained in good to excellent yields as
monomeric, salt and solvent free compounds, in
marked contrast to other bis-cyclopentadienyl rare
earth metal derivatives and thus enhance the synthetic
value of the compounds described here considerably. In
contrast to comparable cyclopentadienyl ligands with
donor functionalized side chains (OR, SR, NR2 donors)
[6–8], the coordination of the R2P donor functionality
to the metal is more labile and strongly dependent on
the P substituents. Moreover, this functionality offers
the possibility of further derivatisation at phosphorus
and thus changing the ligation property considerably
[25].
as
a colorless solid by reaction of the ligand
Li2[(C5H4CH2CH2)2PCH3] with one equivalent Lu(CF3-
SO3)3 in excellent yield Eq. (8).
4. Experimental
4.1. General considerations
All operations were performed under an atmosphere
of dry, oxygen free nitrogen and with thoroughly dried
glassware by use of standard high-vacuum-line tech-
niques. Pentane, toluene and THF were distilled under
nitrogen from K–Na alloy. Elemental analyses were
obtained with a Vario EL CHN analyzer of the Mikro-
analytisches Laboratorium der TU Mu¨nchen. Due to
the high air and moisture sensitivity of all compounds,
not all analyses were completely satisfactory. Mass
spectra were conclusive in all cases, however. Chemical
ionization (CI) mass spectral data were obtained em-
ploying a Varian Mat 311A spectrometer; peaks are
reported as m/z (assignment, relative intensity). NMR
spectra were recorded on a JEOL GX 270 spectrometer
(1H 270.17 MHz, 13C{1H} 67.94 MHz, 31P{1H} 109.4
(8)
The 31P{1H}-NMR spectrum consists of a singlet at l
−8.86 (cf.: Li2[(C5H4CH2CH2)2PCH3]: −47.56). The
methyl group at the phosphorus appears as a doublet as
1
well in the H- [l 0.92 (6.2 Hz)] and in the 13C{1H}-
NMR spectrum. ABCDX (for CH2CH2P) and ABCD
(for C5H4) spin systems in the 1H-NMR spectrum
correspond to five separate signals for the C5H4 rings in
the 13C{1H}-NMR spectrum at r.t. and indicate a rigid
coordination of the dianionic ligand to the metal cen-
ter. However, whereas for 9 and 10 a distorted pseu-
dotetrahedral geometry is most likely adopted, for 11 a
higher coordination number due to a bidentate triflate
coordination can not be ruled out. It should be men-
tioned, that comparable ansa-lanthanoidocene com-
plexes with other heteroelements than phosphorus in
the ansa-backbone have been described [24].
7
MHz), a JEOL GX 400 (1H 399.65 MHz, Li, 13C{1H}
100.40 MHz, 31P{1H} 161.7 MHz) and a JEOL JNM-
Lambda 400 (19F 376.10 MHz) spectrometer. Chemical
shifts refer to TMS (l=0) as internal (1H, 13C) stan-
dard, to 80% H3PO4 (31P) and to CF3COOH (19F) and
LiBr 20% in D2O (7Li) as external standard. All chemi-

78
H.H. Karsch et al. / Journal of Organometallic Chemistry 604 (2000) 72–82
cal shifts are reported in ppm and coupling constants J
in Hz. In case of high order spin systems, the distance
N between the two outermost lines of a symmetrical
multiplet t or q is given. The symbol m* denotes a
superposition of an A2B2 spin system (XꢀCH2CH2ꢀY)
Calc. for C15H19Li2P: C, 73.79; H, 7.84; Li, 5.69; P,
12.69. Found: C, 74.10; H, 8.00; Li, 5.71; P, 12.80%.
4.4. [C5H4CH2CH2P(CH3)2]2YCl (1)
with an AnXX%A% spin system. All measurements were
To
a
mixture of 14.4 mmol (2.3 g) of
n
carried out at 25°C in C6D6. Exceptions were given
separately. Temperature dependent-NMR spectra were
recorded with [D8]toluene as solvent.
Li[C5H4CH2CH2PMe2] and 7.0 mmol (1.38 g) YCl3, 40
ml of THF was added at −78°C. The reaction mixture
was slowly warmed up to r.t. and stirred for another 12
h. The solvent was removed and the product was
extracted with 50 ml of toluene. The toluene extract
was concentrated and 1 was isolated as colorless crys-
tals. Yield: 1.1 g (97%). 1H-NMR (C6D6, r.t.): l 0.86 [d,
2JHP=1.7, 12 H, P(CH3)2], 1.60 [br, 4H, C5H4CH2-
CH2P(CH3)2], 2.39 [br, 4 H, C5H4CH2CH2P(CH3)2],
Sc(CF3SO3)3, Y(CF3SO3)3, La(CF3SO3)3, Lu(CF3-
SO3)3 [26], Cy2PH [27a], Cy2PLi [27a], Li2PMe [27b],
Li[C5H4CH2CH2PMe2] [9], Li[C5H4CH2CH2P(t-Bu)2]
[15b] and spiro[2,4]hepta-4,6-diene [14] were prepared
according to literature procedures. YCl3 was prepared
from the hexahydrate by drying in vacuo (140°C 10−3
Torr) for 5 days. The lanthanoid hexahydrate chlorides
were purchased from commercial sources.
5.58 [br,
4 H, C5H4CH2CH2], 5.69 [br, 4 H,
1
C5H4CH2CH2]. H-NMR ([d8]toluene, −80°C): l 0.67
[s, br, PMe], 1.18 [s, br, PMe], 1.23 [br, CH2P], 1.18 [br,
CH2C5H4], 2.07 [br, CH2P], 2.77 [br, CH2C5H4], 5.61,
6.14, 6.29 [br, C5H4]. 13C{1H}-NMR ([d8]toluene, −
80°C): l 9.61 [br, CH3], 10.20 [br, CH3], 24.39 [br,
CH2P], 33.42 [br, CH2C5H4], 101.83, 106.52, 108.06,
110.20 [br, C5H4], 131.84 [br, Cipso].
4.2. Li[C5H4CH2CH2PCy2]
To a solution of 4.36 mmol (0.89 g) LiPCy2 in 50 ml
of THF 4.36 mmol (0.4 g) spiro[2.4]hepta-4,6-diene in
20 ml of THF were added by means of a pipette. After
stirring the reaction mixture for 12 h at r.t. the solvent
was removed and the product was washed three times
with pentane. After removing the solvent and drying a
colorless solid is obtained. Yield: 0.72 g (56%). 1H-
NMR ([d8]dioxane, r.t.): l 1.23–1.76 [m, 24 H, Cy,
13C{1H}-NMR (C6D6, r.t.): l 10.22 [s, CH3], 24.39 [t,
N=12.3, CH2PMe2], 33.45 [t, N=13.1, C5H4CH2],
107.20 [s, br, CH (C5H4)], 129.45 [t, N=6.1, Cipso].
1
31P{1H}-NMR (C6D6, r.t.): l −34.65 [d, JPꢀY=74.0].
1
31P{1H}-NMR ([d8]THF, r.t): l −33.90 [d, JPꢀY
=
3
3
CH2PCy2: superposition], 2.64 [dtr, JHH=7.8, JHP
=
74.0]. 31P{1H}-NMR ([d8]toluene, −80°C): l −34.65
[d, JPꢀY=74.0]. Mass spectrum (CI); m/z (%): 430 (49)
1
2.9, 2 H, C5H4CH2CH2P(CH3)2], 5.53 [A2B2 spin sys-
tem, lA, 5.49; lB, 5.58; JAB=2.4, 4 H C5H4].
[M], 395 (100) [MꢀC5H4(CH2)2P(CH3)2], 154 (12)
[C5H5(CH2)2P(CH3)2]. Anal. Calc. for C18H28ClP2Y: C,
50.19; H, 6.55. Found: C, 51.22; H, 6.84%.
2
13C{1H}-NMR ([d8]dioxan, r.t.): l 25.35 [d, JCP=6.6,
C5H4CH2], 27.23 [m, C3,4, Cy], 29.96 [d, 1JCP=7.7,
CH2PCy2], 31.21 [d, 2JCP=13.2, C2, Cy], 33.63 [d,
1JCP=9.4, C1, Cy], 102.85 [s, CH, C5H4], 103.25 [s,
4.5. [C5H4CH2CH2PCy2]2YCl (3)
3
CH, C5H4], 120.75 [d, JCP=9.9, Cipso]. 31P{1H}-NMR
([d8]dioxan, r.t.):
l
−8.76 (s). Anal. Calc. for
To
a
mixture of 4.05 mmol (1.2 g) of
C19H30PLi: C, 77.00; H, 10.20; P, 10.45. Found: C,
75.91; H, 10.32; P, 10.74%.
Li[C5H4CH2CH2PCy2] and 2.05 mmol (0.4 g) YCl3, 40
ml of THF was added at −78°C. The reaction mixture
was slowly warmed up to r.t. and stirred for another 12
h. The solvent was removed and the product was
extracted with 50 ml of toluene. The toluene extract
was concentrated and 3 was isolated as colorless crys-
tals. Yield: 1.13 g (78%). 1H-NMR (C6D6, r.t.): l
1.02–1.90 [m, 48 H, CH2P(C6H11)2], 2.80 [q, N=28.7,
CH2C5H4], 5.84 [A2B2 Spin system, uncompletely re-
solved lA, 5.79; lB, 5.88; 8 H, C5H4CH2CH2PCy2].
13C{1H}-NMR (C6D6, r.t.): l 26.20 [d, 2JCP=9.3,
C5H4CH2], 27.58 [d, 4JCP=8.3, C4, Cy], 28.15 [d,
4.3. Li2[(C5H4CH2CH2)2PMe]
To a suspension of 0.068 mol (4.07 g) Li2PMe in 50
ml of THF 0.14 mol (12.90 g) spiro[2.4]hepta-4,6-diene
in 20 ml of THF were added by means of a pipette.
After stirring the reaction mixture for 12 h at r.t. the
solvent was removed and the product was washed three
times with pentane. After evaporation of the solvent
and drying a colorless solid is obtained. Yield: 7.23 g
1
1
(44%). H-NMR ([d8]THF, r.t.): l 0.98 [s, 3H, CH3P],
3JCP=18.7, C3, Cy], 29.65 [d, JCP=6.7, CH2P], 30.22
2
1
1.67 [m, 4 H, CH2C5H4], 2.57 [m, 4 H, MePCH2], 5.41
[m, 8 H, C5H4]. 13C{1H}-NMR ([d8]THF, r.t.): l 10.05
[d, 1JCP=13.8, CH3P], 25.79 [d, 2JPC=12.3, PCH2],
32.57 [d, 1JCP=6.1, CH2(C5H4)2], 101.68 [s, CH,
[d, JCP=9.3, C2, Cy], 34.30 [d, JCP=9.9, C1, Cy],
3
106.33 [s, C5H4], 111.49 [s, C5H4], 126.50 [d, JCP
10.9, Cipso]. 31P{1H}-NMR (C6D6, r.t.): l −2.30 [d,
PY=29.4]. 31P{1H}-NMR ([d8]toluene, −80°C): l −
=
J
3
(C5H4)], 101.84 [s, CH, (C5H4)], 119.54 [d, JCP=10.8,
2.30 [d, JPY=29.4]. Anal. Calc. for C38H60ClP2Y: C,
64.91; H, 8.60. Found: C, 65.20; H, 9.11%.
Cipso]. 31P{1H}-NMR ([d8]THF, r.t.): l −47.56. Anal.

H.H. Karsch et al. / Journal of Organometallic Chemistry 604 (2000) 72–82
79
4.6. [C5H4CH2CH2P(t-Bu)2]2Y(CF3SO3) (4)
toluene extract was concentrated and 6 was isolated as
colorless crystals. Yield: 0.83 g (78%). H-NMR (C6D6,
1
To a mixture of 5.48 mmol (1.34 g) of Li[C5H4CH2-
CH2P(t-Bu)2] and 1.77 mmol (0.95 g) Y(CF3SO3)3, 40
ml of THF was added at −78°C. The reaction mixture
was slowly warmed up to r.t. and stirred for another 12
h. The solvent was removed and the product was
extracted with 50 ml of toluene. The toluene extract
was evaporated and 4 was isolated as a colorless foam.
r.t.): l 0.94 [m*, N=4.7, 12 H, P(CH3)2], 1.58 [m*,
N=37.6, 4 H, CH2PMe2], 2.36 [m*, N=30.9, 4 H,
C5H4CH2], 5.63 [s, 4 H, C5H4], 5.70 [s, 4 H, C5H4].
13C{1H}-NMR (C6D6, r.t.):
l 10.34 [t, N=7.3,
P(CH3)2], 23.7 [t, N=11.4, C5H4CH2], 33.25 [t, N=
16.1, CH2PMe2], 106.62 [s, C5H4], 131.37 [t, N=7.8,
Cipso]. 31P {1H}-NMR (C6D6, r.t.): l −26.27(s).
31P{1H}-NMR ([d8]toluene, −80°C): l-26.27(s). Mass
spectrum (CI); m/z (%): 630 (48.02) [M+], 562 (3.85)
[M+−CF3], 477 (100) [M+−C5H4(CH2)2P(CH3)2].
Anal. Calc. for C19H28P2O3SF3Lu: C, 36.20; H, 4.48.
Found: C, 34.56; H, 4.28%.
1
Yield: 0.72 g (98%). H-NMR (C6D6, r.t.): l 1.12 [d,
3JHP=10.8, 18 H, PC(CH3)3], 1.73 [m*, N=14.1, 2 H,
CH2CH2P(tBu)2], 2.93 [m*, N=20.2, 2 H, CH2CH2-
P(tBu)2], 5.98 [A2B2 spin system, uncompletely resolved
lA, 5.93; lB, 6.04; 4 H, C5H4]. 13C{1H}-NMR (C6D6,
r.t.): l 25.41 [d, 2JCP=26.4, CH2C5H4], 30.08 [d,
1
2JCP=12.7, C(CH3)3], 31.19 [d, JCP=33.6, C(CH3)3],
4.9. [C5H4CH2CH2PMe2]2La(CF3SO3) (8)
31.71 [s, CH2P(t-Bu)2], 108.17 [s, C5H4], 113.477 [s,
1
3
C5H4], 120.03 [q, JCF=318.4, CF3], 133.39 [d, JCP
10.5, Cipso]. 31P{1H}-NMR (C6D6, r.t.): l 31.94 [d,
PY=7.1]. 31P{1H}-NMR ([d8]toluene, −80°C):
=
To a mixture of 5.06 mmol (0.81 g) of Li[C5H4CH2-
CH2PMe2] and 2.53 mmol (1.48 g) La(CF3SO3)3, 40 ml
of THF was added at −78°C. The reaction mixture
was slowly warmed up to r.t. and stirred for another 12
h. The solvent was removed and a colorless solid was
isolated by extraction with 50 ml of toluene and evapo-
ration of the solvent. 31P{1H}-NMR (C6D6, r.t.): l
−43.58 [br, La(C5H4CH2CH2PMe2)3], 50%, −30.31
(br, [C5H4CH2CH2PMe2]2LaCF3SO3), 50%. 7Li{1H}-
NMR (C6D6, r.t.): l −0.75 (s). Mass spectrum (CI);
m/z (%): 593 (37.6) [M++1], 440 (53.92) [M+−
CF3SO3)], 154 (100) [C5H5CH2CH2PMe2].
J
l
31.94 [d, JPY=7.1]. Mass spectrum (CI); m/z (%): 713
(12.53) [M+], 563 (8.11) [M+−C5H4CH2CH2(t-Bu)2)],
477 (100) {[C5H4CH2CH2P(t-Bu)2]2}.
4.7. [C5H4CH2CH2P(t-Bu)2]2YCl (5)
To
a
mixture of 5.48 mmol (1.34 g) of
Li[C5H4CH2CH2Pt-Bu2] and 1.77 mmol (0.95 g) YCl3,
40 ml of THF was added at −78°C. The reaction
mixture was slowly warmed up to r.t. and stirred for
another 12 h. The solvent was removed and the product
was extracted with 50 ml of toluene. On concentration
of the solvent, 5 was isolated as colorless crystals.
4.10. Reaction of Li[C5H4CH2CH2PMe2] with
Sc(CF3SO3)3
1
Yield: 0.72 g (51%). H-NMR (C6D6, r.t.): l 1.06 [d,
To a mixture of 5.99 mmol (0.96 g) of Li[C5H4CH2-
CH2PMe2] and 1.99 mmol (0.98 g) Sc(CF3SO3)3, 40 ml
of THF was added at −78°C. The reaction mixture
was slowly warmed up to r.t. and stirred for another 12
h. The solvent was removed and a colorless solid was
isolated by extraction with 50 ml of toluene and evapo-
ration, Yield: 0.80 g. 1H-NMR (C6D6, r.t.): l 1.05 [s, 12
H, PMe2], 1.78 [m*, N=48.0, CH2PMe2], 2.57 [m*,
N=30.21, C5H4CH2], 6.03 [A2B2 spin system uncom-
pletely resolved, lA, 5.96; lB, 6.09; 8 H, C5H4CH2-
CH2PMe2]. 13C{1H}-NMR ([d8]toluene, r.t.): l 11.71 [s,
PMe2], 25.05 [d, 2JCP=13.0, CH2C5H4], 34.66 [d,
1JCP=5.2, CH2PMe2], 110.70 [s, C5H4CH2], 111.78 [s,
C5H4CH2], 120.15 [q, 1JCF=318.3, CF3], 133.77 [d,
3JCP=9.3, Cipso]. 31P{1H}-NMR ([d8]toluene, r.t.): l
−31.94 [s, br, 40%], −37.66 [s, br, 60%]. 31P{1H}-
NMR ([d8]toluene, −80 C°): l −31.25 [s, (C5H4CH2-
CH2PMe2)2ScCF3SO3, 90%], −26.07 [(C5H4CH2CH2-
PMe2)3Sc, 5%], −25.49 [(C5H4CH2CH2PMe2)3Sc, 5%].
19F{1H}-NMR (C6D6, r.t.): l −78.6 [s, CF3]. Mass
spectrum (CI); m/z (%): 501 (5.25) [M++1], 351 (100)
[M+−CF3SO3)], 154 [34.03] [C5H5CH2CH2PMe2].
3JHP=11.2, 36 H, PC(CH3)3], 1.74 [m*, N=21.5, 4 H,
CH2C5H4], 2.87 [dtr, 3JHH=7.8, 2JHP=12.2, 4 H,
CH2P(t-Bu)2], 6.11 [s, 8 H, C5H4]. 13C{1H}-NMR
2
(C6D6, r.t.): l 24.33 [d, JCP=8.8, CH2C5H4], 29.01 [d,
2
1JCP=20.2, C(CH3)3], 29.42 [d, JCP=10.4, C(CH3)3],
1
31.82 [d, JCP=10.4, CH2P(t-Bu)2], 108.70 [s, C5H4],
3
111.42 [s, C5H4], 131.80 [d, JCP=9.9, Cipso]. 31P{1H}-
NMR (C6D6, r.t.): l 32.56 [d, JPY=48.5]. 31P{1H}-
NMR ([d8]toluene, −80°C): l 32.56 [d, JPY=48.5].
Mass spectrum (CI); m/z (%): 599 (12.91) [M+], 563
(6.27) [M+−Cl], 541 (27.76) [M+−C4H10], 238 (100)
[C5H4CH2CH2P(t-Bu)2]. Anal. Calc. for C30H52ClP2Y:
C, 60.15; H, 8.75. Found: C, 58.21; H, 8.53%.
4.8. [C5H4CH2CH2PMe2]2Lu(CF3SO3) (6)
To
a
mixture of 3.37 mmol (0.54 g) of
Li[C5H4CH2CH2PMe2] and 1.69 mmol (1.05 g)
Lu(CF3SO3)3, 40 ml of THF was added at −78°C. The
reaction mixture was slowly warmed up to r.t. and
stirred for another 12 h. The solvent was removed and
the product was extracted with 50 ml of toluene. The

80
H.H. Karsch et al. / Journal of Organometallic Chemistry 604 (2000) 72–82
50.80; H, 5.40; Cl, 10.00. Found: C, 49.92; H, 6.00; Cl,
11.5%.
4.11. Reaction of YCl3 with Li2[(C5H4CH2CH2)2PCH3]
To a suspension of 4.06 mmol (0.79 g) YCl3 in 40 ml
THF were added 4.06 mmol (0.99 g) Li2(C5H4CH2-
CH2)2PCH3 at −78°C and then allowed to warm up to
r.t. The reaction mixture shows signals of compound 9
(vide infra). On evaporation of the solvent, a colorless
solid remains, which is insoluble in hydrocarbons.
4.14. (CF3SO3)Lu[(C5H4CH2CH2)2PCH3] (11)
To
a
mixture of 2.05 mmol (0.50 g) of
Li2(C5H4CH2CH2)2PCH3 and 2.04 mmol (1.27 g)
Lu(CF3SO3)3, 40 ml of THF was added at −78°C. The
reaction mixture was slowly warmed up to r.t. and
stirred for another 12 h. The solvent was removed and
the product was extracted with 50 ml of toluene. The
toluene extract was evaporated and 11 was isolated as a
4.12. (Me3Si )2NY[(C5H4CH2CH2)2PCH3] (10)
To a suspension of 3.99 mmol (0.78 g) YCl3 in 40 ml
THF were added with stirring 4.02 mmol (0.98 g)
Li2(C5H4CH2CH2)2PCH3 at −78°C and then allowed
to warm up to r.t.. To the reaction mixture 4.1 mmol
(0.69 g) LiN(SiMe3)2 were added. After 12 h reaction
time the solvent was removed and the residue was
extracted three times with 30 ml of toluene. The toluene
was removed and a colorless solid remained. Yield: 1.56
g (81%). 1H-NMR (C6D6, r.t.): l 0.14 [s, br, 9 H,
SiMe3], 0.38 [s, br, 9 H, SiMe3], 0.72 [d, 2JHP=5.5,
CH3P, 3 H], 1.37 [m*, N=23.1, 4 H, CH2Cp], 2.32
[m*, N=94.1, 4 H, CH2PMe], 5.53 [m*, N=7.7, 1 H,
CH (C5H4)], 5.90 [m*, N=8.1, 1 H, CH (C5H4)], 6.07
[m*, N=7.7, 1 H, CH (C5H4)], 6.41 [m*, N=7.7, 1 H,
CH (C5H4)]. 13C{1H}-NMR (C6D6, r.t.): l 5.54 [s, br,
1
colorless solid. Yield: 1.10 g (97%). H-NMR (C6D6,
r.t.): l 0.92 [d, 2JHP=6.2, 3 H, CH3P], 1.34 [m*,
N=48.3, 4 H, CH2 C5H4], 2.29 [m*, N=137.7, 4 H,
MePCH2], 5.47 [m, 2 H C5H4], 5.94 [m, 2 H, C5H4],
6.20 [m, 2 H, C5H4], 6.49 [m, 2 H, C5H4]. 13C{1H}-
1
NMR (C6D6, r.t.): l 7.52 [d, JCP=7.3, CH3P], 24.18
[d, 2JPC=13.0, CH2C5H4], 29.90 [d, 1JCP=17.6,
PCH2], 102.55 [s, CH, (C5H4)], 107.19 [s, CH, (C5H4)],
108.49 [s, CH (C5H4)], 115.18 [s, CH (C5H4)], 128.76
[d,3JCP=8.1, Cipso]. 31P{1H}-NMR (C6D6, r.t.): l −
8.86 (s). 19F-NMR (C6D6, r.t.): l 0.46 [s, CF3]. Mass
spectrum (CI); m/z (%): 553 (32) [M−1], 404.9 (100)
[MꢀCF3SO3], 232 (63) [CH3P(CH2CH2C5H5)2].
4.15. X-ray crystallography
1
2
SiMe3], 6.27 [s, br, SiMe3], 9.57 [dd, JCP=9.2, JCY
=
1.5, CH3P], 24.05 [d, 2JCP=10.0, CH2Cp], 30.57 [d,
1JCP=16.1, CH2PMe], 104.01 [d, JCY=1.5, C5H4],
109.28 [s, C5H4], 110.75 [s, C5H4], 114.79 [d, JCY=1.5,
C5H4], 128.91 [d, 3JCP=6.9, Cipso]. 31P {1H}-NMR
Suitable single crystals of complex 1 for a X-ray
diffraction study were obtained by slowly removing the
solvent. The structure was solved by a combination of
direct methods, difference-Fourier syntheses and least-
squares methods. Neutral atom scattering factors for all
atoms and anomalous dispersion corrections for the
non-hydrogen atoms were taken from the International
Tables for X-ray Crystallography [28]. All calculations
were performed on a Linux PC using the programs
PLATON [29], SIR-92 [30], and SHELX-93 [31].
1
(C6D6, r.t.): l −19.95 [d, JPY=110.8]. Mass spectrum
(CI); m/z (%): 479 (19.48) [M+1], 464 (42.77) [M+−
CH3], 319 (100) [M+−N(SiMe3)2]. Anal. Calc. for
C21H37NPYSi2: C, 52.59; H, 7.78; N, 2.92. Found: C,
49.90; H, 7.63; N, 2.41%.
4.13. ClY[(C5H4CH2CH2)2PCH3] (9)
4.15.1. Data collection, structure solution and
refinement
A summary of the collection and refinement data are
reported in Table 2. Single crystal data for 1 were
collected on a kappa-CCD system from Nonius with a
rotating anode generator (Nonius FR591; Mo–Ka, u=
To a solution of 1.65 mmol (0.79 g) 10 in 40 ml
toluene were added with stirring 1.50 mmol (0.08 g)
NH4Cl at −78°C and then allowed to warm up to
room temperature. The formation of a colorless solid is
observed. After filtration the solid was washed with
1
toluene and dried in vacuo. Yield: 0.45 g (84%). H-
,
0.71073 A) in rotation mode (€-scans) using Mo–Ka
NMR (THF+C6D6, r.t.): l 1.06 [d, 2JHP=5.9, 3H,
CH3], 1.30–1.38 [m, 4H, CH2 C5H4], 2.45–2.59 [m, 4H
PCH2], 5.54 [m, 2 H C5H4], 5.60 [m, 2 H, C5H4], 5.78
[m, 2 H, C5H4], 5.98 [m, 2 H, C5H4]. 13C{1H}-NMR
radiation (graphite monochromator). The data collec-
tion was performed at 193 K within the q-range of
4BqB26.4° (€=0.0–360° with D€=1°). A total
number of 15 344 reflections were collected. After
merging 4049 independent reflections remained and
were used for all calculations. Data were corrected for
Lorentz and polarization effects. Corrections for inten-
sity decay and/or absorption effects with the program
Scalepack [32] were applied. All ‘heavy’ atoms of the
asymmetric unit were anisotropically refined. Only car-
1
(THF+C6D6, r.t.): l 8.40 [d, JCP=4.7, PCH3], 24.65
[d, 2JCP=15.6, CH2 C5H4], 29.53 [d, 1JCP=11.9,
PCH2], 103.07 [s, CH, (C5H4)], 107.07 [s, CH, (C5H4)],
107.52 [s, CH (C5H4)], 115.71 [s, CH (C5H4)], 129.9 [d,
3JCP=8.3, Cipso]. 31P{1H}-NMR (THF+C6D6, r.t.): l
−21.29 [d, JYP=84.3]. Anal. Calc. for C15H19PYCl: C,

H.H. Karsch et al. / Journal of Organometallic Chemistry 604 (2000) 72–82
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Allg. Chem. 625 (1999) 1107.
bon atom C15 was refined isotropically with two split-
ted positions due to disorder in the ethylene backbone
of the second phosphine ligand and all hydrogen atoms
were calculated in ideal positions (riding model). Full-
matrix least-squares refinements of 193 parameters were
carried out by minimizing Dw(F2o−Fc2)2 with SHELXL
weighting scheme and stopped at shift/errB0.001.
4.16. Supplementary material
Crystallography data for the structural analysis has
been deposited with the Cambridge Crystallographic
Data Center, CCDC no. 139688. Copies of the data can
be obtained free of charge from The Director, CCDC,
12 Union Road, Cambridge CB2 1EZ, UK (fax: +44-
1223-336033; e-mail: deposit@ccdc.cam.ac.uk or www:
http://www.ccdc.cam.ac.uk). A listing (25 pages) can
also be ordered from the ACS, and can be downloaded
from the internet; see any current masthead page for
ordering and Internet access instructions.
Acknowledgements
This research was financially supported by the
Deutsche Forschungsgemeinschaft.
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