Synthesis, structure, and reactivity of ruthenium(II) complexes with a hemilabile tetradentate etherdiphosphine ligand

Article abstract of DOI:10.1016/S0022-328X(00)00065-6

In refluxing toluene the tetradentate ligand (Ph₂PCH₂CH₂OCH₂-)₂ (1) reacts with Cl₂Ru(PPh₃)₃ to give the stable η⁴-(O,O,P,P)-chelated ruthenium(II) complex trans-Cl₂Ru(Ph₂PCH₂CH₂OCH ₂-)₂ (2). With carbon monoxide no transformation to an η³-(O,P,P)- or η²-(P,P)-chelated complex accompanied by an uptake of CO takes place. However, if [Cl₂Ru(CO)₂]_n is treated with 1 in a mixture of dichloromethane and 2-methoxyethanol, the η³-(O,P,P)-coordinated ruthenium(II) complex trans-Cl₂Ru(CO)(Ph₂PCH₂CH₂OCH ₂-)₂ (3) is formed. Attempts to eliminate carbon monoxide from complex 3 to give 2 failed. Also, 3 does not react with further carbon monoxide to form an η²-(P,P)-chelated dicarbonylruthenium(II) complex. Complexes 2 and 3 have been characterized by X-ray structural analyses.

Full text of DOI:10.1016/S0022-328X(00)00065-6

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Journal of Organometallic Chemistry 601 (2000) 220–225
Synthesis, structure, and reactivity of ruthenium(II) complexes
with a hemilabile tetradentate etherdiphosphine ligand
Ekkehard Lindner * , Joachim Wald, Klaus Eichele, Riad Fawzi 1
Institut fu¨r Anorganische Chemie der Uni6ersita¨t Tu¨bingen, Eberhard-Karls-Uni6ersita¨t, Auf der Morgenstelle 18, D-72076 Tu¨bingen, Germany
Received 22 December 1999
Abstract
In refluxing toluene the tetradentate ligand (Ph2PCH2CH2OCH2ꢀ)2 (1) reacts with Cl2Ru(PPh3)3 to give the stable h4-
(O,O,P,P)-chelated ruthenium(II) complex trans-Cl2Ru(Ph2PCH2CH2OCH2ꢀ)2 (2). With carbon monoxide no transformation to
an h3-(O,P,P)- or h2-(P,P)-chelated complex accompanied by an uptake of CO takes place. However, if [Cl2Ru(CO)2]n is treated
with 1 in a mixture of dichloromethane and 2-methoxyethanol, the h3-(O,P,P)-coordinated ruthenium(II) complex trans-
Cl2Ru(CO)(Ph2PCH2CH2OCH2ꢀ)2 (3) is formed. Attempts to eliminate carbon monoxide from complex 3 to give 2 failed. Also,
3 does not react with further carbon monoxide to form an h2-(P,P)-chelated dicarbonylruthenium(II) complex. Complexes 2 and
3 have been characterized by X-ray structural analyses. © 2000 Elsevier Science S.A. All rights reserved.
Keywords: Ruthenium complexes; Tetradentate ether–phosphine ligands; Crystal structures
1. Introduction
trolled by steric and conformational factors of the
ligand backbone. Obviously this is the reason why in
the complex chemistry with hemilabile ligands in most
cases a direct connection between the oxygen donors
was avoided [7]. Recently however, Mathieu and co-
workers reported on a bis(diphenylphosphino)-3,6-
dioxaoctane complex of rhodium(I) showing some
catalytic activity in the hydroformylation of 1-hexene
[8]. The present investigation reports on the first h3-
and h4-coordinated ruthenium(II) complexes with this
ligand and their behavior toward carbon monoxide.
Ether–phosphines belong to the group of hemilabile
ligands and have attracted considerable interest in re-
cent years [1–4]. They are equipped with a soft phos-
phorus and a hard oxygen donor function. Whereas the
phosphorus atom is strongly coordinated to a late
transition-metal center, the ether oxygen atom forms
only a weak contact to this metal. Therefore, the ether
moiety behaves like an intramolecular solvent being
easily replaced by an incoming substrate [5]. Addition-
ally, the oxygen function is able to stabilize coordina-
tively unsaturated transition-metal fragments, an
important feature in catalysis [6]. The reversible protec-
tion of one or more coordination sites by an in-
tramolecular solvent is the most important property of
hemilabile ligands like ether–phosphines, which often
leads to an improvement in both catalytic and
organometallic model reactions. It has to be considered
that the ability of the weakly coordinated ether func-
tion to afford empty coordination sites is also con-
* Corresponding author. Tel.: +49-7071-2972039; fax: +49-7071-
295306.
E-mail address: ekkehard.lindner@uni-tuebingen.de (E. Lindner)
1 Deceased.
Scheme 1.
0022-328X/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(00)00065-6

E. Lindner et al. / Journal of Organometallic Chemistry 601 (2000) 220–225
221
2. Results and discussion
roborate this dynamic behavior the temperature was
gradually decreased. First, a broadening of the 31P
signal takes place, then it disappears at −70°C. The
metal–oxygen contact is also indicated in the 13C{1H}-
NMR spectrum of 3. The 13C signals of the methylene
groups that are in the vicinity of the ether oxygen
donor are shifted to lower field. Carbon nuclei adjacent
to phosphorus show signals appearing as pseudo
triplets. Their signals correspond to the X part of an
ABX spin system [11]. The intensity ratio of the central
line and the two N lines indicates that the coupling
between the two phosphorus nuclei is much stronger
than anticipated for typical 2J(P,P)cis coupling con-
stants [7b], suggesting a trans arrangement of both
phosphorus atoms.
Attempts to eliminate carbon monoxide from com-
plex 3 by heating the yellow solid over a period of
about 16 h at 90°C failed [12]. If a solution of 3 in
CH2Cl2 is treated with carbon monoxide at room tem-
perature or under more drastic conditions (60 bar,
60°C, 24 h) in an autoclave [12], the reaction does not
proceed selectively to one product; only a mixture
of different (dppoo)ruthenium(II) complexes was
obtained.
2.1. Synthesis of p4- and p3-dppoo complexes of
ruthenium(II)
If Cl2Ru(PPh3)3 is reacted with one equivalent of the
dppoo ligand 1 in boiling toluene, a nearly quantitative
reaction takes place and the thermally rather stable
(h4-dppoo)ruthenium(II) complex 2 precipitates as an
orange–brown solid if the reaction mixture is cooled to
ambient temperature (Scheme 1). Compound 2 dis-
solves readily in organic solvents of medium polarity
(e.g. dichloromethane, chloroform). The composition of
2 was established by a FD mass spectrum, revealing the
molecular peak at m/z=658. A singlet in the 31P{1H}-
NMR spectrum of 2 (in CD2Cl2) points to the equiva-
lence of both phosphorus atoms and the chemical shift
of 66.3 ppm is typical for five-membered rings which
means that the ligand 1 is coordinated to ruthenium(II)
in an h4-fashion. In agreement with this observation the
1H and 13C signals of the oxygen adjacent methylene
1
groups in the H- and 13C{1H}-NMR spectra of 2 are
also shifted to lower field compared to 1.
A typical reaction for ruthenium(II) and other transi-
tion-metal complexes containing at least two bidentate
h2(O,P)-chelated ether–phosphine ligands [9] is the
consecutive cleavage of both metalꢀoxygen bonds in the
presence of small donor molecules like sulfur dioxide,
carbon disulfide, nitriles or isonitriles, phenylacetylene
or carbon monoxide. Since dppoo (1) represents for-
mally the combination of two bidentate O,P ligands in
the ruthenium(II) complex 2, a similar reactivity toward
such small molecules should be expected. However, if a
solution of [Cl2Ru(h4-dppoo)] (2) in CH2Cl2 is sub-
jected to an atmosphere of carbon monoxide at ambi-
ent temperature, no transformation from an h4- to an
h3- or h2-complex accompanied by a concomitant up-
take of CO takes place. Therefore, the behavior of 1
toward [Ru(CO)2Cl2]n was investigated. In a mixture of
dichloromethane and 2-methoxyethanol both starting
materials were reacted in a 1:1 ratio at room tempera-
ture under high dilution conditions to avoid the forma-
tion of bridged oligomeric products [10]. After work-up
of the reaction mixture, the yellow h3-dppoo coordi-
nated ruthenium(II) complex 3 was obtained (Scheme
1). It dissolves readily in chlorinated hydrocarbons and
is thermally rather stable. The FAB mass spectrum of 3
displays a molecular peak at m/z=686. In the IR
spectrum of 3 (KBr) an intense absorption at 1934
cm−1 is observed, which is ascribed to the carbonyl
ligand. The location of this band is characteristic for a
trans position to an ether oxygen function. The
31P{1H}-NMR spectrum of 3 (in CD2Cl2) reveals only a
signal at room temperature (l 34). Obviously a rapid
exchange between both oxygen donors in the coordina-
tion sphere of ruthenium(II) takes place [7b]. To cor-
2.2. Discussion of the X-ray crystal structures of 2 and
3
The crystal structure of 2 (Fig. 1) is analogous to that
of [Rh(dppoo)Cl2][PF6] [8]. Selected bond distances and
angles are collected in Table 1. Ruthenium is coordi-
nated in an octahedral manner with the h4-coordinated
dppoo ligand occupying and effectively shielding the
equatorial plane. Both chlorine atoms adopt a trans
arrangement in axial positions. Although the atoms of
the equatorial plane, Ru(1), P(1), P(2), O(1), and O(2),
,
deviate by less than 0.07 A from the least-squares
plane, the in-plane PꢀRuꢀP and OꢀRuꢀO angles,
108.79(8) and 74.45(16)°, respectively, deviate drasti-
cally from an ideal octahedral geometry, presumably
due to the steric constraints imposed by the three fused
five-membered chelate rings. The two chlorine atoms
are forced away from their ideal axial positions and are
slightly bent towards the oxygen atoms. Altogether, the
molecule crystallizes with pseudo C2 symmetry. This
fact is reflected in the conformation of the three five-
membered chelate rings: the two outer rings adopt
envelope conformations with the tip atoms C(26) and
,
C(29) located about 0.6 A above and below their
respective ring planes, while the center chelate prefers a
twist conformation with C(27) and C(28) being 0.31
,
and 0.46 A below and above the O(1)ꢀRu(1)ꢀO(2)
plane. The flap angle of both envelope conformations
lies at about 135°.
In 3, the h3-coordination mode of the dppoo ligand
results in the formation of a bicyclic system. Ruthenium

222
E. Lindner et al. / Journal of Organometallic Chemistry 601 (2000) 220–225
Fig. 1. ORTEP plot of the molecular structure of compound 2. Thermal ellipsoids are drawn at 20% probability level, except for H atoms. Solvent
molecules are omitted for clarity.
and the coordinated ether oxygen are the bridgeheads
of the annealed rings and connect a five- and eight-
membered ring. The five-membered ring favors a dis-
torted conformation between an envelope and twist
conformation, with a C(25)ꢀP(1)ꢀRu(1)ꢀO(1) torsional
angle of 7.5°, and C(25) and C(26) being −0.25(1)
the h3-coordination is established by single-crystal X-
ray diffraction.
3. Conclusions
,
and 0.51(1) A below and above the plane defined by
Although the tetradentate dppoo ligand 1 is able to
coordinate to ruthenium(II) via one or even both oxy-
gen donor functions as demonstrated in the case of
complexes 3 and 2, attempts to activate small molecules
like carbon monoxide with cleavage of the weak RuꢀO
bonds were not successful. This behavior is in marked
contrast to corresponding (O,P)-bis(chelated) ruthen-
ium(II) complexes containing two bidentate ether–phos-
phine ligands [7b,9,12]. The main difference between
both ligand types is a bridging ethylene function between
both ether oxygen donors in 1. Hence polycyclic chelate
rings are formed as soon as one or both oxygen atoms
coordinate to ruthenium(II). By this coordination mode
not only the mobility of the whole ligand system is
reduced, but also the reactive centers are shielded. In this
way the cleavage of the RuꢀO bonds is impeded and the
hemilabile character of the ligand is weakened.
Ru(1), P(2), and O(1), respectively. The eight-mem-
bered ring adopts a conformation that is uncommon
for ring systems of this size: a slightly distorted
chair–boat conformation. The two rutheniumꢀ
phosphorus bond lengths are equal within error lim-
its. The trigonal geometry of O(1) is slightly dis-
torted; the relatively small Ru(1)ꢀO(1)ꢀC(26) angle of
the five-membered ring, 113.1(4)°, is counterbalanced
by an enlarged Ru(1)ꢀO(1)ꢀC(27) angle in the eight-
membered ring, 125.5(4)°. The other oxygen atom of
,
the dppoo ligand, O(2), is with 4.296 A clearly too
remote from the ruthenium to take part in any kind
of coordination. The position of the CO group trans
to the ether oxygen, deduced from IR spectroscopy, is
confirmed by the X-ray diffraction data (Fig. 2).
Compound 3 is the first complex of dppoo for which

E. Lindner et al. / Journal of Organometallic Chemistry 601 (2000) 220–225
223
4. Experimental
4.2. trans-Dichloro-cis-1,8-bis[(diphenylphosphino)-
3,6-dioxaoctane-O,O,P,P]ruthenium(II) (2)
4.1. General procedures
To a solution of Cl2Ru(PPh3)3 (0.958 g, 1.0 mmol)
in 250 ml of boiling toluene a solution of bis-
(diphenylphosphino)-3,6-dioxaocatane (1) (0.486 g, 1.0
mmol) in 150 ml of toluene was added dropewise. To
complete the reaction, the mixture was refluxed for 16
h. The solution was cooled to room temperature and 2
precipitated as an orange–brown solid, which was iso-
lated by filtration (P3). Yield: 0.53 g (82%); m.p. 243°C.
MS (FD, 35°C): m/z 657.9 [M+]. Anal. Calc. for
C30H32P2O2RuCl2 (658.405): C, 54.72; H, 4.90; Cl,
10.77%. Found: C, 54.22; H, 4.85; Cl, 10.97%. 31P{1H}-
All manipulations were carried out under an atmo-
sphere of argon by use of standard Schlenk techniques.
Solvents were dried with appropriate reagents, distilled,
degassed and stored under argon. IR data were ob-
tained with a Bruker IFS 48 FTIR spectrometer. FD
mass spectra were taken on a Finnigan MAT 711 A
instrument, modified by AMD; FAB mass spectra were
recorded on a Finnigan TSQ 70. Elemental analyses
were performed with a Carlo Erba 1106 analyzer; Cl
analyses were carried out according to Scho¨niger [13].
1H-, 31P{1H}-, and 13C{1H}-NMR spectra were
recorded on a Bruker DRX 250 spectrometer at 250.13,
1
NMR (101.26 MHz, CDCl3, 25°C): l=66.3 (s). H-
1
NMR (250.13 MHz, CDCl3, 25°C): l=7.0–7.2 (m,
20H, PPh2); l=4.3 (s, br, 8H, Ph2PCH2CH2OCH2);
l=3.0 (s, br, 4H, PPh2CH2). 13C{1H}-NMR (62.90
MHz, CD2Cl2, 25°C): l=136.1 (m, N2=45.5 Hz [11],
1J(PC)=44 Hz, 3J(PC)=1.5 Hz, 2J(P,P%)=33 Hz,
ipso-C of PPh2); l=133.3 (m, N2=9.3 Hz [11], o-C of
PPh2); l=129.0 (s, p-C of PPh2); l=126.9 (m, N2=
10.0 Hz [11], m-C of PPh2); l=73.3 (s,
PPh2CH2CH2OCH2); l=70.2 (s, PPh2CH2CH2OCH2);
l=34.7 (m, N2=24.2 Hz [11], PPh2CH2CH2OCH2).
101.25, and 62.90 MHz, respectively at 25°C. H and
13C chemical shifts were measured relative to partially
deuterated solvent peaks and to deuterated solvent
peaks, respectively, which are reported relative to TMS.
31P chemical shifts were measured relative to 85%
H3PO4 (l=0). 31P{1H}-NMR spectra were also
recorded on a Bruker AC 80 instrument operating at
32.44 MHz with external standard. At low tempera-
tures, 0 to −80°C, 1% H3PO4 in acetone-d6 was used
as an external standard and above 0°C, 1% H3PO4 in
D2O. The temperatures of the variable-temperature
31P{1H}-NMR spectra were calibrated using the
method of van Geet [14] and are considered accurate to
91 K. The diphosphine ligand 1 was synthesized ac-
cording to a procedure published by Dapporto and
Sacconi [15].
4.3. Carbonyl(trans-dichloro)-trans-1,8-
abis[(diphenylphosphino)-3,6-dioxaoctane-O,P,P]-
ruthenium(II) (3)
RuCl3·xH2O (510 mg, 2.02 mmol) was dissolved in
200 ml of boiling 2-methoxyethanol. Carbon monoxide
was bubbled through the refluxing solution for 5 h until
the color of the reaction mixture turned to yellow,
indicating the formation of the precursor [Ru-
(CO)2Cl2]n. Bis(diphenylphosphino)-3,6-dioxaocatane
(1) (980 mg, 2.02 mmol) was dissolved in a mixture of
250 ml of 2-methoxyethanol and of dichloromethane
(1:1). Both solutions were transferred in two different
dropping funnels and the solutions were added slowly
within 6 h under vigorous stirring to a reaction vessel
charged with 500 ml of dichloromethane. To complete
the reaction, the mixture was stirred for 16 h at ambient
temperature. After the solvent mixture was removed
under reduced pressure, the remainder was dissolved in
50 ml of dichloromethane. The product precipitated by
the addition of 25 ml of n-pentane and was collected by
filtration (P3). Yield: 1.05 g (76%) of 3, yellow powder;
decomposition 225°C; MS (FAB, 30°C): m/z 686.0
[M+], 651.1 [M+−Cl], 587.2 [M+−2Cl−CO]. Anal.
Calc. for C31H32P2O3RuCl2 (686.514): C, 54.23; H, 4.69;
Cl, 10.32%. Found: C, 53.87; H, 4.74; Cl, 10.43%. IR
Table 1
,
Selected bond lengths (A) and angles (°) for 2 and 3
2·H2O
3·CH2Cl2·H2O
Bond lengths
Ru(1)ꢀCl(1)
Ru(1)ꢀCl(2)
Ru(1)ꢀP(1)
Ru(1)ꢀP(2)
Ru(1)ꢀO(1)
Ru(1)ꢀO(2)
Ru(1)ꢀC(31)
2.393(2)
2.386(2)
2.135(2)
2.2689(19)
2.116(4)
2.248(4)
2.401(3)
2.377(3)
2.401(2)
2.360(2)
2.207(6)
1.828(9)
Bond angles
O(1)ꢀRu(1)ꢀO(2)
O(2)ꢀRu(1)ꢀP(2)
Cl(2)ꢀRu(1)ꢀCl(1)
P(1)ꢀRu(1)ꢀP(2)
Cl(2)ꢀRu(1)ꢀP(1)
Cl(1)ꢀRu(1)ꢀP(1)
P(1)ꢀRu(1)ꢀO(2)
C(26)ꢀO(1)ꢀC(27)
C(26)ꢀO(1)ꢀRu(1)
C(27)ꢀO(1)ꢀRu(1)
C(29)ꢀO(2)ꢀC(28)
C(29)ꢀO(2)ꢀRu(1)
C(28)ꢀO(2)ꢀRu(1)
74.47(16)
163.15(11)
172.76(5)
108.79(8)
90.00(7)
93.64(8)
87.96(12)
117.2(4)
110.6(3)
112.6(3)
112.1(4)
112.0(3)
112.5(3)
172.36(8)
172.55(7)
94.88(9)
86.06(9)
114.2(6)
113.5(4)
125.5(5)
115.1(6)
.
(KBr): w(CO)=1934 cm−1 31P{1H}-NMR (101.26
m
n
2 X part of an ABX spin system, N=ꢀ J(AX)ꢀ+ꢀ J(BX)ꢀ.

224
E. Lindner et al. / Journal of Organometallic Chemistry 601 (2000) 220–225
Fig. 2. ORTEP plot of the molecular structure of compound 3. Thermal ellipsoids are drawn at 20% probability level, except for H atoms. Solvent
molecules are omitted for clarity.
MHz, CD2Cl2, 25°C): l=34.0 (s). 13C{1H}-NMR
(62.90 MHz, CD2Cl2, 25°C): l=131.6 (m, N1=46.2
Hz [11], ipso-C of PPh2); l=132.5 (m, N1=10.6 Hz
[11], o-C of PPh2); l=127.1 (m, N1=9.9 Hz [11], m-C
of PPh2); l=129.0 (m, N1=2.8 Hz [11], p-C of PPh2);
using Bruker SHELXTL 5.10. Non-hydrogen atoms were
refined with anisotropic displacement parameters,
except for the atoms of the solvent molecules. Hydro-
gen atoms were constrained to idealized positions
using a riding model (with free rotation for methyl
groups). Solvent molecules present in crystals of both 2
and 3 were disordered and not clearly defined and
hence refined isotropically. The largest difference peak
l=81.4
(s,
PCH2CH2OCH2);
l=72.4
(s,
PCH2CH2OCH2); 26.4 (m, N1=24.9 Hz [11],
PCH2CH2OCH2).
,
and holes are located less than 1 A away from ruthe-
nium.
4.4. Single-crystal X-ray diffraction analyses
Crystals of 3 were grown from a mixture of
dichloromethane and ethyl acetate (1:4). Data for 2 and
3 were collected on a Siemens P4 diffractometer operat-
ing in the ꢀ scan mode, using graphite monochromated
5. Supplementary material
Crystallographic data for the structural analysis has
been deposited with the Cambridge Crystallographic
Data Center, CCDC nos. 137576 for compound 2 and
137575 for complex 3. Copies of this information may
be obtained free of charge from The Director, CCDC,
,
Mo–Ka radiation (u=0.71073 A). Full details of crys-
tal data, data collection and structure refinement are
given in Table 2. The structures were solved by direct
methods and refined by full-matrix least-squares on F2

E. Lindner et al. / Journal of Organometallic Chemistry 601 (2000) 220–225
225
Table 2
Crystal data and structure refinement details for complexes 2 and 3
Acknowledgements
Support of this research by the Fonds der Chemis-
chen Industrie is gratefully acknowledged. K.E. appre-
ciates discussions with Dr Christiane Nachtigal.
2·H2O
3·CH2Cl2·H2O
Empirical formula
Formula weight
Crystal color
C30H34Cl2O3P2Ru C32H36Cl4O4P2Ru
676.48
Orange-brown
789.42
Yellow
Crystal size (mm)
Unit cell dimensions
0.50×0.35×0.10 0.31×0.24×0.11
References
,
a (A)
10.285(6)
10.296(6)
16.334(11)
84.52(6)
71.84(4)
63.80(4)
Triclinic
14.602(9)
12.739(9)
18.143(14)
90
91.81(6)
90
Monoclinic
P21/c
4
173(2)
11 813/5943
0.1142
−17–17,
−15–0,
−21–21
2.12–25.03
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145.
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Organometallics 16 (1997) 1401. (b) P. Braunstein, Y. Chauvin,
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488 (1995) 169. (f) H. Werner, A. Stark, P. Steinert, G. Gru¨nwald,
J. Wolf, Chem. Ber. 128 (1995) 49.
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M. Steimann Chem. Ber. 126 (1993) 1317. (b) E. Lindner, A.
Mo¨ckel, H.A. Mayer, H. Ku¨hbauch, R. Fawzi, M. Steimann,
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Acta 215 (1994) 165.
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
Crystal system
Space group
Z
Temperature (K)
Reflections collected/unique 13 514/6757
(
P1
2
173(2)
Rint
0.0582
Limiting indices hkl
−13–13,
−13–13,
−21–21
2.21–28.94
q Range for data
collection (°)
Completeness to q (%)
Absorption coefficient
87.0
0.853
99.7
0.912
(mm−1
)
Absorption correction
Max./min. transmission
None
„ scans
0.541/0.475
5943/0/369
0.944
Data/restraints/parameters 6757/0/338
Goodness-of-fit on F2
1.114
Final R indices [I\2|(I)], 0.0706 a/0.1741 b 0.0737 a/0.1925 b
R1/wR2
R indices (all data), R1/wR2 0.0857 a/0.1851 b 0.1070 a/0.2124 b
Extinction coefficient
Largest diff. peak and hole 2.107, −3.010
(e A
0.0003(10)
0.0000(3)
1.802, −1.226
[8] M. Alvarez, N. Lugan, R. Mathieu, J. Organomet. Chem. 468
(1994) 249.
[9] E. Lindner, M. Gepra¨gs, K. Gierling, R. Fawzi, M. Steimann,
Inorg. Chem. 34 (1995) 6106.
[10] L. Rossa, F. Vo¨gtle, in: F. Vo¨gtle (Ed.), Synthesis of Medio- and
Macrocyclic Compounds by High Dilution Principle Techniques:
Topics in Current Chemistry. Cyclophanes I, vol. 113, Springer,
Heidelberg, 1983.
−3
,
)
a R1=ꢁ ꢀꢀFoꢀ−ꢀFcꢀꢀ/ ꢁ ꢀFoꢀ.
b wR2=ꢀ ꢁ [w(Fo2−Fc2)2]/ ꢁ [w(F2o)2]ꢀ
.
0.5
[11] R.K. Harris, Can. J. Chem. 42 (1964) 2275.
[12] E. Lindner, U. Schober, R. Fawzi, W. Hiller, U. Englert, P.
Wegner, Chem. Ber. 120 (1987) 1621.
[13] W. Scho¨niger, Microchim. Acta (1955) 123.
[14] A.L. van Geet, Anal. Chem. 40 (1968) 2227.
[15] P. Dapporto, L. Sacconi, J. Chem. Soc. A (1971) 1914.
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).