Synthesis of achiral and racemic catenanes based on terpyridine and a directionalized terpyridine mimic, pyridyl-phenanthroline

Article abstract of DOI:10.1039/b506101f

Concatenated macrocycles containing manisyl-substituted tridentate ligands 2,2′:6′,2″-terpyridine and 2-pyridin-2-yl-1,10-phenanthroline (simply referred to as terpyridine and pyridyl-phenanthroline herein) have been prepared via dual cyclization procedur

Full text of DOI:10.1039/b506101f

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A R T I C L E
Synthesis of achiral and racemic catenanes based on terpyridine and
a directionalized terpyridine mimic, pyridyl-phenanthroline
Jon C. Loren,a Peter Gantzel,a Anthony Lindenb and Jay S. Siegel*b
a The Department of Chemistry, University of California San Diego, 9500 Gilman Drive,
La Jolla, California 92093-0358, USA
b The Organic Chemistry Institute, University of Zu¨rich, Winterthurerstrasse 190, 8057, Zu¨rich,
Switzerland. E-mail: jss@oci.unizh.ch
Received 29th April 2005, Accepted 12th July 2005
First published as an Advance Article on the web 2nd August 2005
Concatenated macrocycles containing manisyl-substituted tridentate ligands 2,2ꢀ:6ꢀ,2ꢀꢀ-terpyridine and
2-pyridin-2-yl-1,10-phenanthroline (simply referred to as terpyridine and pyridyl-phenanthroline herein) have been
prepared via dual cyclization procedures. The manisyl derivative (manisyl = 4-methoxy-2,6-dimethylphenyl) was
chosen for its ability to improve solubility while simultaneously incorporating functionality. Deprotection of the
methoxy groups provided a soluble ligand that was re-alkylated with an array of terminal alkyne and alkene linkers.
The tridentate coordinating ability of these ligands enabled complexation with Ru(II) and Fe(II), generating achiral
and racemic octahedral complexes for terpyridine and pyridyl-phenanthroline, respectively. Subsequent
macrocyclization via olefin metathesis or copper-mediated alkyne coupling afforded the corresponding catenanes,
and in some cases a figure-eight macrocycle. The difference in symmetry and the presence of the manisyl group
allowed the distinction between the catenane and the undesired figure-eight to be made directly by 1H
NMR. Metal-free achiral and racemic catenanes were obtained by liberating Fe(II) from the octahedral bound title
ligands by treatment with hydrogen peroxide.
copper-mediated alkyne coupling26 for macrocyclization were
Introduction
implemented, and the relative advantages of each method are
Molecular representations of complex topologies are aestheti-
discussed. Symmetry analysis for the identification of catenane
cally attractive constructs that present challenges in structural
vs. figure-eight isomeric products by counting manisyl signals
design and synthesis.1,2 Borromean Links,2a catenanes,2b and
in the 1H or 13C NMR is presented as confirmation of the
knots2b are representative of this class of structures, and
stereoselective synthesis. To our knowledge, the synthesis of
along with their precursors, have been noticed for their po-
metal-free achiral/racemic catenanes from these ligands has not
tential applications.3 Many of these assemblies rely on pre-
been reported.17
organized templates4 that include rigid complexes between
chelating ligands and transition metals.5 This approach, termed
metal-templated, requires a coordinating component, of which
Results and discussion
the polypyridines, 2,2ꢀ-bipyridine,6 1,10-phenanthroline,7 and
The metal-templated synthesis of catenanes commences with
2,2ꢀ:6ꢀ,2ꢀꢀ-terpyridine8 are commonly employed and are of con-
tridentate ligands 3a and 4a, previously prepared from commer-
cially available and literature-known intermediates in two and
siderable interest to our research group.9,10
three steps, respectively.23 Deprotection of the methoxy groups
with molten pyridinium hydrochloride provides soluble phenolic
derivatives, 3b and 4b, that serve as backbones to the chiral
and racemic catenanes presented here (Scheme 1). The terminal
acetylene and olefin linkers used for macrocyclization, 21–24b,
were prepared in two steps as indicated from commercially
available materials (Scheme 2).27
The bidentate ligand 1,10-phenanthroline and its tetrahedral
coordination complex with copper(I) is the pioneering model for
metal-templated synthesis of molecular catenanes.11 The ease
of introducing alkyl- and aryl-substituents into the 2- and 9-
positions of commercially available 1,10-phenanthroline makes
this ligand synthetically desirable for scaffolding.12 In contrast,
there are fewer examples of catenanes where the template is
an octahedral center,13–15 or that include terpyridine within their
framework.16,17 The first catenane built solely around terpyridine
precluded removal of the templating metal,15 while subsequent
attempts to prepare a template-free version resulted in exclusive
formation of a figure-eight macrocycle.18
Chiral variants of a catenane can be made by introducing
asymmetry in the tethering or ring-closing steps,14,19 or by
incorporating directionality within the macrocycles.20 For exam-
ple, coordination complexes of the directionalized terpyridine
mimic, pyridyl-phenanthroline,21 are chiral and make practical
building blocks for concatenated species.
Advances in poly-pyridine ligand synthesis, via cross-coupling
methods, makes terpyridine and pyridyl-phenanthroline readily
accessible;9,22,23 and thus, prime candidates for the synthesis
of achiral and racemic catenanes, respectively. To broaden the
family of concatenated topological isomers and demonstrate
proof-of-principle, a series of catenanes from octahedral Ru(II)
and Fe(II) templates of manisyl-substituted terpyridine and
pyridyl-phenanthroline were targeted.24 Olefin metathesis25 and
Scheme 1
Ru(II)-templated catenanes
Coordination of ligand 3b with Ru(II) was achieved by reaction
with RuCl2(DMSO)4 in refluxing ethylene glycol.28 Aqueous
workup with potassium hexafluorophosphate provided the
T h i s j o u r n a l i s
T h e R o y a l S o c i e t y o f C h e m i s t r y 2 0 0 5
O r g . B i o m o l . C h e m . , 2 0 0 5 , 3 , 3 1 0 5 – 3 1 1 6
3 1 0 5
©

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Scheme 2 Reagents and conditions: a) NaH, 0 ◦C → RT, 5-bromopentene, reflux, 12 h, 55%. b) Triethylamine, tosyl chloride, DMAP, dichloromethane,
0 ◦C → RT, 87% for 21b and 78% for 23b. c) NaH, 0 ◦C → RT, 6-chlorohexyne, reflux, 15 h, 56%. d) NaH, 0 ◦C → RT, allyl bromide, reflux, 12 h,
76%. e) NaH, 0 ◦C → RT, 1,2-dichloroethane, reflux, 15 h, 67%. f) NaH, 0 ◦C → RT, propargyl bromide, reflux, 10 h, 56%. g) NaH, 0 ◦C → RT,
1,2-dibromoethane, reflux, 8 h, 70%.
Scheme 3 Reagents and conditions: a) RuCl2(DMSO)4, ethylene glycol, 160 ◦C, 12 h, 91%. b) 21b, Cs2CO3, CH3CN, reflux, 12 h, 66%. c)
RuCl2(PCy3)2CHPh, CH2Cl2, 60 h, 74%. d) H2, 10% Pd/carbon, CH2Cl2–EtOH, 12 h, 95%.
octahedral complex 5 as a deep red crystalline solid. As a result
of the C2v symmetry of 3b, complex 5 has D2d symmetry and
is the template to the Ru(II) achiral catenanes. Alkylation of
the tetra-phenolate of 5 with the terminal olefin linker 21b
using cesium carbonate in acetonitrile afforded pre-catenane 6.
Exposure of 6 to high dilution olefin metathesis conditions with
Grubbs catalyst,29 RuCl2(PCy3)2CHPh, followed by immediate
catalytic hydrogenation, generated both the catenane 7a and the
unexpected figure-eight macrocycle 7b in a 1 : 2 ratio (Scheme 3).
Distinction between 7a and 7b was made directly by 1H
NMR due to the difference in molecular symmetry (D2d and D2,
respectively) and the orthogonal conformation of the manisyl–
pyridyl plane. Comparison of the signal for the manisyl aromatic
proton f (∼6.6 ppm), in compounds 6, 7a and 7b is displayed
in Fig. 1. After cyclization, this signal remains a singlet of
isochronous enantiotopic signals for catenane 7a, and splits into
two diastereotopic singlets, f and fꢀ, for figure-eight 7b due to a
reduced local symmetry, Cs to C1, in the manisyl group. This is
also observed for the protons of the methyl groups on manisyl
(not pictured here). Additionally, the slight up-field shift in the
peripheral pyridyl proton a associated with catenane formation
is also observed for 7a while those signals for 7b remain relatively
unchanged.
An undesired feature of olefin metathesis was the lack of
thermodynamic drive to produce products and consume starting
materials or intermediates. Tedious chromatographic separation
was required in order to remove unreacted 6, as well as
the mono-ring-closed adducts of catenane as well as figure-
eight. To circumvent this matter and to eliminate the need
for hydrogenation we opted for a copper-mediated acetylenic
3 1 0 6
O r g . B i o m o l . C h e m . , 2 0 0 5 , 3 , 3 1 0 5 – 3 1 1 6

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Fig. 1 500 MHz 1H NMR spectra of compounds 6, 7a, and 7b.
Scheme 4 Reagents and conditions: a) 23b or 24b, Cs2CO3, CH3CN, reflux, 12 h, 54% for 8 and 70% for 10. b) Cu(OAc)2, CH3CN, reflux, 12–15 h,
61% for 9a/b and 57% for 11a/b.
coupling using modified Eglington conditions as the cyclization
step.
ligand 4b with Ru(II) using RuCl2(DMSO)4 in ethylene glycol
gave complex 12 in racemic form (Scheme 5). Here the Cs
symmetry of 4b renders complex 12 with C2 symmetry and
provides the template for a racemic catenane. Alkylation of
the racemic tetra-phenolate of 12 with linker 23b gave pre-
catenane 13. Exposure of 13 to excess copper(II) acetate under
high dilution conditions provided the chiral catenane 14a and a
set of diastereomeric figure-eights 14b/c (not reported in detail
due to the difficulties in their separation) in a 1 : 2 ratio.
Pre-catenane 8 was prepared in an analogous manner to
6 using linker 23b, which replaces the terminal olefins by
terminal acetylenes. High dilution acetylenic coupling with
excess copper(II) acetate gave the catenane 9a and the figure-
eight 9b in approximately the same 1 : 2 ratio obtained for
7a and 7b by the olefin metathesis–hydrogenation procedure;
however, precursor 8 was completely consumed to give 9a and
9b as monomeric products that are easily separable by column
chromatography (Scheme 4). A similar symmetry analysis to
that described above allowed the structural assignment.
Synthesis of the racemic modification of a chiral catenane was
achieved using an analogous coupling strategy to that which
afforded 9a and 9b. Coordination of the asymmetric tridentate
The chiral nature of the pyridyl-phenanthroline Ru(II) com-
plex makes distinction between catenane and figure-eight more
difficult. The local symmetry of the manisyl group is lost upon
coordination to Ru(II) and requires the distinction to be made
1
on the basis of chemical shift changes in the H NMR after
cyclization. As in the reaction to form 9a and 9b, this reaction
O r g . B i o m o l . C h e m . , 2 0 0 5 , 3 , 3 1 0 5 – 3 1 1 6
3 1 0 7

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Scheme 5 Reagents and conditions: a) RuCl2(DMSO)4, ethylene glycol, 160 ◦C, 12 h, 87%. b) 23b, Cs2CO3, CH3CN, reflux, 12 h, 56%. c) Cu(OAc)2,
CH3CN, reflux, 12 h, 51% for 14a and 14b/c.
yields two sets of products that are easily separable by column
chromatography from each other and from polymeric material.
The racemic catenane 14a product displays a single set of
1H NMR aromatic signals with the expected up-field shift in
the pyridyl-phenanthroline peripheral protons; whereas product
composed of the diastereomeric mixture 14b/c displays two sets
by way of Fe(III). To avoid complications possibly arising from
a more labile metal system, alkylations were completed prior to
coordination with Fe(II), and cyclization via copper-mediated
actylenic coupling was not explored fully. Alkylation of 3b
with biphenyl linker 22b using cesium carbonate gave ligand
15 (Scheme 6). Coordination of 15 with Fe(II) was achieved
by treatment with iron(II) sulfate in acetone–water. Aqueous
workup with potassium hexafluorophosphate gave pre-catenane
16 in its pure form. The mild conditions of olefin metathesis
allowed for cyclization and preserved the Fe(II) complex. High
dilution olefin metathesis of 16 surprisingly resulted in exclusive
formation of the catenane and its mono-ring closed adduct
as the only monomeric products; no figure-eight isomer was
detected. The catenane was isolated as a mixture of cis/trans
isomers in a 30% yield and immediately hydrogenated with
catalytic Pt/alumina to afford 17. As in the analysis of 7a,
9a, and 11a, the symmetry of the manisyl group aids in the
1H NMR identification of the catenane isomer. The expected
up-field shifts in the pyridyl-proton aromatic signals are also
observed. Removal of the Fe(II) template was achieved by the
slow addition of aqueous hydrogen peroxide to a basic solution
of 17 in acetonitrile–water. The purified achiral catenane 1 was
isolated in 59% yield. The characteristic fragmentation pattern
in the high resolution MALDI mass spectrum of 1 confirms
formation of the catenane (Fig. 3).
1
of H NMR signals in the aromatic region with little change
in the chemical shift of the peripheral protons. High-resolution
MALDI mass spectroscopy confirms that 14a and 14b/c are
isomers with the expected monomeric mass.
Selective formation of the catenane was attempted by incorpo-
rating a biphenyl linker with the hope of sterically discouraging
figure-eight formation. Alkylation of 5 with linker 24b provided
precursor 10.30 Exposure of 10 to acetylenic coupling conditions
unfortunately still provided catenane 11a and figure-eight 11b,
albeit in an improved 1 : 1 ratio (Scheme 4). Incorporating
the biphenyl linker coincided with formation of X-ray quality
crystals of 11a, providing proof of structure and confirmation
to our 1H NMR assignment of the catenanes (Fig. 2).31 Due to
the thermodynamic stability of the octahedral Ru(II) complexes,
removal of the ruthenium atom to form the metal-free catenanes
was not effected.
Fig. 2 X-Ray crystal structure of Ru(II) [2]catenane 11a. Solvent
−
molecules and PF6 counter-ion omitted for clarity.
Fe(II)-templated catenanes
Octahedral coordination complexes between Fe(II) and triden-
tate ligands produce complexes that are stable under mild
conditions, but are labile under basic and oxidative conditions
Fig. 3 MALDI high resolution mass spectrum of the template-free
catenane 1.
3 1 0 8
O r g . B i o m o l . C h e m . , 2 0 0 5 , 3 , 3 1 0 5 – 3 1 1 6

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Scheme 6 Terpyridine = terpy; pyridyl-phenanthroline = pphen. Reagents and conditions: a) 22b, Cs2CO3, DMF, 80 ◦C, 12 h, 88% for 15 and
92% for 18. b) FeSO4·7H2O, acetone–H2O, 98% for 16 and 91% for 19. c) RuCl2(PCy3)2CHPh, CH2Cl2, 72 h, 30% for 17-(cis/trans) and 21% for
20-(cis/trans). d) Pt/alumina, CH2Cl2–EtOH, 16 h, 91% for 17 and 96% for 20. e) H2O2, NaOH, CH3CN–H2O 1 : 1, 59% for 1 and 20% for 2.
Racemic Fe(II)-templated catenane was prepared in an anal-
ogous fashion to that used to prepare 17. Alkylation of 4b with
linker 22b afforded 18. Complex 19 was prepared by coordina-
tion between 18 and Fe(II) using iron(II) sulfate. High dilution
olefin metathesis of 19 yields similar results to those seen for the
reaction of 16; only the catenane is produced in a 21% yield as
a mixture of cis/trans isomers. Unreacted starting material and
the mono-ring closed adduct comprise the majority of recovered
materials and could be resubmitted to the reaction conditions
to produce more product. Immediate hydrogenation of the
cis/trans mixture with catalytic Pt/alumina gave the catenane
20. Identification of 20 can be made by the characteristic up-field
shifts in the aromatic region of the 1H NMR spectrum. Removal
of the Fe(II) was achieved by oxidation with hydrogen peroxide
under basic conditions to give the racemic catenane 2 in 20%
yield.
We conjecture that the absence of the figure-eight macrocycle
arises from the decreased bite angle that the tridentate ligands
form around Fe(II) relative to Ru(II). CPK modeling of 16
indicates that with enough pinching of the ligand around the
metal center, the terminal olefins on opposing ligands become
distant enough to prevent figure-eight formation, resulting in
the preferential formation of the catenane.
To test this conjecture, the parent homoleptic complexes
Ru(3a)2·2PF6 and Fe(3a)2·2PF6 were prepared and suitable
crystals for X-ray crystallography were grown from slow evapo-
ration of a dichloromethane solution in the presence of benzene
(Fig. 4).32
X-Ray analysis reveals the N1–M–N3 ligand–metal bite angles
for Ru(3a)2·2PF6 and Fe(3a)2·2PF6 to be 158.4(2) and 161.7(2)◦
respectively. Furthermore, the distances between opposing
manisyl oxygen atoms of the same ligand are 16.646(6) and
˚
16.481(6) A for Ru(3a)2·2PF6 and Fe(3a)2·2PF6 respectively,
and indicate an increased pinching of the ligands around Fe(II)
relative to the Ru(II) cognate. This is further supported by
the difference in N1–N3 distances, roughly 0.15 A. Finally, the
Fig. 4 X-Ray crystal structure and selected data for Ru(3a)2·2PF6 (left)
˚
and Fe(3a)2·2PF6 (right). Counter-ions omitted for clarity.
O r g . B i o m o l . C h e m . , 2 0 0 5 , 3 , 3 1 0 5 – 3 1 1 6
3 1 0 9

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smaller ligand proximity around Fe(II) is demonstrated by the
9.0 Hz, 1H), 8.04 (d, J = 9.0 Hz, 1H), 7.87 (dd, J = 2.0, 8.0 Hz,
1H), 6.64 (s, 2H), 6.60 (s, 2H), 1.99 (s, 6H), 1.98 (s, 6H). 13C
NMR (125 MHz, DMSO-d6, d): 156.98, 156.84, 155.14, 153.86,
151.42, 150.12, 145.06, 143.89, 138.92, 137.56, 137.26, 137.09,
137.04, 137.01, 135.84, 128.79, 128.59, 128.38, 128.26, 127.22,
126.83, 121.42, 119.95, 114.57, 114.51, 20.85, 20.77. EI HRMS
m/z: found 498.2192 (MH+); calcd (C33H28N3O2) 498.2182.
ꢀ
distances between central nitrogen atoms on terpyridine, N2–N2 ,
˚
which vary by 0.19 A and are consistent with our notion about
the basis for the absence of figure-eight macrocycle formation
with the Fe(II) templates.
Conclusions
We have demonstrated successfully that achiral and racemic
catenanes can be synthesized using a metal-templated approach
with terpyridine and pyridyl-phenanthroline ligands with ei-
ther Ru(II) or Fe(II). Moreover, we have debuted pyridyl-
phenanthroline in its first racemic templated topological isomer
synthesis. Macrocyclization via olefin metathesis or copper-
mediated alkyne coupling with Ru(II)-templated pre-catenanes
resulted in both the catenane and the undesired figure-eight
macrocycle, while olefin metathesis with Fe(II)-templated pre-
catenanes resulted in preferential formation of a catenane. The
labile Fe(II) core could easily be liberated to yield template-free
achiral and racemic catenanes. Additionally, the aryl substituent
2-[2-(2-Pent-4-enyloxyethoxy)ethoxy]ethanol (21a). To a so-
lution of triethylene glycol (15.0 g, 100 mmol) in THF (300 mL)
at 0 ◦C was slowly added NaH (2.8 g, 70 mmol, 60% in mineral
oil) as a solid. The resulting solution was allowed to reach
room temperature while stirring over 1 h. Subsequently, 5-
bromopentene (11.2 g, 75 mmol) was added via syringe and the
contents heated at reflux for 12 h. The reaction was cooled to
room temperature and the solvent was reduced to one half on a
rotary evaporator. The residue was extracted with ether (200 mL)
and water (100 mL). The organic layer was separated, dried over
magnesium sulfate, filtered, and solvent evaporated to give an
oil. The crude oil was purified by column chromatography on
silica gel with hexane–ethyl acetate 1 : 3 as the eluant to yield
1
manisyl served as an internal H NMR probe for topological
isomer identification of the achiral catenane.
1
a clear yellow viscous oil, Rf = 0.30 (8.43 g, 55%). H NMR
(400 MHz, CDCl3, d): 7.74 (m, 1H), 4.94 (d, J = 17.0 Hz, 1H),
4.88 (d, J = 10.0 Hz, 1H), 3.65 (bs, 2H), 3.60–3.58 (m, 6H),
3.56–3.52 (m, 4H), 3.40 (t, J = 8.0 Hz, 2H), 2.95 (bs, 1H),
2.04 (q, J = 7.0 Hz, 2H), 1.62 (q, J = 7.0 Hz, 2H). 13C NMR
(100 MHz, CDCl3, d): 137.85, 114.39, 72.33, 70.49, 70.39, 70.34,
70.11, 69.83, 61.43, 30.08, 28.59. EI HRMS m/z: found 219.1593
(MH+); calcd (C11H23O4) 219.1596.
Experimental
Materials and methods
1H and 13C NMR spectra were recorded on Varian (Mercury
300/400 MHz and Unity 500 MHz) spectrometers with tetram-
ethylsilane (TMS) as an internal standard. High-resolution
mass spectral (HRMS) analyses were performed by the Uni-
versity California Riverside mass spectrometry facility in either
MALDI or EI mode, as indicated for each compound. All
experiments were carried out under argon in freshly distilled an-
hydrous solvents unless otherwise noted. Commercial chemicals
were used as supplied. Column chromatography was performed
on neutral aluminum oxide (Brockmann II) and silica gel (230–
425 mesh) from Fisher Scientific Co. Centrifugal chromatog-
raphy was performed on a Harrison Research Chromatotron
with 1 mm silica gel plates. UV–Vis spectra were recorded on a
Perkin–Elmer UV/VIS/NIR spectrometer Lambda 19. Melting
points were recorded on a Mel-Temp Laboratory Device and are
uncorrected. Overlapping, non-symmetry-equivalent 13C NMR
signals for pyridyl-phenanthroline adducts are indicated by *.
Toluene-4-sulfonic acid 2-[2-(2-pent-4-enyloxyethoxy)ethoxy]
ethyl ester (21b). To an anhydrous solution of 21a (8.43 g,
39 mmol), triethylamine (8.07 mL, 58 mmol) and 4-
(dimethylamino)pyridine (0.47 g, 3.9 mmol) in dichloromethane
(500 mL) at 0 ◦C was added p-toluenesulfonyl chloride (7.35 g,
39 mmol) as a solid. The reaction was slowly warmed to
room temperature and stirred for an additional 8 h. The crude
reaction mixture was quenched with water (150 mL), the organic
layer separated, and the aqueous layer extracted with fresh
dichloromethane (2 × 50 mL). The combined organic layers were
dried over magnesium sulfate, filtered, and reduced to dryness
to yield a viscous oil. The crude oil was purified by column
chromatography on silica gel with hexane–ethyl acetate 1 : 1 as
the eluant to yield a clear and colorless viscous oil, Rf = 0.50
5ꢀ,5ꢀꢀ -Bis(4-hydroxy-2,6-dimethylphenyl)-2,2ꢀ:6ꢀ,2ꢀꢀ-terpyridine
(3b). To anhydrous molten pyridine hydrochloride (11.00 g,
90 mmol) at 150 ◦C was added 3a (1.00 g, 2.1 mmol) and heated
to 185 ◦C for 4 h. The hot solution was quenched with boiling
water (20 mL). The resulting yellow precipitate was filtered,
washed thoroughly with water, aqueous NH4OH, and dried
under vacuum overnight to yield a tan solid (0.92 g, 97%). Mp
1
(3.50 g, 87%). H NMR (400 MHz, CDCl3, d): 7.79 (d, J =
8.0 Hz, 2H), 7.34 (d, J = 8.0 Hz, 2H), 5.80 (m, 1H), 4.99 (d, J =
17.0 Hz, 1H), 4.94 (d, J = 10.0 Hz, 1H), 4.15 (t, J = 5.0 Hz,
2H), 3.68 (t, J = 5.0 Hz, 2H), 3.62–3.54 (m, 8H), 3.46 (t, J =
6.0 Hz, 2H), 2.44 (s, 3H), 2.10 (q, J = 7.0 Hz, 2H), 1.67 (q, J =
7.0 Hz, 2H). 13C NMR (100 MHz, CDCl3, d): 144.41, 137.85,
132.54, 129.47, 127.58, 114.37, 70.47, 70.41, 70.38, 70.27, 69.83,
69.09, 68.40, 30.09, 28.62, 21.52. EI HRMS m/z: found 390.1952
◦
1
212 C (dec.). H NMR (400 MHz, CDCl3, d): 8.75 (d, J =
8.0 Hz, 2H), 8.53 (d, J = 2.0 Hz, 2H), 8.52 (d, J = 8.0 Hz, 2H),
8.03 (t, J = 8.0 Hz, 1H), 7.70 (dd, J = 2.0, 8.0 Hz, 2H), 6.68 (s,
4H), 2.07 (s, 12H). 13C NMR (100 MHz, CH3OD, d): 158.43,
152.93, 151.27, 148.22, 144.49, 140.85, 140.64, 138.45, 128.12,
124.05, 124.02, 115.57, 21.21. EI HRMS m/z: found 473.2111
(M+); calcd (C31H27N3O2) 473.2103.
+
(MNH4 ); calcd (C18H32NO6S) 390.1950.
◦
4ꢀ-Allyloxybiphenyl-4-ol (22a). To a 0 C solution of 4,4ꢀ-
biphenol (10.0 g, 54 mmol) in THF (125 mL) was added NaH
(1.5 g, 38 mmol, 60% in mineral oil) as a solid. The resulting
solution was allowed to reach room temperature while stirring
over 1 h. Subsequently, allyl bromide (4.88 g, 40 mmol) was
added via syringe and the contents heated at reflux for 12 h. The
crude reaction mixture was cooled to room temperature, filtered,
and reduced to dryness. The crude white solid was purified by
column chromatography on silica gel with dichloromethane–
methanol 50 : 1 as the eluant to yield◦a white crystalline solid,
Rf = 0.25 (5.72 g, 66%). Mp 172–173 C. 1H NMR (500 MHz,
CDCl3, d): 7.45 (d, J = 9.0 Hz, 2H), 7.43 (d, J = 9.0 Hz, 2H), 6.97
(d, J = 9.0 Hz, 2H), 6.88 (d, J = 9.0 Hz, 2H), 6.08 (m, 1H), 5.43
(dd, J = 2.0, 18.0 Hz, 1H), 5.30 (dd, J = 2.0, 11.0 Hz, 1H), 4.75
(s, 1H), 4.58 (d, J = 5.0 Hz, 2H). 13C NMR (125 MHz, CDCl3, d):
157.83, 154.68, 133.78, 133.64, 133.38, 128.03, 127.76, 117.78,
8-(4-Hydroxy-2,6-dimethylphenyl)-2-[5-(4-hydroxy-2,6-
dimethylphenyl)pyridin-2-yl]-1,10-phenanthroline (4b). To
anhydrous molten pyridine hydrochloride (11.00 g, 90 mmol)◦at
◦
150 C was added 4a (1.00 g, 2.0 mmol) and heated to 185 C
for 4 h. The hot solution was quenched with boiling water
(20 mL). The resulting yellow precipitate was filtered, washed
thoroughly with water, aqueous NH4OH, and dried under
vacuum overnight to yield a yellowish solid (0.84 g, 93%). Mp
◦
1
264–266 C (dec.). H NMR (500 MHz, DMSO-d6, d): 9.42
(bs, 1H), 9.37 (bs, 1H), 8.96 (d, J = 2.0 Hz, 1H), 8.91 (d, J =
8.0 Hz, 1H), 8.81 (d, J = 8.0 Hz, 1H), 8.66 (d, J = 8.0 Hz, 1H),
8.54 (d, J = 2.0 Hz, 1H), 8.35 (d, J = 2.0 Hz, 1H), 8.09 (d, J =
3 1 1 0
O r g . B i o m o l . C h e m . , 2 0 0 5 , 3 , 3 1 0 5 – 3 1 1 6

View Article Online
115.63, 115.05, 68.90. EI HRMS m/z: found 226.1000 (M+);
calcd (C15H14O2) 226.0994.
4ꢀ-Prop-2-ynyloxybiphenyl-4-ol (24a). To a 0 ◦C solution of
4,4ꢀ-biphenol (3.0 g, 16 mmol) in THF (100 mL) was added NaH
(0.71 g, 17 mmol, 60% in mineral oil) as a solid. The resulting
solution was allowed to reach room temperature while stirring
over 1 h. Subsequently, propargyl bromide (2.11 g, 18 mmol) was
added via syringe and the contents heated at reflux for 10 h. The
crude reaction mixture was cooled to room temperature, filtered,
and reduced to dryness. The crude solid was purified by column
chromatography on silica gel with dichloromethane as the eluant
to yield a white crystalline solid, Rf = 0.40 (1.30 g, 36%). Mp
133–136 ◦C. 1H NMR (300 MHz, CDCl3, d): 7.47 (d, J = 8.0 Hz,
2H), 7.43 (d, J = 8.0 Hz, 2H), 7.03 (d, J = 8.0 Hz, 2H), 6.88 (d,
J = 8.0 Hz, 2H), 4.73 (d, J = 2.5 Hz, 2H), 2.54 (t, J = 2.5 Hz,
1H). 13C NMR (100 MHz, CDCl3, d): 156.39, 154.55, 134.18,
133.29, 127.87, 127.58, 115.50, 115.03, 78.55, 75.56, 55.92. EI
HRMS m/z: found 224.0835 (M+); calcd (C15H12O2) 224.0837.
4ꢀ-Allyloxy-4-(2-chloroethoxy)biphenyl (22b). To an anhy-
drous solution of 22a (2.84 g, 13 mmol) in THF (150 mL)
at 0 ◦C was added NaH (0.53 g, 13 mmol, 60% in mineral
oil) as a solid. The resulting solution was stirred for 1 h while
warming to room temperature. Subsequently, an excess of 1,2-
dichloroethane (50 mL) was added and the contents heated to
reflux for 15 h. After cooling the reaction to room temperature,
diethyl ether (100 mL), and water (50 mL) were added. The
organic layer was separated and the aqueous layer extracted with
fresh diethyl ether (2 × 50 mL). The combined organic layers
were dried over magnesium sulfate, filtered, and the solvent
removed to yield a crude yellow solid. The crude product was
purified by column chromatography on silica gel with hexane–
dichloromethane 1 : 3 as the eluant to yield a white crystalline
solid, Rf = 0.75 (1.70 g, 47%). Mp 142–144 ◦C. 1H NMR
(500 MHz, CDCl3, d): 7.49 (d, J = 8.0 Hz, 2H), 7.46, (d, J =
8.0 Hz, 2H), 6.98 (d, J = 8.0 Hz, 2H), 6.97 (d, J = 8.0 Hz, 2H),
6.08 (m, 1H), 5.44 (dd, J = 2.0, 17.0 Hz, 1H), 5.31 (d, J = 2.0,
10.0 Hz, 1H), 4.58 (d, J = 4.0 Hz, 2H), 4.26 (t, J = 6.0 Hz, 2H),
3.83 (t, J = 6.0 Hz, 2H). 13C NMR (125 MHz, CDCl3, d): 157.92,
157.39, 134.26, 133.47, 133.36, 127.87, 127.78, 117.74, 115.05,
115.04, 68.86, 68.10, 41.83. EI HRMS m/z: found 288.0927
(M+); calcd (C17H17O2Cl) 288.0917.
4ꢀ-(2-Bromoethoxy)-4-prop-2-ynyloxybiphenyl (24b). To an
anhydrous solution of 24a (0.572 g, 3 mmol) in THF (50 mL)
at 0 ◦C was added NaH (0.15 g, 4 mmol, 60% in mineral
oil) as a solid. The resulting solution was stirred for 1 h
while warming to room temperature. Subsequently, an excess
of 1,2-dibromoethane (6 mL) was added and the contents
heated to reflux for 8 h. The reaction was cooled to room
temperature, filtered, and solvent evaporated. The crude product
was purified by column chromatography on silica gel with
hexane–dichloromethane 1 : 3 as the eluant to yield a white
◦
2-[2-(2-Hex-5-ynyloxyethoxy)ethoxy]ethanol (23a). To a so-
lution of triethylene glycol (6.22 g, 40 mmol) in THF (250 mL)
at 0 ◦C was added NaH (1.58 g, 40 mmol, 60% in mineral oil) as
a solid. The solution was stirred for 1 h and slowly warmed
to room temperature. Subsequently, 6-chlorohexyne (4.81 g,
40 mmol) was added via syringe and the reaction was heated
at reflux for 15 h. The reaction was cooled to room temperature
and solvent was reduced to one half on a rotary evaporator. The
residue was extracted with ether (300 mL) and water (100 mL).
The organic layer was separated, dried over magnesium sulfate,
filtered, and solvent evaporated. The crude oil was purified by
column chromatography on silica gel with ethyl acetate–hexane
3 : 1 as the eluant to yield a clear viscous oil, Rf = 0.30 (3.28 g,
36%). 1H NMR (500 MHz, CDCl3, d): 3.73 (bs, 2H), 3.67–3.65
(m, 6H), 3.63–3.59 (m, 4H), 3.49 (t, J = 7.0 Hz, 2H), 2.71 (bs,
1H), 2.22 (dt, J = 2.0, 7.0 Hz, 2H), 1.95 (t, J = 2.0 Hz, 1H),
1.71 (q, J = 7.0 Hz, 2H), 1.60 (q, J = 7.0 Hz, 2H). 13C NMR
(125 MHz, CHCl3, d): 84.31, 72.45, 70.72, 70.60, 70.55, 70.33,
70.02, 68.35, 61.69, 28.50, 25.04, 18.10. EI HRMS m/z: found
1
crystalline solid, Rf = 0.60 (0.60 g, 70%). Mp 118–119 C. H
NMR (300 MHz, CDCl3, d): 7.49 (d, J = 8.7 Hz, 2H), 7.48
(q, J = 8.7 Hz, 2H), 7.03 (d, J = 8.7 Hz, 2H), 6.97 (d, J =
8.7 Hz, 2H), 4.73 (d, J = 2.4 Hz, 2H), 4.33 (t, J = 6.0 Hz, 2H),
3.66 (t, J = 6.0 Hz, 2H), 2.54 (t, J = 2.4 Hz, 1H). 13C NMR
(100 MHz, CDCl3, d): 157.05, 156.49, 134.02, 133.89, 127.76,
127.63, 115.05, 114.93, 78.54, 75.57, 67.96, 55.90, 29.23. EI
HRMS m/z: found 330.0248 (M+); calcd (C17H15O2Br) 330.0255.
Ru[5ꢀ,5ꢀꢀ -bis(4-hydroxy-2,6-dimethylphenyl)-2,2ꢀ:6ꢀ,2ꢀꢀ -terpyri-
dine]2·2PF6 (5). A degassed solution of ethylene glycol
(30 mL), 3b (0.500 g, 1.1 mmol) and RuCl2(DMSO)4 (0.255 g,
0.5 mmol) was heated to 160 ◦C for 12 h to produce a deep
red solution. The reaction was cooled to room temperature,
poured into aqueous KPF6 (50 mL) and filtered over Celite.
The red precipitate was washed with water and dissolved into
a clean flask with acetone. The resulting red solution was dried
over magnesium sulfate, filtered, and the solvent evaporated.
Purification by column chromatography on silica gel with
CH3CN–H2O–aqueous KPF6 96 : 4 : 0.04 as the eluant yielded
+
248.1853 (MNH4 ); calcd (C12H26NO4) 248.1862.
◦
1
a red solid, Rf = 0.40 (0.59 g, 84%). Mp >350 C. H NMR
(300 MHz, CD3CN, d): 8.81 (d, J = 8.0 Hz, 4H), 8.63 (d, J =
8.0 Hz, 4H), 8.43 (t, J = 8.0 Hz, 2H), 7.89 (dd, J = 2.0, 8.0 Hz,
4H), 7.30 (d, J = 2.0 Hz, 4H), 7.08 (bs, 4H), 6.61 (s, 8H), 1.67
(s, 24H). 13C NMR (100 MHz, acetone-d6, d): 157.88, 157.07,
155.93, 153.51, 141.29, 140.34, 137.47, 136.71, 126.91, 124.61,
124.19, 115.16, 20.49. MALDI HRMS m/z: found 1048.3250
(M+); calcd (C62H54N6O4 Ru) 1048.3250. UV–Vis (CH3CN),
kmax/nm (log e): 201 (5.4), 272 (4.7), 312 (4.8), 478 (4.1).
Toluene-4-sulfonic acid 2-[2-(2-hex-5-ynyloxyethoxy)ethoxy]
ethyl ester (23b). To an anhydrous solution of 23a (1.67 g,
7
mmol), triethylamine (1.52 mL, 11 mmol) and 4-
(dimethylamino)pyridine (0.09 g, 0.7 mmol) in dichloromethane
(200 mL) at 0 ◦C was added p-toluenesulfonyl chloride (1.39 g,
7 mmol) as a solid. The reaction was slowly warmed to room
temperature and stirred for an additional 8 h. The crude
reaction mixture was quenched with water (75 mL). The organic
layer was separated and the aqueous layer extracted with fresh
dichloromethane (2 × 20 mL). The combined organic layers were
dried over magnesium sulfate, filtered, and reduced to dryness
to yield a viscous oil. The crude oil was purified by column
chromatography on silica gel with hexane–ethyl acetate 1 : 1 as
the eluant to yield a clear and colorless oil, Rf = 0.50 (2.29 g,
Ru[8-(4-hydroxy-2,6-dimethylphenyl)-2-[5-(4-hydroxy-2,6-
dimethylphenyl)pyridin-2-yl]-1,10-phenanthroline]2·2PF6
(12).
A degassed solution of ethylene glycol (30 mL), 4b (0.500 g,
1.0 mmol) and RuCl2(DMSO)4 (0.243 g, 0.5 mmol was heated
to 160 ◦C for 12 h to produce a deep red solution. The reaction
was cooled to room temperature, poured into aqueous KPF6
(50 mL) and filtered over Celite. The red precipitate was washed
with water and dissolved into a clean flask with acetone.
The resulting red solution was dried over magnesium sulfate,
filtered, and the solvent removed. Purification by column
chromatography on silica gel with CH3CN–H2O–aqueous
KPF6 95 : 5 : 0.05 as the eluant yielded a red solid, Rf = 0.40
1
82%). H NMR (400 MHz, CDCl3, d): 7.80 (d, J = 8.0 Hz,
2H), 7.34 (d, J = 8.0 Hz, 2H), 4.16 (t, J = 5.0 Hz, 2H), 3.69
(t, J = 5.0 Hz, 2H), 3.61–3.56 (m, 8H), 3.47 (t, J = 8.0 Hz,
2H), 2.45 (s, 3H), 2.21 (dt, J = 2.0, 8.0 Hz, 2H), 1.94 (t, J =
2.0 Hz, 1H), 1.68 (q, J = 7.0 Hz, 2H), 1.59 (q, J = 7.0 Hz,
2H). 13C NMR (100 MHz, CHCl3, d): 144.55, 132.93, 129.64,
127.82, 84.30, 70.77, 70.72, 70.65, 70.56, 70.08, 69.23, 68.70,
68.37, 28.74, 25.27, 21.74, 18.32. EI HRMS m/z: found 402.1938
◦
1
(0.61 g, 87%). Mp >350 C. H NMR (500 MHz, acetone-d6,
d): 9.20 (d, J = 8.5 Hz, 4H), 9.00 (d, J = 8.0 Hz, 4H), 8.94
+
(MNH4 ); calcd (C19H32NO6S) 402.1950.
O r g . B i o m o l . C h e m . , 2 0 0 5 , 3 , 3 1 0 5 – 3 1 1 6
3 1 1 1

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(d, J = 8.5 Hz, 4H), 8.52 (d, J = 9.0 Hz, 4H), 8.46 (d, J =
2.0 Hz, 4H), 8.40 (s, 4H), 8.39 (s, 4H), 8.37 (d, J = 9.0 Hz, 4H),
7.98 (dd, J = 2.0, 8.0 Hz, 4H), 7.90 (d, J = 2.0 Hz, 4H), 7.70
(d, J = 2.0 Hz, 4H), 6.49 (s, 4H), 6.46 (s, 4H), 6.42 (s, 4H), 6.39
(s, 4H), 1.57 (s, 12H), 1.56 (s, 12H), 1.34 (s, 12H), 1.32 (s, 12H).
13C NMR (125 MHz, acetone-d6, d): 158.34*, 158.11, 156.35,
156.14, 155.41, 149.55, 147.30, 141.73, 140.92, 140.42, 138.29,
137.98, 137.90, 137.81, 137.72, 135.12, 131.76, 130.97, 129.97,
128.89, 127.65, 127.18, 125.60, 123.12, 115.44*, 115.38*, 20.59,
20.51, 20.33, 20.21. MALDI HRMS m/z: found 1096.3292
(M+); calcd (C66H54N6O4 Ru) 1096.3250. UV–Vis (CH3CN),
kmax/nm (log e): 201 (5.5), 239 (5.0), 296 (5.0), 343 (4.8), 499 (4.2).
(5 mL) was added anhydrous cesium carbonate (0.192 g,
0.59 mmol), 24b (0.123 g, 0.37 mmol), and triglyme (100 lL).
The contents were heated at reflux for 36 h. The reaction
was cooled to room temperature, poured into aqueous KPF6
(25 mL) and filtered over Celite. The red oily precipitate
was washed with water and transferred to a clean flask
with dichloromethane. The resulting red solution was dried
over magnesium sulfate, filtered, and the solvent removed.
Purification by column chromatography on silica gel eluted with
CH3CN–H2O–aqueous KPF6 96 : 4 : 0.04 afforded a red solid
(0.12 g, 70%). Mp 154–155 ◦C. 1H NMR (400 MHz, acetone-d6,
d): 8.95 (d, J = 8.0 Hz, 4H), 8.70 (d, J = 8.0 Hz, 4H), 8.38 (t,
J = 8.0 Hz, 2H), 7.98 (dd, J = 2.0, 8.0 Hz, 4H), 7.66 (d, J =
2.0 Hz, 4H), 7.56 (d, J = 8.0 Hz, 16H), 7.07 (d, J = 8.0 Hz,
8H), 7.04 (d, J = 8.0 Hz, 8H), 6.69 (s, 8H), 4.83 (d, J = 2.4 Hz,
8H), 4.36 (bd, J = 4.5 Hz, 16H), 3.12 (t, J = 2.4 Hz, 4H), 1.63
(s, 24H). 13C NMR (125 MHz, acetone-d6, d): 159.78, 158.99,
157.90, 157.70, 156.39, 153.86, 141.52, 140.74, 138.07, 137.17,
134.71, 134.20, 128.63, 128.46, 128.32, 125.06, 124.63, 116.11,
115.80, 114.72, 79.82, 77.05, 67.43, 67.39, 56.32, 20.62. MALDI
HRMS m/z: found 2048.7409 (M+); calcd (C130H110N6O12Ru)
2048.7220. UV–Vis (CH3CN), kmax/nm (log e): 201 (5.9), 266
(5.3), 312 (4.9), 478 (4.1).
Ru(5,5ꢀꢀ -bis-(2,6-dimethyl-4-{2-[2-(2-pent-4-enyloxyethoxy)-
ethoxy]ethoxy}phenyl)-[2,2ꢀ;6ꢀ,2ꢀꢀ]-terpyridine)2·2PF6 (6). To
an anhydrous solution of 5 (0.222 g, 0.17 mmol) in acetonitrile
(35 mL) was added anhydrous cesium carbonate (0.61 g,
1.9 mmol) and 21b (0.418 g, 1.1 mmol). The contents were
heated at reflux for 10 h. The reaction was cooled to room
temperature, poured into aqueous KPF6 (50 mL) and filtered
over Celite. The red oily precipitate was washed with water and
transferred to a clean flask with dichloromethane. The resulting
red solution was dried over magnesium sulfate, filtered, and
the solvent removed. Purification by column chromatography
on silica gel eluted with CH3CN–H2O–aqueous KPF6 96 : 4 :
0.04 afforded a red glassy solid, Rf = 0.70 (0.23 g, 66%). Mp
Ru(8-(4-{2-[2-(2-hex-5-ynyloxyethoxy)ethoxy]ethoxy}-2,6-
dimethylphenyl)-2-[5-(4-{2-[2-(2-hex-5-ynyloxyethoxy)ethoxy]-
ethoxy}-2,6-dimethylphenyl)pyridin-2-yl]-[1,10]-phenanthroline)2·
2PF6 (13). To an anhydrous solution of 12 (0.70 g, 0.051 mmol)
in acetonitrile (10 mL) was added anhydrous cesium carbonate
(0.132 g, 0.40 mmol) and 23b (0.155 g, 0.40 mmol). The contents
were heated at reflux for 12 h. The reaction was cooled to room
temperature, poured into aqueous KPF6 (15 mL) and filtered
over Celite. The red oily precipitate was washed with water and
transferred to a clean flask with dichloromethane. The resulting
red solution was dried over magnesium sulfate, filtered, and
the solvent removed. Purification by column chromatography
on silica gel eluted with CH3CN–H2O–aqueous KPF6 96 : 4 :
0.04 afforded a red glassy solid (63 mg, 56%). Mp 58–62 ◦C.
1H NMR (500 MHz, acetone-d6, d): 9.22 (d, J = 8.0 Hz, 2H),
9.02 (d, J = 8.0 Hz, 2H), 8.95 (d, J = 8.0 Hz, 2H), 8.53 (d, J =
8.0 Hz, 2H), 8.49 (d, J = 2.0 Hz, 2H), 8.39 (d, J = 8.0 Hz, 2H),
8.01 (dd, J = 2.0, 8.0 Hz, 2H), 7.93 (d, J = 2.0 Hz, 2H), 7.72 (d,
J = 2.0 Hz, 2H), 6.62 (s, 2H), 6.59 (s, 2H), 6.55 (s, 2H), 6.53 (s,
2H), 4.052 (t, J = 5.0 Hz, 4H), 4.05 (t, J = 5.0 Hz, 4H), 3.76 (t,
J = 5.0 Hz, 4H), 3.75 (t, J = 5.0 Hz, 4H), 3.63–3.51 (m, 32H),
3.45 (t, J = 6.0 Hz, 8H), 2.31 (t, J = 2.0 Hz, 4H), 2.18 (dt, J =
2.0, 7.0 Hz, 8H), 1.64–1.62 (m, 8H), 1.63 (s, 12H), 1.57–1.54 (m,
8H), 1.40 (s, 6H), 1.37 (s, 6H). 13C NMR (100 MHz, acetone-d6,
d): 159.42*, 157.76, 155.75, 155.67, 154.84, 149.19, 146.84,
141.10, 140.49, 139.79, 137.88, 137.64, 137.57, 137.46, 137.37,
134.79, 131.39, 130.64, 129.65, 128.59, 128.44, 127.97, 125.33,
122.84, 114.31*, 114.24*, 84.71*, 71.17*, 71.06*, 71.02*, 70.84*,
70.66*, 70.04*, 69.84*, 68.05*, 29.44*, 26.04*, 20.75, 20.66,
20.49, 20.36, 18.48*. MALDI HRMS m/z: found 1944.8859
(M+); calcd (C114H134N6O16Ru) 1944.8894. UV–Vis (CH3CN),
kmax/nm (log e): 202 (5.4), 273 (5.2), 349 (4.7), 499 (4.0).
◦
1
49–52 C. H NMR (400 MHz, acetone-d6, d): 8.94 (d, J =
8.0 Hz, 4H), 8.86 (d, J = 8.0 Hz, 4), 8.37 (t, J = 8.0 Hz, 2H),
7.95 (dd, J = 2.0, 8.0 Hz, 4H), 7.64 (d, J = 2.0 Hz, 4H), 6.62 (s,
8H), 5.81 (m, 4H), 4.99 (dd, J = 2.0, 17.0 Hz, 4H), 4.91 (dd,
J = 2.0, 10.0 Hz, 4H), 4.08 (t, J = 5.0 Hz, 8H), 3.78 (t, J =
5.0 Hz, 8H), 3.65–3.57 (m, 24H), 3.52 (t, J = 5 Hz, 8H), 3.43
(t, J = 6.0 Hz, 8H), 2.14 (q, J = 7.0 Hz, 2H), 1.61 (s, 24H),
1.60 (q, J = 7.0 Hz, 2H). 13C NMR (100 MHz, acetone-d6, d):
159.40, 157.17, 155.88, 153.36, 141.05, 140.29, 138.98, 137.46,
136.75, 128.01, 124.68, 124.25, 114.70, 114.28, 71.15, 71.05,
71.01, 70.68, 70.66, 70.15, 68.01, 30.93, 29.68, 20.61. MALDI
HRMS m/z: found 1848.8969 (M+); calcd (C106H134N6O16Ru)
1848.8900. UV–Vis (CH3CN), kmax/nm (log e): 202 (5.5), 234
(sh, 4.8), 272 (4.7), 312 (4.8), 478 (4.1).
Ru(5,5ꢀꢀ -bis-(4-{2-[2-(2-hex-5-ynyloxyethoxy)ethoxy]ethoxy}-
2,6-dimethylphenyl)-[2,2ꢀ;6ꢀ,2ꢀꢀ]-terpyridine)2·2PF6 (8). To an
anhydrous solution of 5 (0.100 g, 0.075 mmol) in acetonitrile
(15 mL) was added anhydrous cesium carbonate (0.243 g,
0.74 mmol) and 23b (0.229 g, 0.60 mmol). The contents were
heated at reflux for 12 h. The reaction was cooled to room
temperature, poured into aqueous KPF6 (25 mL) and filtered
over Celite. The red oily precipitate was washed with water and
transferred to a clean flask with dichloromethane. The resulting
red solution was dried over magnesium sulfate, filtered, and
the solvent removed. Purification by column chromatography
on silica gel eluted with CH3CN–H2O–aqueous KPF6, 96 : 4 :
0.04 afforded a red glassy solid (0.09 g, 56%). Mp 54–58 ◦C. 1H
NMR (500 MHz, acetone-d6, d): 8.97 (d, J = 8.0 Hz, 4H), 8.87
(d, J = 8.0 Hz, 4H), 8.39 (t, J = 8.0 Hz, 2H), 7.97 (dd, J = 2.0,
8.0 Hz, 4H), 7.65 (d, J = 2.0 Hz, 4H), 6.63 (s, 8H), 4.09 (t, J =
4.5 Hz, 8H), 3.79 (t, J = 4.5 Hz, 8H), 3.65–3.58 (m, 24H), 3.53
(t, J = 4.5 Hz, 8H), 3.45 (t, J = 5.0 Hz, 8H), 2.31 (t, J = 2.5 Hz,
4H), 2.18 (dt, J = 2.5, 5.0 Hz, 8H), 1.65–1.62 (m, 8H), 1.62 (s,
24H), 1.57–1.54 (m, 8H). 13C NMR (125 MHz, acetone-d6, d):
159.03, 156.78, 155.51, 152.98, 140.65, 139.82, 137.03, 136,20,
127.51, 124.14, 123.71, 113.81, 84.01, 70.44, 70.32, 70.29, 70.10,
69.91, 69.32, 69.06, 67.33, 25.14, 19.74, 19.67, 17.56. MALDI
HRMS m/z: found 1896.8874 (M+); calcd (C110H134N6O16Ru)
1896.8900. UV–Vis (CH3CN), kmax/nm (log e): 201 (5.6), 273
(4.9), 312 (5.0), 478 (4.3).
Ru(terpy-catenane)·2PF6 (7a). To a solution of RuCl2-
(PCy3)2CH2Ph (3 mg, 3.5 lmol) in degassed dichloromethane
(50 mL) at room temperature was added a solution of 6 (0.15 g,
0.07 mmol) in dichloromethane (10 mL) via syringe pump over
12 h. After stirring for an additional 48 h, the red solution was
reduced to dryness and purified by column chromatography
on silica gel with CH3CN–H2O–aqueous KPF6 95 : 5 : 0.05
as the eluant to yield a red glassy solid (0.04 g, 27%) as a
mixture of cis/trans isomers. This mixture was dissolved in
dichloromethane–ethanol (1 : 1, 4 mL) and to it was added
Pd/C (10 mol%). The suspension was stirred for 20 h under
a hydrogen atmosphere. The slurry was filtered and reduced to
dryness to yield a red glassy solid (0.04 g, 98%). Mp 118–120 ◦C.
1H NMR (500 MHz, acetone-d6, d): 8.94 (d, J = 8.0 Hz, 4H),
Ru(5,5ꢀꢀ -bis-{2,6-dimethyl-4-[2-(4ꢀ -prop-2-ynylbiphenyl-4-
yloxy)ethoxy]phenyl}-[2,2ꢀ;6ꢀ,2ꢀꢀ]-terpyridine)2·2PF6 (10). To
an anhydrous solution of 5 (0.100 g, 0.075 mmol) in acetonitrile
3 1 1 2
O r g . B i o m o l . C h e m . , 2 0 0 5 , 3 , 3 1 0 5 – 3 1 1 6

View Article Online
8.86 (d, J = 8.0 Hz, 4H), 8.32 (t, J = 8.0 Hz, 2H), 8.02 (dd,
J = 2.0, 8.0 Hz, 4H), 7.61 (d, J = 2.0 Hz, 4H), 6.64 (s, 8H),
4.13 (bt, J = 5.0 Hz, 8H), 3.77 (bt, J = 5.0 Hz, 8H), 3.64–3.56
(m, 32H), 3.49 (t, J = 7.0 Hz, 8H), 1.63 (bs, 8H), 1.60 (s, 24H),
1.44 (bs, 16H). 13C NMR (125 MHz, acetone-d6, d): 160.02,
157.58, 156.43, 154.01, 141.69, 140.49, 137.87, 136.85, 128.30,
125.08, 124.58, 114.77, 71.93, 71.52, 71.29, 71.24, 70.88, 70.33,
68.48, 30.75, 30.56, 27.11, 20.59. MALDI HRMS m/z: found
1796.8537 (M+); calcd (C102H130N6O16Ru) 1796.8587. UV–Vis
(CH3CN), kmax/nm (log e): 202 (5.5), 235 (sh, 5.0), 272 (4.9), 312
(5.0), 479 (4.2).
124.68, 115.02, 114.88, 78.20, 71.59, 71.44, 71.32, 70.89, 70.86,
70.29, 68.47, 66.28, 29.65, 25.90, 20.81, 20.64, 19.18. MALDI
HRMS m/z: found 1892.8663 (M+); calcd (C110H130N6O16Ru)
1892.8581. UV–Vis (CH3CN), kmax/nm (log e): 202 (5.2), 236
(4.8), 272 (4.9), 311 (4.8), 478 (4.0).
Ru(terpy-biphencatenane)·2PF6 (11a). A red solid (0.021 g,
29%). Mp >340 ◦C. 1H NMR (500 MHz, acetone-d6, d): 8.78 (d,
J = 8.0 Hz, 4H), 8.76 (d, J = 8.5 Hz, 4H), 8.19 (t, J = 8.0 Hz,
2H), 7.93 (dd, J = 2.0, 8.5 Hz, 4H), 7.60 (d, J = 9.0 Hz, 8H), 7.58
(d, J = 2.0 Hz, 4H), 7.57 (d, J = 9.0 Hz, 8H), 7.12 (d, J = 9.0 Hz,
8H), 7.03 (d, J = 9.0 Hz, 8H), 6.64 (s, 8H), 5.01 (s, 8H), 4.41 (bd,
J = 8.0 Hz, 16H), 1.55 (s, 24H). 13C NMR (125 MHz, acetone-
d6, d): 159.34, 158.58, 157.69, 157.05, 156.24, 153.84, 141.50,
140.50, 137.94, 135.05, 134.20, 128.54, 128.50, 128.47, 124.95,
124.55, 116.22, 116.17, 114.72, 106.00, 76.50, 71.12, 66.90, 66.55,
56.72, 20.53. MALDI HRMS m/z: found 2044.6826 (M+); calcd
(C130H106N6O12Ru) 2044.6907. UV–Vis (CH3CN), kmax/nm (log
e): 202 (5.6), 268 (5.2), 314 (4.8), 478 (4.0).
Ru(terpy-macrocycle)·2PF6 (7b). Prepared simultaneously
and hydrogenated in an identical manner to compound 7a
(0.068 g, 47%) cis/trans isomers. Hydrogenation yielded a red
glassy solid, 7b (0.065 g, 97%). Mp 132–134 ◦C. 1H NMR
(500 MHz, acetone-d6, d): 8.96 (d, J = 8.0 Hz, 4H), 8.88 (d,
J = 8.0 Hz, 4H), 8.40 (t, J = 8.0 Hz, 2H), 7.96 (dd, J = 2.0,
8.0 Hz, 4H), 7.67 (d, J = 2.0 Hz, 4H), 6.66 (s, 4H), 6.64 (s, 4H),
4.13 (t, J = 5.0 Hz, 8H), 3.77 (t, J = 5.0 Hz, 8H), 3.62 (t, J =
5.0 Hz, 8H), 3.57–3.53 (m, 16H), 3.45 (t, J = 5.0 Hz, 8H), 3.33 (t,
J = 7.0 Hz, 8H), 1.73 (s, 12H), 1.51 (s, 12H), 1.43 (q, J = 7.0 Hz,
8H), 1.19 (bs, 16H). 13C NMR (125 MHz, acetone-d6, d): 160.13,
157.73, 156.45, 153.91, 141.61, 140.83, 137.89, 137.70, 137.26,
128.41, 125.07, 124.67, 115.16, 115.06, 71.81, 71.61, 71.39, 71.28,
70.83, 70.35, 68.54, 30.65, 30.40, 26.99, 20.82, 20.62. MALDI
HRMS m/z: found 1796.8624 (M+); calcd (C102H130N6O16Ru)
1796.8581. UV–Vis (CH3CN), kmax/nm (log e): 203 (5.4), 236
(sh, 4.9), 273 (4.8), 311 (4.9), 479 (4.1).
Ru(terpy-biphenmacrocyle)·2PF6 (11b). A red solid (0.021 g,
◦
1
21%). Mp > 340 C. H NMR (500 MHz, acetone-d6, d): 8.96
(d, J = 8.0 Hz, 4H), 8.85 (d, J = 8.0 Hz, 4H), 8.40 (t, J = 8.0 Hz,
2H), 7.93 (dd, J = 2.0, 8.5 Hz, 4H), 7.65 (d, J = 2.0 Hz, 4H),
7.52 (d, J = 8.5 Hz, 8H), 7.50 (d, J = 8.5 Hz, 8H), 7.04 (d,
J = 8.5 Hz, 8H), 7.00 (d, J = 8.5 Hz, 8H), 4.98 (s, 8H), 4.41
(bd, 16H), 1.73, (s, 12H), 1.45 (s, 12H). 13C NMR (125 MHz,
acetone-d6, d): 159.70, 158.87, 157.72, 157.64, 156.48, 153.89,
141.46, 140.85, 138.01, 137.89, 137.19, 135.03, 134.33, 128.68,
128.44, 128.40, 125.04, 124.64, 116.31, 116.18, 115.69, 115.03,
76.54, 70.99, 67.54, 65.02, 56.58, 20.78, 20.62. MALDI HRMS
m/z: found 2044.7012 (M+); calcd (C130H106N6O12Ru) 2044.6907.
UV–Vis (CH3CN), kmax/nm (log e): 202 (5.5), 266 (5.1), 311 (4.7),
479 (4.0).
Standard reaction conditions for copper-mediated coupling
(compounds 9, 11, and 14a–b). To enough acetonitrile to
generate a 1.0 mM solution of the corresponding pre-catenane
Ru(II) complex (1.0 mol eq.) was added copper(II) acetate
monohydrate (20 mol eq.), and the mixture heated at reflux for
12–32 h, or until no starting material was visible by TLC (SiO2,
CH3CN–H2O–aqueous KPF6 95 : 5 : 0.05). The reactions were
cooled and reduced to dryness. The residues were suspended
in dichloromethane, filtered and the solvent evaporated to
yield the crude red compounds. The crude mixtures were
purified by column chromatography on silica gel with 100%
CH3CN → CH3CN–H2O–aqueous KPF6 95 : 5 : 0.05 as the
eluant, except for compounds 11a–b which required centrifugal
chromatography on silica gel with 100% CH2Cl2 → 2% MeOH
as the eluant.
Ru(pherpy-catenane)·2PF6 (14a). A red glassy solid (0.012 g,
20%). Mp 122–128 ◦C. 1H NMR (500 MHz, acetone-d6, d): 9.12
(d, J = 9.0 Hz, 2H), 9.00 (d, J = 8.0 Hz, 2H), 8.93 (d, J =
9.0 Hz, 2H), 8.53 (d, J = 9.0 Hz, 2H), 8.53 (d, J = 2.0 Hz, 2H),
8.41 (d, J = 9.0 Hz, 2H), 8.04 (dd, J = 2.0, 8.0 Hz, 2H), 7.89
(d, J = 2.0 Hz, 2H), 7.69 (d, J = 2.0 Hz, 2H), 6.62 (s, 2H),
6.60 (s, 2H), 6.55 (s, 2H), 6.52 (s, 2H), 4.08 (bt, J = 6.0 Hz,
8H), 3.74 (bt, J = 6.0 Hz, 8H), 3.61–3.59 (m, 24H), 3.55 (bt,
J = 6.0 Hz, 8H), 3.49 (bt, J = 6.0 Hz, 8H), 2.39 (bt, J =
6.0 Hz, 8H), 1.70–1.664 (m, 16H), 1.62 (s, 6H), 1.61 (s, 6H),
1.39 (s, 6H), 1.36 (s, 6H). 13C NMR (125 MHz, acetone-d6, d):
160.00, 159.98, 158.15, 156.36, 156.13, 155.46, 149.63, 147.31,
141.65, 140.74, 140.32, 138.11, 138.01, 137.95, 137.84, 137.76,
135.05, 131.82, 130.98, 130.14, 128.87, 128.71, 128.24, 125.67,
123.14, 114.77*, 114.71*, 78.53*, 71.50*, 71.31*, 71.22*, 70.99*,
70.91*, 70.26*, 68.49*, 66.56*, 29.72*, 26.01*, 20.74, 20.65,
20.48, 20.35, 19.32*. MALDI HRMS m/z: found 1940.8534
(M+); calcd (C114H130N6O16Ru) 1940.8581. UV–Vis (CH3CN),
kmax/nm (log e): 202 (5.3), 236 (4.9), 297 (4.8), 343 (4.6), 501
(4.0).
5–5ꢀꢀ -Bis{4-[2-(4ꢀ -allyloxybiphenyl-4-yloxy)ethoxy]-2,6-
dimethylphenyl}-[2,2ꢀ:6ꢀ2ꢀꢀ]-terpyridine (15). An anhydrous
solution of 3b (0.197 g, 0.42 mmol), 22b (0.330 g, 1.14 mmol),
and cesium carbonate (0.689 g, 2.11 mmol) in DMF (10 mL)
was heated at 80 ◦C for 12 h with an oil bath. The crude reaction
mixture was quenched with water (30 mL) and extracted with
chloroform (30 mL). The organic layer was separated, washed
with water (3 × 20 mL), dried over magnesium sulfate, filtered
and reduced to dryness. Purification by column chromatography
on alumina with dichloromethane–hexane 3 : 1 as the eluant
afforded a white solid (0.357 g, 88%). Mp 188–189 ◦C. 1H NMR
(500 MHz, CDCl3, d): 8.73 (d, J = 8.0 Hz, 2H), 8.53 (d, J =
2.0 Hz, 2H), 8.52 (d, J = 8.0 Hz, 2H), 8.02 (t, J = 8.0 Hz, 1H),
7.69 (dd, J = 2.0, 8.0 Hz, 2H), 7.50 (d, J = 9.0 Hz, 4H), 7.48 (d,
J = 9.0 Hz, 4H), 7.03 (d, J = 9.0 Hz, 4H), 6.98 (d, J = 9.0 Hz,
4H), 6.80 (s, 4H), 6.09 (m, 2H), 5.44 (dd, J = 2.0, 18.0 Hz,
Ru(terpy-acteylcatenane)·2PF6 (9a).
A red glassy solid
◦
1
(0.012 g, 25%). Mp 65–70 C. H NMR (500 MHz, acetone-
d6, d): 8.95 (d, J = 8.0 Hz, 4H), 8.87 (d, J = 8.0 Hz, 4H), 8.36
(t, J = 8.0 Hz, 2H), 8.01 (dd, J = 2.0, 8.0 Hz, 4H), 7.62 (d,
J = 2.0 Hz, 4H), 6.34 (s, 8H), 4.12 (t, J = 5.0 Hz, 8H), 3.78 (t,
J = 5.0 Hz, 8H), 3.64–3.60 (m, 24H), 3.55 (t, J = 5.0 Hz, 8H),
3.50 (t, J = 6.0 Hz, 8H), 2.36 (t, J = 6.0 Hz, 8H), 1.69–1.63 (m,
16H), 1.62 (s, 24H). 13C NMR (125 MHz, acetone-d6, d): 159.11,
156.71, 155.51, 153.07, 140.75, 139.72, 136.98, 136.21, 127.43,
124.16, 123.69, 113.85, 77.50, 70.60, 70.40, 70.31, 70.07, 69.99,
69.36, 67.56, 65.54, 25.06, 19.73, 19.69, 18.35. MALDI HRMS
m/z: found 1892.8710 (M+); calcd (C110H130N6O16Ru) 1892.8581.
UV–Vis (CH3CN), kmax/nm (log e): 201 (5.2), 235 (sh, 4.7), 272
(4.6), 312 (4.7), 480 (3.9).
Ru(terpy-acetylmacrocycle)·2PF6 (9b). A red glassy solid
◦
1
(0.017 g, 36%). Mp 79–84 C. H NMR (500 MHz, acetone-
d6, d): 8.98 (d, J = 8.0 Hz, 4H), 8.88 (d, J = 8.0 Hz, 4H), 8.42
(t, J = 8.0 Hz, 2H), 7.98 (dd, J = 2.0, 8.0 Hz, 4H), 7.65 (d,
J = 2.0 Hz, 4H), 6.66 (s, 4H), 6.65 (s, 4H), 4.12 (t, J = 5.0 Hz,
8H), 3.79 (t, J = 5.0 Hz, 8H), 3.64 (t, J = 5.0 Hz, 8H), 3.58, (t,
J = 5.0 Hz, 8H), 3.56 (t, J = 5.0 Hz, 8H), 3.48 (t, J = 5.0 Hz,
8H), 3.37 (t, J = 7.0 Hz, 8H), 2.15 (t, J = 7.0 Hz, 8H), 1.69 (s,
12H), 1.59 (s, 12H), 1.52 (q, J = 7.0 Hz, 8H), 1.44 (q, J = 7.0 Hz,
8H). 1H NMR (125 MHz, acetone-d6, d): 160.09, 157.67, 156.45,
153.95, 141.60, 140.85, 137.92, 137.86, 137.31, 128.37, 125.12,
O r g . B i o m o l . C h e m . , 2 0 0 5 , 3 , 3 1 0 5 – 3 1 1 6
3 1 1 3

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2H), 5.31, (dd, J = 2.0, 12.0 Hz, 2H), 4.58 (d, J = 6.0 Hz, 4H),
4.39 (bs, 8H), 2.10 (s, 12H). 13C NMR (125 MHz, CDCl3, d):
158.08, 157.83, 157.80, 155.40, 154.67, 150.03, 138.35, 138.09,
138.01, 136.69, 133.91, 133.56, 133.34, 130.88, 127.79, 127.75,
125.55, 120.90, 117.74, 115.03, 115.00, 113.79, 68.88, 66.61,
66.42, 21.19. MALDI HRMS m/z: found 978.4525 (M+); calcd
(C65H60N3O6) 978.4477.
purple precipitate, which was filtered and washed with water.
The precipitate was dissolved in dichloromethane, dried over
magnesium sulfate, filtered, and reduced to dryness to yield
a purple solid (0.233 g, 91%). Mp 160–163 ◦C. 1H NMR
(500 MHz, acetone-d6, d): 9.45 (d, J = 8.8 Hz, 2H), 9.23 (d, J =
8.8 Hz, 2H), 9.03 (d, J = 8.4 Hz, 2H), 8.64 (d, J = 8.8 Hz, 2H),
8.44 (d, J = 2.0 Hz, 2H), 8.41 (d, J = 8.8 Hz, 2H), 7.97 (dd, J =
2.0, 8.4 Hz, 2H), 7.56 (d, J = 10.0 Hz, 8H), 7.55 (d, J = 2.0 Hz,
2H), 7.54 (d, J = 10.0 Hz, 8H), 7.45 (d, J = 2.0 Hz, 2H), 7.03
(d, J = 10.0 Hz, 8H), 7.01 (d, J = 10.0 Hz, 8H), 6.66 (s, 2H),
6.64 (s, 2H), 6.58 (s, 2H), 6.56 (s, 2H), 6.09 (m, 4H), 5.45 (d,
J = 17.2 Hz, 4H), 5.27 (d, J = 10.8 Hz, 4H), 4.62 (m, 8H), 4.35
(bs, 8H), 4.32 (bs, 8H), 1.56 (s, 6H), 1.54 (s, 6H), 1.26 (s, 12H).
13C NMR (125 MHz, CD2Cl2, d): 161.92*, 159.70*, 158.89*,
158.84, 158.06, 158.00, 156.41, 151.79, 148.68, 141.76, 141.29,
140.41, 138.80, 138.04, 137.91, 137.87, 137.73, 137.12, 134.80*,
134.32*, 134.06*, 130.80, 130.67, 130.03, 129.02, 128.56,
128.36*, 128.33, 128.31*, 125.22, 123.68, 117.41*, 115.93*,
115.80*, 114.70*, 114.63*, 69.32*, 67.43*, 67.36*, 20.66, 20.59,
20.31, 20.19. MALDI HRMS m/z: found 2058.8076 (M+);
calcd (C134H118N6O12Fe) 2058.8152. UV–Vis (CH3CN), kmax/nm
(log e): 203(5.7), 267 (5.2), 357 (4.7), 579 (4.0).
8-{4-[2-(4ꢀ -Allyloxybiphenyl-4-yloxy)ethoxy]-2,6-dimethyl-
phenyl}-2-(5-{4-[2-(4ꢀ -allyloxybiphenyl-4-yloxy)ethoxy]-2,6-
dimethylphenyl}pyridin-2-yl)-[1,10]-phenanthroline (18). An
anhydrous solution of 4b (0.256 g, 0.52 mmol), 22b (0.447 g,
1.55 mmol), and cesium carbon◦ate (0.840 g, 2.58 mmol) in
DMF (13 mL) was heated at 80 C for 12 h with an oil bath.
The crude reaction mixture was quenched with water (30 mL)
and extracted with chloroform (30 mL). The organic layer
was separated, washed with water (3 × 20 mL), dried over
magnesium sulfate, filtered and reduced to dryness. Purification
by column chromatography on alumina with dichloromethane–
hexane 3 : 1 as the eluant afforded a white solid (0.473 g, 92%).
◦
1
Mp 203–204 C. H NMR (400 MHz, CDCl3, d): 9.07 (d, J =
8.0 Hz, 1H), 9.08 (d, J = 2.0 Hz, 1H), 8.86, (d, J = 8.0 Hz,
1H), 8.56 (d, J = 2.0 Hz, 1H), 8.42 (d, J = 8.0 Hz, 1H), 8.07
(d, J = 2.0 Hz, 1H), 7.88 (d, J = 8.0 Hz, 1H), 7.82 (d, J =
8.0 Hz, 1H), 7.75 (dd, J = 2.0, 8.0 Hz, 1H), 7.49 (d, J = 8.0 Hz,
4H), 7.47 (d, J = 8.0 Hz, 4H), 7.02 (d, J = 8.0 Hz, 4H), 6.97
(d, J = 8.0 Hz, 4H), 6.82 (s, 2H), 6.79 (s, 2H), 6.06 (m, 2H),
5.43 (dd, J = 2.0, 18.0 Hz, 2H), 5.28, (dd, J = 2.0, 12.0 Hz,
2H), 4.55 (d, J = 6.0 Hz, 4H), 4.38 (s, 4H), 4.37 (s, 4H), 2.10
(s, 6H), 2.07 (s, 6H). 13C NMR (125 MHz, CDCl3, d): 158.18*,
158.00*, 157.75*, 156.39, 154.67, 151.99, 149.83, 145.74, 144.93,
138.50, 138.06, 137.91, 137.06, 137.01, 136.53, 135.93, 133.81,
133.78, 133.47, 133.45, 133.28*, 130.84, 130.61, 128.81, 128.66,
127.71*, 127.65*, 126.78, 126.74, 122.54, 120.70, 117.62*,
114.97*, 114.94*, 113.79, 113.73, 68.78*, 66.54*, 66.38, 66.35,
21.20, 21.12. MALDI HRMS m/z: found 1002.4458 (M+);
calcd (C67H60N3O6) 1002.4477.
Fe(terpycat)·2PF6 (17). To a solution of RuCl2(PCy3)2CH2Ph
(8 mg, 0.20 mmol) in dichloromethane (20 mL) was added a
solution of 16 (0.115 g, 0.05 mol) in dichloromethane (20 mL)
via syringe pump over 12 h. The resulting purple solution was
stirred for an additional 60 h. The crude reaction mixture was
reduced to dryness and purified by column chromatography
on silica gel with CH3CN–H2O–aqueous KPF6 96 : 4 : 0.04
as the eluant. Subsequent centrifugal chromatography with
dichloromethane–methanol 100 : 3 as the eluant afforded
a purple solid (0.033 g, 30%) as a mixture of cis/trans
isomers. This mixture (0.022 g, 0.010 mmol) was dissolved in
dichloromethane–ethanol 1 : 1 (6 mL), and to it was added
Pt/alumina (5 mol%). The resulting solution was stirred under
a hydrogen atmosphere for 36 h. The crude mixture was
filtered, and the solution reduced to◦dryness to afford a purple
Fe(5–5ꢀꢀ -bis{4-[2-(4ꢀ -Allyloxybiphenyl-4-yloxy)ethoxy]-2,6-
dimethylphenyl}-[2,2ꢀ:6ꢀ2ꢀꢀ]-terpyridine)2·2PF6 (16). To a sus-
pension of 15 (0.174 g, 0.18 mmol) in acetone (20 mL), at 55 ◦C,
was added a solution of FeSO4·7H2O (0.049 g, 0.18 mmol) in
water (12 mL) dropwise to generate an intense purple solution,
which was heated at reflux for 1 h. The crude reaction was
quenched with aqueous KPF6 to generate a purple precipitate,
which was filtered and washed with water. The precipitate was
dissolved in dichloromethane, dried over magnesium sulfate,
filtered, and reduced◦to dryness to yield a purple solid (0.203 g,
1
solid (0.020 g, 91%). Mp 218–223 C. H NMR (500 MHz,
acetone-d6, d): 8.91 (d, J = 8.0 Hz, 4H), 8.73 (d, J = 8.0 Hz,
4H), 8.42 (t, J = 8.0 Hz, 2H), 7.87 (dd, J = 2.0, 8.0 Hz, 4H),
7.56 (d, J = 8.8 Hz, 8H), 7.55 (d, J = 8.8 Hz, 8H), 7.24 (d, J =
2.0 Hz, 4H), 7.06 (d, J = 8.8 Hz, 8H), 7.03 (d, J = 8.8 Hz, 8H),
6.61 (s, 8H), 4.44 (d, J = 2.8 Hz, 8H), 4.37 (d, J = 2.8 Hz, 8H),
4.21 (bs, 8H), 3.06 (bs, 8H), 1.46 (s, 24H). 13C NMR (125 MHz,
acetone-d6, d): 161.11, 159.26, 159.22, 158.28, 157.54, 154.59,
141.47, 141.35, 139.33, 137.87, 134.40, 133.83, 128.62, 128.34,
128.31, 124.58, 124.30, 116.24, 115.87, 114.67, 67.99, 66.67,
66.34, 26.26, 20.45. MALDI HRMS m/z: found 1958.7705
(M+); calcd (C126H114N6O12Fe) 1958.7839. UV–Vis (CH3CN),
kmax/nm (log e): 201 (5.5), 272 (5.0), 334 (4.5), 554 (3.8).
1
99%). Mp 158–159 C. H NMR (500 MHz, acetone-d6, d):
9.14 (d, J = 8.0 Hz, 4H), 8.87 (d, J = 8.0 Hz, 4H), 8.67 (t, J =
8.0 Hz, 2H), 7.97 (dd, J = 2.0, 8.0 Hz, 4H), 7.56 (d, J = 8.0 Hz,
8H), 7.54 (d, J = 8.0 Hz, 8H), 7.35 (d, J = 2.0 Hz, 4H), 7.04
(d, J = 8.0 Hz, 8H), 7.03 (d, J = 8.0 Hz, 8H), 6.83 (s, 8H),
6.10 (m, 4H), 5.43 (dd, J = 2.0, 17.0 Hz, 4H), 5.27 (dd, J =
2.0, 11.0 Hz, 4H), 4.62 (bd, J = 5.0 Hz, 8H), 4.37 (bd, J =
8.0 Hz, 16H), 1.56 (s, 24H). 13C NMR (125 MHz, CD2Cl2, d):
160.42, 159.43, 158.40, 158.29, 156.20, 153.91, 1491.78, 139.90,
137.52, 134.16, 134.14, 134.13, 134.01, 133.72, 128.10, 128.03,
127.56, 124.08, 117.67, 115.50, 115.38, 114.75, 69.28, 67.14,
67.08, 20.74. MALDI HRMS m/z: found 2010.8226 (M+);
calcd (C130H118N6O12Fe) 2010.8152. UV–Vis (CH3CN), kmax/nm
(log e): 202 (5.6), 269 (5.1), 333 (4.7), 556 (3.9).
Terpy catenane (1). To a solution of 17 (0.020 g, 0.009 mmol)
in acetonitrile–water 1 : 1 (12 mL) was added 10% sodium
hydroxide (1 mL) followed by a slow addition of hydrogen
peroxide (35% in water) until no purple color remained. The
resulting solution was extracted with chloroform (20 mL).
The organic layer was removed, washed with water (3 ×
15 mL), dried over magnesium sulfate, filtered and reduced to
dryness. Purification by column chromatography on alumina
with chloroform–hexane 3 : 1 as the eluant afforded a white
solid (0.010 g, 59%). 1H NMR (500 MHz, CDCl3, d): 8.60
(d, J = 8.0 Hz, 4H), 8.50 (d, J = 2.0 Hz, 4H), 8.39 (d, J =
8.0 Hz, 4H), 7.93, (t, J = 8.0 Hz, 2H), 7.32 (dd, J = 2.0, 8.0 Hz,
4H), 7.28 (d, J = 9.0 Hz, 8H), 7.27 (d, J = 9.0 Hz, 8H), 6.82
(d, J = 9.0 Hz, 8H), 6.80 (d, J = 9.0 Hz, 8H), 6.74 (s, 8H),
4.43 (t, J = 4.0 Hz, 8H), 4.27 (t, J = 4.0 Hz, 8H), 3.90 (t,
J = 6.0 Hz, 8H), 1.95 (s, 24H), 1.87 (t, J = 6.0 Hz, 8H). 13C
NMR (125 MHz, CDCl3, d): 157.94, 157.23, 157.21, 155.07,
154.67, 149.46, 138.57, 138.14, 137.83, 136.67, 133.81, 133.10,
131.01, 127.59, 127.57, 121.27, 120.37, 115.32, 114.73, 114.57,
Fe(8-{4-[2-(4ꢀ-allyloxybiphenyl-4-yloxy)ethoxy]-2,6-dimethyl-
phenyl}-2-(5-{4-[2-(4ꢀ -allyloxybiphenyl-4-yloxy)ethoxy]-2,6-
dimethyl-phenyl}pyridin-2-yl)-[1,10]-phenanthroline)2·2PF6 (19).
To a suspension of 18 (0.218 g, 0.22 mmol) in acetone (20 mL),
at 55 ◦C, was added a solution of FeSO4·7H2O (0.060 g,
0.22 mmol) in water (15 mL) dropwise to generate an intense
purple solution, which was heated at reflux for 1 h. The crude
reaction was quenched with aqueous KPF6 to generate a
3 1 1 4
O r g . B i o m o l . C h e m . , 2 0 0 5 , 3 , 3 1 0 5 – 3 1 1 6

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66.82, 66.23, 65.63, 25.23, 21.12. MALDI HRMS m/z: found
689–691; (f) V. Balzani, A. Credi, F. M. Raymo and J. F. Stoddart,
Angew. Chem., Int. Ed., 2000, 39(19), 3348–3391; (g) V. Balzani,
A. Credi and M. Venturi, in Stimulating Concepts in Chemistry,
M. Shibasaki, J. F. Stoddart and F. Vo¨gtle, eds., Wiley-VCH,
Weinheim, 2001, p. 255; (h) V. Balzani, M. Gomez-Lopez and J. F.
Stoddart, Acc. Chem. Res., 1998, 31(7), 405–414; (i) J. P. Sauvage,
Acc. Chem. Res., 1998, 31(10), 611–619.
4 (a) T. J. Hubin and D. H. Busch, Coord. Chem. Rev., 2000, 200(202),
5–52; (b) T. J. Hubin, A. G. Kolchinski, A. L. Vance and D. H. Busch,
‘Template Control of Supramolecular Architecture’, in Advances in
Supramolecular Chemistry, G. W. Gokel, ed., JAI Press, Connecticut,
USA, 1999, vol. 5, pp. 237–357.
5 (a) G. F. Swiegers and T. J. Malefetse, Chem. Rev., 2000, 100,
3483–3537; (b) J.-P. Sauvage, Transition Metals in Supramolecular
Chemistry, John Wiley & Sons, New York, 1999.
6 C. Kaes, A. Katz and M. W. Hosseini, Chem. Rev., 2000, 100, 3553–
3590.
1903.8420 (M+); calcd (C126H114N6O12) 1903.8568.
Fe(pherpycat)·2PF6 (20). To a solution of 19 (0.33 g,
0.14 mmol) in dichloromethane (200 mL) was added a solution
of RuCl2(PCy3)2CH2Ph (12 mg, 0.01 mmol) in dichloromethane
(20 mL) via cannula. The purple solution was stirred for 72 h.
The crude reaction mixture was reduced to dryness and purified
by column chromatography on silica gel with CH3CN–H2O–
aqueous KPF6 97 : 3 : 0.03 as the eluant. Subsequent centrifugal
chromatography with dichloromethane–methanol 100 : 3 as the
eluant afforded a purple solid (0.063 g, 20%) as a mixture of
cis/trans isomers. This mixture (0.023 g, 0.010 mmol) was dis-
solved in a solution of dichloromethane–ethanol 1 : 1 (6 mL) and
to it was added Pt/alumina (5 mol%). The resulting solution was
stirred under a hydrogen atmosphere for 12 h. The crude mixture
was filtered and the solution reduced to dryness to afford a pur-
ple solid (0.022 g, 96%). Mp 224–230 ◦C. 1H NMR (500 MHz,
CDCl3, d): 9.20 (d, J = 9.0 Hz, 2H), 8.98 (d, J = 9.0 Hz, 2H), 8.88
(d, J = 8.5 Hz, 2H), 8.45 (d, J = 9.5 Hz, 2H), 8.35 (d, J = 2 Hz,
2H), 8.29 (d, J = 9.5 Hz, 2H), 7.88 (dd, J = 2.0, 8.5 Hz, 2H), 7.60
(d, J = 8.5 Hz, 8H), 7.58 (d, J = 8.5 Hz, 8H), 7.44 (d, J = 2.0 Hz,
2H), 7.36 (d, J = 2.0 Hz, 2H), 7.10 (d, J = 8.5 Hz, 8H), 7.01 (d,
J = 8.5 Hz, 8H), 6.59 (s, 2H), 6.57 (s, 2H), 6.51 (s, 2H), 6.49 (s,
2H), 4.4 (bt, J = 4.0 Hz, 8H), 4.44 (bt, J = 4.0 Hz, 8H), 4.23
(bt, J = 4.0 Hz, 8H), 2.09 (bt, J = 4.0 Hz, 8H), 1.45 (s, 6H), 1.44
(s, 6H), 1.15 (s, 12H). 13C NMR (125 MHz, CDCl3, d): 161.83*,
159.32*, 159.14, 158.26*, 158.04, 157.94, 156.36, 151.67, 148.68,
141.59, 141.25, 140.33, 138.67, 137.98, 137.86, 137.81, 137.68,
136.96, 134.38*, 13384*, 130.64, 129.81,128.94, 128.50, 128.36*,
128.30, 128.28*, 126.36, 125.09, 123.60, 116.22*, 115.91*,
114.61*, 114.58*, 67.95*, 66.63*, 66.24*, 26.24*, 20.57, 20.50,
20.23, 20.12. MALDI HRMS m/z: found 2006.7866 (M+); calcd
(C130H114N6O12Fe) 2006.7839. UV–Vis (CH3CN), kmax/nm (log
e): 202 (5.6), 260 (5.2), 356 (4.5), 579 (3.9).
7 W. W. Brandt, Chem. Rev., 1954, 54, 959–1017.
8 A. M. W. C. Thompson, Coord. Chem. Rev., 1997, 160, 1–52.
9 M. Benaglia, F. Ponzini, C. R. Woods and J. S. Siegel, Org. Lett.,
2001, 3(7), 967–969.
10 (a) S. Toyota, C. R. Woods, M. Benaglia, R. Haldimann, K.
Warnmark, K. Hardcastle and J. S. Siegel, Angew. Chem., Int. Ed.,
2001, 40(4), 751–754; (b) C. R. Woods, M. Benaglia, S. Toyota, K.
Hardcastle and J. S. Siegel, Angew. Chem., Int. Ed., 2001, 40(4), 749–
751.
11 (a) C. O. Dietrich-Buchecker, J. P. Sauvage and J. P. Kintzinger,
Tetrahedron Lett., 1983, 24(46), 5095–5098; (b) M. Weck, B. Mohr,
J. P. Sauvage and R. H. Grubbs, J. Org. Chem., 1999, 64(15), 5463–
5471; (c) C. Dietrich-Buchecker, G. Rapenne and J. P. Sauvage, Coord.
Chem. Rev., 1999, 186(V186), 167–176.
12 C. O. Dietrich-Buchecker, P. A. Marnot and J. P. Sauvage, Tetrahe-
dron Lett., 1982, 23(50), 5291–5294.
13 (a) J.-C. Chambron, J.-P. Collin, V. Heitz, D. Jouvenot, J.-M. Kern,
P. Mobian, D. Pomeranc and J.-P. Sauvage, Eur. J. Org. Chem., 2004,
8, 1627–1638; (b) P. Mobian, J.-M. Kern and J.-P. Sauvage, Inorg.
Chem., 2003, 42(26), 8633–8637; (c) P. Mobian, J. M. Kern and J. P.
Sauvage, J. Am. Chem. Soc., 2003, 125(8), 2016–2017; (d) F. Arico,
P. Mobian, J. M. Kern and J. P. Sauvage, Org. Lett., 2003, 5(11),
1887–1890; (e) D. A. Leigh, P. J. Lusby, S. J. Teat, A. J. Wilson and
J. K. Y. Wong, Angew. Chem., Int. Ed., 2001, 40(8), 1538–1543.
14 C. Piguet, G. Bernardinelli, A. F. Williams and B. Bocquet, Angew.
Chem., Int. Ed. Engl., 1995, 34, 582–584.
15 J. P. Sauvage and M. Ward, Inorg. Chem., 1991, 30(20), 3869–3874.
16 (a) D. J. Cardenas, P. Gavina and J.-P. Sauvage, J. Am. Chem. Soc.,
1997, 119(11), 2656–2664; (b) D. J. Cardenas, J. P. Collin, P. Gavina,
J. P. Sauvage, A. De Cian, J. Fischer, N. Armaroli, L. Flamigni, V.
Vicinelli and V. Balzani, J. Am. Chem. Soc., 1999, 121(23), 5481–
5488; (c) A. Livoreil, C. O. Dietrich-Buchecker and J. P. Sauvage,
J. Am. Chem. Soc., 1994, 116(20), 9399–9400.
Pherpy catenane (2). To a solution of 20 (0.022 g, 10 lmol) in
acetonitrile–water 1 : 1 (6 mL) was added 10% sodium hydroxide
(1 mL) followed by a slow addition of hydrogen peroxide (35% in
water) until no purple color remained. The resulting solution was
extracted with dichloromethane (15 mL). The organic layer was
removed, washed with water (3 × 15 mL), dried over magnesium
sulfate, filtered and reduced to dryness. Purification by column
chromatography on silica with 2–3% MeOH in chloroform as the
eluant afforded a white solid (5 mg, 27%). 1H NMR (500 MHz,
CDCl3, d): 8.98 (d, J = 8.0 Hz, 2H), 8.83 (d, J = 2.0 Hz, 2H),
8.77 (d, J = 8.5 Hz, 2H), 8.54 (d, J = 2.0 Hz, 2H), 8.40 (d,
J = 8.0 Hz, 2H), 8.07 (d, J = 2.0 Hz, 2H), 7.86 (d, J = 9.0 Hz,
2H), 7.80 (d, J = 9.0 Hz, 2H), 7.41 (dd, J = 2.0, 8.5 Hz, 2H),
7.30–7.25 (m, 8H), 8.86 (d, J = 8.5 Hz, 4H), 6.79 (d, J = 8.5 Hz,
4H), 6.77 (s, 4H), 6.73 (s, 4H), 4.44 (bt, J = 5.0 Hz, 8H), 4.31
(bs, 8H), 3.88 (bt, J = 5.0 Hz, 8H), 1.97 (s, 6H), 1.97 (s, 6H),
1.96 (s, 6H), 1.94 (s, 6H), 1.85 (bs, 8H). MALDI HRMS m/z:
found 1951.8663 (MH+); calcd (C130H115N6O12) 1951.8568.
17 For a recent report on a metal-free catenane templated by Zn(II) with
terpyridine and phenanthroline, see: C. Hamann, J. M. Kern and J. P.
Sauvage, Inorg. Chem., 2003, 42, 1877–1883.
18 N. Belfrekh, C. Dietrich-Buckecker and J.-P. Sauvage, Inorg. Chem.,
2000, 39, 5169–5172.
19 (a) Doubly interlocked catenanes from symmetric components are
also chiral by virtue of a helical twist. For examples of these
analogs, see: A. C. Try, M. M. Harding, D. G. Hamilton and
J. K. M. Sanders, Chem. Commun., 1998, 6, 723–724; (b) C. Dietrich-
Buchecker and J. P. Sauvage, Chem. Commun., 1999, 7, 615–616;
(c) J. F. Nierengarten, C. O. Dietrich-Buchecker and J. P. Sauvage,
New J. Chem., 1996, 20(6), 685–693; (d) J. F. Nierengarten, C. O.
Dietrich-Buchecker and J. P. Sauvage, J. Am. Chem. Soc., 1994,
116(1), 375–376; (e) F. Ibukuro, M. Fujita, K. Yamaguchi and
J.-P. Sauvage, J. Am. Chem. Soc., 1999, 121(47), 11014–11015.
20 (a) J. C. Chambron, D. K. Mitchell and J. P. Sauvage, J. Am. Chem.
Soc., 1992, 114(12), 4625–4631; (b) D. K. Mitchell and J. P. Sauvage,
Angew. Chem., Int. Ed. Engl., 1988, 27(7), 930–931; (c) C. P. McArdle,
S. Van, M. C. Jennings and R. J. Puddephatt, J. Am. Chem. Soc., 2001;
(d) A. Mohry, F. Vo¨gtle, M. Nieger and H. Hupfer, Chirality, 2000,
12(2), 76–83; (e) C. Yamamoto, Y. Okamoto, T. Schmidt, R. Ja¨ger
and F. Vo¨gtle, J. Am. Chem. Soc., 1997, 119(43), 10547–10548; (f) S.
Ottens-Hildebrandt, T. Schmidt, J. Harren and F. Vo¨gtle, Liebigs
Ann., 1995, 10, 1855–60; (g) P. R. Ashton, I. Iriepa, M. V. Reddington,
N. Spencer, A. M. Z. Slawin, J. F. Stoddart and D. J. Williams,
Tetrahedron Lett., 1994, 35(27), 4835–4838.
References and notes
1 (a) G. Schill, Catenanes, Rotaxanes, and Knots. 1971, New York,
Academic Press Inc.; (b) J. S. Siegel, Science, 2004, 304, 1256–59.
2 (a) K. S. Chichak, S. J. Cantrill, A. R. Pease, S.-H. Chiu, G. W. V.
Cave, J. L. Atwood and J. F. Stoddart, Science, 2004, 304, 1308–1312;
(b) J. P. Sauvage and C. Dietrich-Buchecker, Molecular Catenanes,
Rotaxanes and Knots: A Journey Through the World of Molecular
Topology, Wiley-VCH, Weinheim, 1999.
3 (a) A. H. Flood, R. J. A. Ramirez, W.-Q. Deng, R. P. Muller,
W. A. Goddard, III and J. F. Stoddart, Aust. J. Chem., 2004,
57(4), 301–322; (b) B. Korybut-Daszkeiwicz, A. Wieckowska, R.
Ilewicz, S. Domagala and K. Wozniak, Angew. Chem., Int. Ed., 2004,
43(13), 1668–1672; (c) P. Mobian, J.-M. Kern and J.-P. Sauvage,
Angew. Chem., Int. Ed., 2004, 43(18), 2392–2395; (d) M. Cavallini,
F. Biscarini, S. Leon, F. Zerbetto, G. Bottari and D. A. Leigh,
Science, 2003, 299(5606), 531; (e) T. Da Ros, D. M. Guldi, A. F.
Morales, D. A. Leigh, M. Prato and R. Turco, Org. Lett., 2003, 5(5),
21 (a) J. J. Moore, J. J. Nash, P. E. Fanwick and D. R. McMillin, Inorg.
Chem., 2002, 41(24), 6387–6396; (b) F. Barigelletti, B. Ventura, J. P.
Collin, R. Kayhanian, P. Gavina and J. P. Sauvage, Eur. J. Inorg.
Chem., 2000, 1, 113–119; (c) J. P. Collin, P. Gavina, J. P. Sauvage,
A. DeCian and J. Fischer, Aust. J. Chem., 1997, 50(10), 951–957;
O r g . B i o m o l . C h e m . , 2 0 0 5 , 3 , 3 1 0 5 – 3 1 1 6
3 1 1 5

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(d) C. Y. Hung, T. L. Wang, Z. Shi and R. P. Thummel, Tetrahedron,
1994, 50, 10685.
0.044, 12817 reflections with I > 2r(I), refinement on F2 with
SHELXL-97, 1116 parameters, R(F)[I > 2r(I) reflections] = 0.098,
−3
wR(F2) [all reflections] = 0.307, S(F2) = 1.088, Dqmax = 1.31 e A
.
˚
22 (a) U. Lehmann, O. Henze and A. D. Schlu¨ter, Chem. Eur. J., 1999,
5(3), 854–859; (b) U. S. Schubert and C. Eschbaumer, Org. Lett.,
1999, 1(7), 1027–1029; (c) U. S. Schubert, C. Eschbaumer and G.
Hochwimmer, Synthesis, 1999, 5, 779–782.
CCDC reference number 270917. See http://dx.doi.org/10.1039/
b506101f for crystallographic data in CIF or other electronic
format.
23 J. C. Loren and J. S. Siegel, Angew. Chem., Int. Ed., 2001, 40(4),
32 (a) Crystal structure analysis of the Fe(II) complex with 3a: crystal ob-
tained from dichloromethane–benzene; empirical formula including
solvent molecules C66H64F12FeN6O5P2, Mr = 1367.0, orthorhombic,
754–757.
24 The prefix [n] is often associated with term catenane to indicate the
number of interlocking molecular cycles per molecule, a convention
that is useful when comparing multi-component catenanes. This
paper designates [2]catenane simply as catenane.
25 A. Fu¨rstner, Angew. Chem., Int. Ed., 2000, 39, 3012–3043.
26 P. Siemsen, R. C. Livingston and F. Diederich, Angew. Chem., Int.
Ed., 2000, 39, 2632–2657.
27 (a) A. Merz and H. Bachmann, J. Am. Chem. Soc., 1995, 117, 901–
908; (b) M. Delgado and J. D. Martin, J. Org. Chem., 1999, 64,
4798–4816.
˚
space group Pbcn, a = 23.3906(5), b = 11.4829(2), c = ◦23.2945(6) A,
3
V = 6256.7(2) A , Z = 4, Dx = 1.451 g cm−3, T = −113 C, crystal di-
˚
mensions: 0.20 × 0.10 × 0.07 mm, Nonius KappaCCD area-detector
−1
˚
diffractometer, MoKa radiation, k = 0.71073 A, l = 0.384 mm
,
hmax = 25◦, 75497 measured reflections, 5489 independent reflections,
3041 reflections with I > 2r(I), absorption correction based on
analysis of equivalent reflections (SORTAV), refinement on F2 with
SHELXL-97,33 481 parameters, R(F) [I > 2r(I) reflections] = 0.075,
−3
wR(F2) [all reflections] = 0.234, S(F2) = 1.021, Dqmax = 1.25 e A
.
˚
28 I. P. Evans, A. Spencer and G. Wilkinson, J. Chem. Soc., Dalton
The hexafluorophosphate anion is highly disordered; the asymmet-
ric unit includes one 50%-occupied site for a water molecule. CCDC
reference number 274362. See http://dx.doi.org/10.1039/b506101f
for crystallographic data in CIF or other electronic format; (b) Crys-
tal structure analysis of the Ru(II) complex with 3a: crystal obtained
from dichloromethane–benzene; empirical formula including solvent
molecules C66H64F12N6O5P2Ru, Mr = 1412.2, orthorhombic, space
Trans., 1973, 204–209.
29 (a) B. Mohr, M. Weck, J. P. Sauvage and R. H. Grubbs, Angew. Chem.,
Int. Ed., 1997, 36(12), 1308–1310; (b) P. Schwab, R. H. Grubbs and
J. Ziller, J. Am. Chem. Soc., 1996, 118, 100–110.
30 Successful alkylation only occurred in the presence of tri(ethylene)
glycol dimethyl ether (triglyme) and cesium carbonate. Little to no
reactivity was observed in the absence of triglyme or when potassium
carbonate was used, suggesting that a cesium–triglyme or cesium–
polyethylene glycol coordinating effect facilitates the alkylation of
the poorly soluble poly-phenoxide ion of 5. This behavior was not
observed when 5 was alkylated with polyethylene glycol linkers 21b
and 23b. Here it is presumed that the linkers play the role of the
triglyme.
˚
group Pbcn, a = 23.1733(3), b = 11.9603(1), c = 22.8083(3) A,
V = 6321.5(1) A , Z = 4, Dx = 1.484 g cm−3, T = −113 ◦C,
3
˚
crystal dimensions: 0.20 × 0.18 × 0.07 mm, Nonius KappaCCD
˚
area-detector diffractometer, MoKa radiation, k = 0.71073 A,
l = 0.390 mm−1, hmax = 25◦, 101070 measured reflections, 5577
independent reflections, 3965 reflections with I > 2r(I), absorption
correction based on analysis of equivalent reflections (SORTAV),
refinement on F2 with SHELXL-97,33 481 parameters, R(F) [I >
2r(I) reflections] = 0.061, wR(F2) [all reflections] = 0.189, S(F2) =
31 Crystal structure analysis of 11a: crystal from dichloro-
methane–benzene; empirical formula including solvent molecules
C172.23H106Cl3.11F12N6O15P2Ru, Mr = 3000.6; crystal system triclinic,
1.044, Dqmax = 1.31 e A−3. The hexafluorophosphate anion is
˚
¯
˚
space group P1, a = 16.1362(14), b = 17.4816(16), c = 30.711(3) A,
highly disordered; the asymmetric unit includes one 50%-occupied
site for a water molecule. CCDC reference number 274363. See
http://dx.doi.org/10.1039/b506101f for crystallographic data in
CIF or other electronic format.
◦
3
˚
a = 77.635(2), b = 75.632(2), c = 65.267(2) , V = 7562.3(12) A ,
Z = 2, Dx = 1.318 g cm−3, T = −173 ◦C; crystal dimensions: 0.19 ×
0.17 × 0.16 mm, Bruker SMART area-detector diffractometer,
MoKa radiation k = 0.71073 A, l = 0.260 mm−1, hmax = 22.57◦,
33 G. M. Sheldrick, SHELXL-97, Program for refinement of crystal
˚
41159 measured reflections, 19541 independent reflections, Rint
=
structures, University of Go¨ttingen, Germany, 1997.
3 1 1 6
O r g . B i o m o l . C h e m . , 2 0 0 5 , 3 , 3 1 0 5 – 3 1 1 6