Building [2]Catenanes around a Tris(diimine)ruthenium(2+) ([Ru(diimine)3]2+) Complex Core Used as Template

Article abstract of DOI:10.1002/hlca.200390345

In the course of the last two decades, the use of transition metals as templates for constructing catenanes has almost exclusively been restricted to tetrahedral copper(I). The present work is dealing with an octahedral metal, ruthenium(II), coordinated t

Full text of DOI:10.1002/hlca.200390345

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Building [2]Catenanes around a Tris(diimine)ruthenium(2‡)
([Ru(diimine)3]2‡) Complex Core Used as Template
by Pierre Mobian, Jean-Marc Kern*, and Jean-Pierre Sauvage*
¬
¬
¬
Laboratoire de Chimie Organo-Minerale, UMR 7513 du CNRS, Universite LouisPasteur, Faculte de Chimie, 4,
rue Blaise Pascal, F-67070 Strasbourg Cedex
(sauvage@chimie.u-strasbg.fr)
Dedicated to Duilio Arigoni on the occasion of his 75th birthday
In the course of the last two decades, the use of transition metals as templates for constructing catenanes has
almost exclusively been restricted to tetrahedral copper(I). The present work is dealing with an octahedral
metal, ruthenium(II), coordinated to three bidentate chelates. Incorporation of two chelates (1,10-phenanthro-
line) in a ring allowsto prepare a C2-symmetric ruthenium complex, the two chelates being disposed cis to one
another (see 142‡ and 162‡ in Scheme 5 and 6, resp.). The ring is large enough to accomodate a third chelate, thus
allowing the metal-directed threading of a long fragment containing the third chelate (2,2'-bipyridine derivative;
see 232‡ and 242‡ in Scheme 8). The last step consists of a ring-closing metathesis reaction with two terminal
olefins. The two ruthenium(II)-complexed catenanes 252‡ and 262‡ were prepared by using this strategy, each
containing a 42-membered ring interlocked to a larger macrocycle (50- or 63-membered ring) incorporating the
two 1,10-phenanthroline chelates. It is expected that these catenanes can be set in motion under light-
irradiation, thusbehaving asphotochemically driven molecular machines.
Introduction. Until now, octahedral transition-metal centers have been rarely
used as templates to construct topologically non-trivial molecules such as catenanes
and knots. The use of a bisterpy (terpy ˆ 2,2':6',2''-terpyridine) to make a [2]catenane
[1] is an early example [1]. More recently, it was shown that it is possible to form
[2]catenanes based on two tridentate ligands entwined around a first-row octahedral
transition metal in an extremely efficient way [2]. The synthesis of knots has been
driven by the use of two octahedral iron(II) centers, each metal being coordinated to
two terpy derivatives[3]. Another spectacular example isthe formation of an −open×
knot by using a long molecular thread incorporating three didentate chelates
embedded around a zinc(II) center [4].
Until now, there was no example of a [2]catenane constructed around a tris-
didentate chelate complex [5]. This is not surprising when we consider that the use of a
tetrahedral copper(I) centre as a template to promote the synthesis of interlocked
molecules has been particularly successful [6]. It may also be explained by the difficulty
to entwine two threadsusing three chelatesgathered around an octahedral transition-
metal center. A fundamental difference between tetrahedral and octahedral systems is
also related to chirality. Whereas tetrahedral complexes consisting of two intertwined
ligands are by nature achiral, tris-didentate octahedral complexes lead to interesting
configurational properties( L and D enantiomers). This particular feature could be
used to afford chiral catenanes, which makes the use of a three-chelate transition-metal

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complex astemplating core epsecially attractive. We would now like to report the
synthesis of [2]catenanes constructed around a [Ru(diimine)3]2‡ complex core1).
The design of the system and the synthetic strategy are depicted in Fig. 1. The main
feature of this system is that it is possible to insert an octahedral metal center in a ring
incorporating two didentate chelates and subsequently to thread a molecular fragment
bearing the third chelate through the ring. This latter step is of course driven by the
coordination of the thread to the metal. Finally, the catenane isobtained in a single
cyclization step.
Fig. 1. a) Schematic representation of a transition-metal-complexed [2]catenane containing two different rings
(one of the macrocyclesincorporatesa didentate chelate whereasthe other containstwo didentate coordinating
fragmentswith a cis arrangement). b) Synthetic strategy leading to the catenane (complexation of the transition
metal by the macrocycle incorporating two didentate moieties, threading of the didentate chelate through the
cavity of the resulting complex, cyclization of the didentate fragment by using a ring-closing metathesis (RCM)
reaction).
Tetradentate ligands consisting of two separate didentate ligands connected by an
appropriate bridge and leading to C2-symmetric complexes have already been
described. Of particular interest are the chiragens, reported by von Zelewsky and co-
workers [7] (a representative example of chiragen consists of two chiral bpy derivatives
(bpy ˆ 2,2'-bipyridine)) [7]. Our group hasreported a related type of C2-symmetric
1
)
A first preliminary communication has recently been published which describes one of the two catenanes
described in the present work [5a]; the second one describes the synthesis of a catenane whose structure is
close to that described in the present work, by using a double ring closing reaction in the last step [5b].

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complexes, with a ligand specifically designed to afford helical complexes with strict
control over the geometry of the compound. Interestingly, this ligand is able to form a
[Ru(phen)3]2‡-derivative complex (phen ˆ 1,10-phenanthroline) with a clearly identi-
fied axis bearing chemical functions [8][9]. In the present work, the substitution
positions on the bis-phen ligand are different from those of the previous axis-containing
complex. From the CPK models, this new ligand seems to be more appropriate for the
formation of cyclic complexes, as shown inScheme 1.
The synthetic procedure starts with the preparation of two new large rings
incorporating two phen units, i.e., of 12 and 13. The former consists of a 50-membered
ring, whereasthe latter, much larger, hasa 63-membered ring. Thees two different
macrocycles, on CPK models, look adapted to the formation of octahedral bis-phen
complexes, the two phen fragments being disposed cis to one another in the metal-
coordination sphere (see Scheme 1, B). Interestingly, the substitution positions of the 4-
alkoxyphenyl group (at C(8) and C(8') of the bis-phen moiety of these macrocycles)
are determining. By contrast, if 4-methoxyphenyl groups are introduced para to the N-
atomsof the phen moieties(at C(7) and C(7 ')), wrapping the corresponding ligand
around an octahedron leads to a system with a clearly identified axis, as shown in
Scheme 1 (see A). The choice of macrocycles 12 and 13 wasdictated by CPK models
and by synthesis considerations.
Macrocycles 12 and 13. Macrocycles 12 and 13 were prepared in five steps from
the 3-bromoquinolin-8-amine (1), which was itself synthetized according to the
literature procedure from the commercially available 8-nitroquinoline [10][11]. The
key intermediate, the bis-phenanthroline ligand 6, bearing two terminal phenol
functionalities, was obtained from 1 in four steps as shown in Scheme 2. Thus, 1 was
transformed to 2 in 67% yield in the presence of methyl vinyl ketone and sulfuric acid.
This procedure, described in the literature, is analogous to the classical Skraup reaction
to make substituted 1,10-phenanthroline, but, in our case, the use of arsenic pentaoxide
is unnecessary [12]. Suzuki coupling [13] between 2 and boronic ester 3 [14] yielded 4 in
80% yield after chromatography (alumina) and recrystallization. Ligand 5 was
prepared by deprotonation of 4 with lithium diisopropylamide (LDA); the corre-
sponding anion was then added to 0.5 equiv. of 1,4-bis(bromomethyl)benzene. The

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Scheme 1. Formation ofan Axial Complex A or a Macrocyclic Complex B. In both cases, connection of two
positions para to the N-atomsof the phen moietiesby the CH 2CH2ÀC6H4ÀCH2CH2 bridge leadsto a cis
arrangement. Introduction of aromatic groupsRC 6H4 at the other para positions leads to the axial complex A,
whereasthe macrocycle complex B can be obtained by utilizing the meta positions (C(8)) to attach the RC6H4
groups and, subsequently connecting these positions, the formation of a macrocyclic complex seems to be very
favorable.
poorly soluble compound 5 wasobtained in 53% yield after precipitation. By using a
classical ether deprotection method [15], i.e., treatment with pyridinium chloride in
refluxing pyridine, 5 wasconverted to 6 in 97% yield.
The dihalogeno fragment needed for the synthesis of macrocycles 12 and 13 from 6
iseither the diiodo derivative of pentaethylene glycol (for 12) or the long-chain

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Scheme 2. Synthesis ofKey Intermediate 6
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dibromide 11 bearing a 4,4'-isopropylidenebis[phenol]-derived moiety (for 13).
Dibromide 11 was easily synthesized starting from 4,4'-isopropylidenebis[phenol] (8)
by connecting a long arm (from 7) at each O-atom in basic medium (Scheme 3). The
oily diol 9 obtained in 87% yield wasthen converted to the dimesylate derivative 10,
and finally to the dibromide 11.
Macrocycles 12 and 13 were prepared in a similar manner by treating the bis-
phenanthroline ligand 6 with the dihalogeno fragment under high-dilution conditionsin
basic medium (Cs2CO3) according to Scheme 4 the productswere isolated in 23 and

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Scheme 3. Synthesis ofDibromide 11 Containing the 4,4'-Isopropylidenebis[phenol]-Derived Moiety
26% yield, respectively. These yields, although modest, are relatively satisfactory when
we consider that neither ligand 6 nor the dihalogeno fragments, the diiodo derivative of
pentaethylene glycol or 11, contain in their backbone oriented groupsable to favor the
formation of macrocyclic species. Macrocycles 12 and 13 gave MS and NMR data in
agreement with their structures (see Exper. Part).
Scheme 4. High-Dilution Reaction Leading to Macrocycles 12 and 13
Ruthenium(II) Complexes 142‡ and 162‡. Complex 142‡ wasformed by reacting
macrocycle 12 and [RuCl2(DMSO)4] [16] in refluxing 1,2-dichloroethane under high-

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dilution conditions( Scheme 5). The intermediate dichloro complex wasnot isolated;
instead the crude reaction mixture was heated under reflux in MeCN/H2O 80 :12 (v/v)
to replace the auxiliary chloro ligandsby MeCN. On TLC of the obtained crude
product, much to our surprise, two major spots were observed. The two corresponding
products were isolated by chromatography, in 21% yield for the less-polar fraction, and
in 26% yield for the more-polar fraction. Both products 142‡ and 152‡ (asPF salts)
À
6
exhibited the same ES-MS with m/z 1205.3 ([14(PF6)] or [15(PF6)] ), 530.2 ([14]2‡ or
‡
‡
[15]2‡), 489.1 ([14 À 2 MeCN]2‡ or [15 À 2 MeCN]2‡).
Scheme 5. Complexation of 12 to Ruthenium(II) Giving Two Different Isomers 142‡ and 152‡. The black dots
represent the ancillary ligands (MeCN).
Single crystals suitable for X-ray crystallography were obtained for both ruthenium
complex fractions by diffusion of a nonsolvent (iPr2O) into MeCN solution at room
temperature. Aview of the complex ion 142‡ corresponding to the first fraction is shown
in Fig. 2. It shows the coiling of the bis-chelate macrocycle around the RuII centre, to
form a C2-symmetric complex. The metal adopts a pseudo-octahedral geometry with
RuÀN distances in the range 2.02 2.06 ä. The coordination sphere of the metal is
slightly distorted, the N(6)ÀRuÀN(2) and N(2)ÀRuÀN(3) anglesbeing 95.6 and
83.168, respectively. Noteworthy is the O(1)ÀO(6) distance. The poly(oxyethane-1,2-

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diyl) chain which connectsO(1) to O(6) ismade up of 5 C ÀC and 10 CÀO bonds, and
the 14.89 ä value observed for the O(1)ÀO(6) distance indicates that the polyoxy-
ethane-1,2-diyl chain is almost fully extended. In other words, its size is just long enough
to allow the coiling-up of the ring around the metal, but it will certainly not allow
significant bending of the CH2(CH2OCH2)4CH2 fragment.
Fig. 2. X-Ray crystal structure of 142‡. H-Atomsare omitted for clarity. Selected bond distances[ä] and angles
[8]: RuÀN(1) 2.06, RuÀN(2) 2.04, RuÀN(3) 2.06, RuÀN(4) 2.05, RuÀN(5) 2.02, RuÀN(6) 2.05,
N(1)ÀRuÀN(2) 96.84, N(1)ÀRuÀN(3) 79.02, N(1)ÀRuÀN(4) 173.77, N(1)ÀRuÀN(5) 90.02,
N(1)ÀRuÀN(6) 98.19, N(2)ÀRuÀN(3) 83.16, N(2)ÀRuÀN(4) 79.07, N(2) RuÀN(5)172.73, N(2)ÀRuÀN(6)
95.60, N(3)ÀRuÀN(4) 95.74, N(3)ÀRuÀN(5) 95.81, N(3)ÀRuÀN(6) 176.81, N(4)ÀRuÀN(5) 93.90,
N(4)ÀRuÀN(6) 86.94, N(5)ÀRuÀN(6) 85.66.
The structure of the complex ion 152‡ corresponding to the second fraction was
unexpected. Contrary to the C2-symmetric complex 142‡, in 152‡, the macrocycle adopts
a C1 symmetry as shown in Fig. 3. The coordination sphere in 152‡ ismore distorted
than in the C2-symmetric analogue. The N(1)ÀRuÀN(4) angle is159.95 8, whereasthe
same angle in 142‡ is173.77 8. It is also interesting to note that the polyether chain is less
stretched in the case of 152‡ (distance O(1)ÀO(6) 7.91 ä), by comparison with 142‡
(distance O(1)ÀO(6) 14.89 ä).

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Fig. 3. X-Ray crystal structure of 152‡. H-Atomsare omitted for clarity. Selected bond distances[ä] and angles
[8]: RuÀN(1) 2.07, RuÀN(2) 2.05, RuÀN(3) 2.03, RuÀN(4) 2.08, RuÀN(5) 2.03, RuÀN(6) 2.03,
N(1)ÀRuÀN(2) 86.94, N(1)ÀRuÀN(3) 79.11, N(1)ÀRuÀN(4) 159.95, N(1)ÀRuÀN(5) 98.18,
N(1)ÀRuÀN(6) 94.97, N(2)ÀRuÀN(3) 91.91, N(2)ÀRuÀN(4) 79.31, N(2)ÀRuÀN(5) 174.78,
N(2)ÀRuÀN(6) 91.56, N(3)ÀRuÀN(4) 86.75, N(3)ÀRuÀN(5) 89.96, N(3)ÀRuÀN(6) 172.96,
N(4)ÀRuÀN(5) 95.94, N(4)ÀRuÀN(6) 99.89, N(5)ÀRuÀN(6) 87.06.
In contrast to the formation of 142‡, coordination of 13 to RuII wasperformed
without using high-dilution conditions. A solution of macrocycle 13 (2.2 ¥ 10À4 m) and
1 equiv. of [RuCl2(DMSO)4] in 1,2-dichloroethane wasrefluxed under Ar during 4 h
(Scheme 6). After evaporation, the residue was dissolved and refluxed for 4 h in
MeCN/H2O 80 :20. Again, two compoundswere isolated after column chromatography
(silica gel). The less-polar one was obtained in 25% yield and attributed to the C2-
symmetric complex 162‡, due to the simplicity of his NMR spectra. The protons of the
phenylene bridge in the free macrocycle 13 are homotopic (see Scheme 4). Splitting of
1
the corresponding signal in the H-NMR of 162‡ was observed, indicating in that case
the diastereotopic nature of these protons. The more-polar compound 172‡ wasisolated
in 25% yield and itsstructure determined by comparing the very complicated aromatic
zone of its 1H-NMR spectrum with the corresponding aromatic zone of 152‡. These two
regions were very similar, and this observation is in full accordance with the C1
symmetry of the bis-acetonitrile complex 172‡.

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Scheme 6. Complexation of 13 to Ruthenium(II) Giving Two Different Isomers 162‡ and 172‡
It isnoteworthy that the complexes 142‡, and 162‡ are rare examplesof a bis-phen,
or, more generally, a bis-didentate octahedral complex with a cis-arrangement,
embedded in a ring.
Threading Reaction and Formation of Catenanes. For the threading reaction, the
2,2'-bipyridine derivative 22 was used. This ligand, substituted at C(6) and C(6') by two
long chainsterminated by olefinic group,s wasprepared in three tsepsfrom 6,6
'-
dimethyl-2,2'-bipyridine (dmbp), asdescribed in Scheme 7. By deprotonation of dmbp
with LDA in THF, followed by addition of 2 equiv. of THP-protected 2-[2-(2-
Scheme 7. Synthesis ofthe −Thread Chelate×, the Bipyridine Derivative 22

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iodoethoxy)ethoxy]ethanol 18 (THP ˆ tetrahydro-2H-pyran-2-yl), 19 wasobtained in
32% yield. Deprotection of 19 afforded diol 20 in 95% yield. Thisdiol wasconverted
into 22 following the Williamson methodology (NaH, DMF) by reaction with 2 equiv.
of the polyether chain 21 bearing a terminal olefin moiety (64% yield).
The reaction conditionsfor threading the third chelate 22 into 142‡ or 162‡ were the
same for both complexes (Scheme 8). Threading took place under relatively harsh
conditions(ethylene glycol; 140 8), and the catenane precursors 232‡ and 242‡ were
obtained in surprisingly good yield (56 and 46%, resp.). This step, which is identical to
passing a long thread (44 atoms) through the eye of a needle, represents also a key
reaction whose success was not guaranteed, especially when one considers that it
requiressevere conditions.
The final catenanes 252‡ and 262‡ were prepared from 232‡ and 242‡, respectively, by
ring-closing metathesis (RCM) [17]. A CH2Cl2 solution of complex 232‡ or 242‡ and
[RuCl2 ˆ CHPh(PCy3)2] (20 mol-%) were stirred under Ar for three days (Scheme 9).
Scheme 8. Threading Reaction Leading to Precatenanes 232‡ and 242‡

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Scheme 9. Ring Closing Methathesis Reactions Affording the Catenanes 252‡ and 262‡
Catenanes 252‡ and 262‡ were isolated in 68 and 76% yield, respectively. These
preparative yields are in the same range as those obtained for making other transition-
metal-containing catenanes and knots by means of a similar RCM-based approach [18].
Catenanes 252‡ and 262‡, which are red-orange solids, were fully characterized by
various spectroscopic techniques. The ES-MS and 1H-NMR spectra afford clear
evidence for their structure.
Another probe to confirm that the synthetic route afforded the expected catenanes
isthe compariosn of the
1H-NMR spectra of the complexes isolated during the
synthesis. Fig. 4 shows the 1H-NMR signals of the aromatic protons of the complexions
142‡, 232‡, and 252‡. A similar comparison can be done for catenane 262‡ (not shown).
The most-relevant change in going from 142‡ to 232‡ is the strong upfield shift of the
signal of HÀC(9,9') of the bis-phenanthroline core (Dd ˆ 1.43 ppm). Thiscould be
explained by the ring-current effect of the bipyridine unit on these two protons when
the third chelate isthreaded into the macrocyclic cavity. When going from the

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precatenane 232‡ to the catenane itself 252‡, disappearance of the two signals of the
olefinic protons is observed, and, simultaneously, one new signal, which appears as a m
at d 5.77, is assigned to the olefinic protons at the CˆC bond formed by the RCM
reaction; however, a definitive assignment of the (Z)- or (E)-configuration of the CˆC
bound can not be made. Moreover, the simplicity of the 1H-NMR spectrum of 252‡ isin
accordance with the expected C2 symmetry of the catenane.
Conclusions. The two new [2]catenanes 252‡ and 262‡ were synthesized by using
the three-dimensional-template effect of an octahedral transition metal (RuII). The
Fig. 4. 1H-NMR Region ofaromatic protons of a) 142‡, b) 232‡, and c) 252‡. H9 ˆ HÀC(9,9') of the bis-
phenanthroline core; H4b ˆ HÀC(4,4') of the bipyridine moiety.

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strategy is such that each catenane consists of two different rings: the smaller, 42-
membered ring incorporatesa bpy fragment, whereasthe other, 50- or 63-membered
ring containsthe two other diimine chelatesof the octahedral metal complex (1,10-
phenanthroline). Interestingly, due to the chiral nature of a tris-chelate complex, both
[2]catenanesare chiral, with a C2 symmetry. These catenanes are with no doubt the first
examples of an interlocking ring system built on a tris-didentate chelate transition-
metal complex used as template. The photochemical properties of these two
ruthenium(II)-complexed [2] catenanesare now under tsudy, in relation to light-
driven molecular machines[19]. They are expected to undergo large amplitude
motionsunder the action of a photonic stimulus.
We thank the CNRS, the European Community, and the French Ministry ofEducation for their financial
support (fellowship to P. M. ).
Experimental Part
General. Oxygen-sensitive reactions were conducted under a positive pressure of Ar by Schlenk techniques.
All solvents and reagents were of the highest quality available and were used as received without further
purification. CC ˆ Column chromatography. Absorption spectra: Uvikon XS spectrometer, lmax (log e) in nm.
1H-NMR Spectra: Bruker AVANCE-300 (300 MHz), Bruker AVANCE-400 (400 MHz), or Bruker AVANCE-
500 (500 MHz) spectrometer; deuterated solvent as lock and residual solvent as internal reference; d in ppm, J
in Hz. MS (in m/z): VG-BIOQ triple-quadrupole spectrometer for electrospray ionization (ES) (positive
mode); ZAB-HF (FAB) spectrometer for fast-atom bombardment (FAB).
3-Bromo-7-methyl-1,10-phenanthroline (2). But-3-en-2-one (1.7 ml, 21 mmol) wasadded dropwise to 70%
sulfuric acid (8.5 ml) containing 3-bromoquinolin-8-amine (1; 2.90 g, 13 mmol) and a cat. amount of NaI
(0.019 g, 0.13 mmol). The soln. became dark and viscous after heating at 1108 for 1 h. After cooling, the pH of
the soln. was raised to 8 by addition of 1m Na2CO3 (100 ml). The precipitate that appeared wasextracted with
CH2Cl2 (150 ml). The resulting org. phase was treated with charcoal, dried (MgSO4), and evaporated, and the
residual solid purified by CC (SiO2, CH2Cl2/MeOH): 2 (2 g, 67%). White solid. M.p. 1708. 1H-NMR (200 MHz,
CDCl3): 9.2 (d, 4J ˆ 2.2, HÀC(2)); 9.06 (d, 3J ˆ 4.6, HÀC(9)); 8.43 (d, 4J ˆ 2.2, HÀC(4)); 8.08 (d, 3J ˆ 9.1,
HÀC(6), or HÀC(5)); 7.77 (d, 3J ˆ 9.1, HÀC(5) or HÀC(6)); 7.51 (d, 3J ˆ 3.9, HÀC(8)); 2.82 (s, Me). Anal.
calc. for C13H9BrN2: C 57.16, H 3.32, N 10.25; found: C 57.20, H 3.10, N 10.09.
3-(4-Methoxyphenyl)-7-methyl-1,10-phenanthroline (4). Under Ar, 2m aq. NaOH (200 ml) wastransferred
by canula to toluene (200 ml) containing 2 (8.29 g, 30.4 mmol) and tetrakis(triphenylphosphine)palladium
(1.77 g, 1.52 mmol). After addition of a MeOH soln. (15 ml) of 3 (8.81 g, 45 mmol), the mixture washeated
overnight at 508. After cooling, the aq. phase was extracted with CH2Cl2 (3Â). The combined org. phase was
dried (MgSO4) and evaporated. The residual solid was purified by CC (alumina, CH2Cl2/MeOH 99 :1), and
crystallized from toluene: 4 (7.35 g, 80%). Beige solid. 1H-NMR (200 MHz, CDCl3): 9.39 (d, 4J ˆ 2.4, HÀC(9));
9.03 (d, 4J ˆ 4.4, HÀC(2)); 8.35 (d, 4J ˆ 2.4, HÀC(7)); 8.04 (d, 3J ˆ 9.1, HÀC(5)); 7.85 (d, 3J ˆ 9.1, HÀC(6)); 7.72
(d, 3J ˆ 8.8, 2 Ho); 7.48 (d, 4J ˆ 4.4, HÀC(3)); 7.10 (d, 3J ˆ 8.8, 2 Hm); 2.82 (s, Me); 3.92 (s, MeO).
4,4'-(1,4-Phenylenediethane-2,1-diyl)bis[8-(4-methoxyphenyl)-1,10-phenanthroline] (5). Under Ar, 1.4m
i
BuLi (1.7 ml) wasadded at 0 8 to freshly distilled Pr2NH (0.3 ml) in THF (7 ml). The mixture wasstirred at
08 for 1 h. A soln. of 4 (700 mg, 2.33 mol) in THF (17.5 ml) wastransferred via canula at 08 to thissoln. (
!
immediately dark-blue). After 20 min stirring at r.t., the soln. was cooled again to 08, and 1,4-bis(bromo-
methyl)benzene (307 mg, 1.15 mmol) in THF (9 ml) wasadded. After tsirring overnight at r.t., EtOH (30
drops) and H2O (100 ml) were successively added. The precipitate that appeared was filtered off and washed
with CH2Cl2: 5 (587 mg, 53%). Yellow solid. 1H-NMR (200 MHz, CDCl3)2): 9.42 (d, 4J ˆ 2.2, 2 H, HÀC(9,9'));
9.08 (d, 3J ˆ 4.4, 2 H, HÀC(2,2')); 8.33 (d, 4J ˆ 2.2, 2 H, HÀC(7,7')); 8.04 (d, 3J ˆ 9.1, 2 H, HÀC(5,5')); 7.83
(d, 3J ˆ 9.1, 2 H, HÀC(6,6')); 7.74 (d, 3J ˆ 8.6, 4 Ho); 7.40 (d, 3J ˆ 4.6, 2 H, HÀC(3,3')); 7.14 (s, C6H4); 7.12
(d, 3J ˆ 8.6, 4 Hm); 3.93 (s, 2 MeO); 3.45 (m, 4 H, HÀC(a,a')); 3.11 (m, 4 H, HÀC(b,b')). MALDI-TOF-MS:
‡
703 ([5 ‡ H] ; calc. 702.3).
2
)
Arbitrary numbering; see Schemes 2 4, 6, and 7.

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4,4'-[1,4-Phenylenebis(ethane-2,1-diyl[1,10]phenanthroline-7,3-diyl]bis[phenol] (6). Under stirring, 12m
HCl (28 ml) wasadded to pyridine (26 ml). H 2O wasditsilled off from the mixture until itsinternal temp.
rose to 2208. The anh. pyridinium chloride soln. was cooled to 1508. Then 5 (1.73 g, 2.4 mmol) wasadded asa
solid under Ar flush, and the mixture was refluxed (2208) under Ar for 4 h. The mixture wascooled to 90 8, hot
H2O was added, and the resulting suspension was poured into lukewarm H2O (100 ml). The precipitate was
filtered off, washed with H2O, suspended in EtOH/H2O 2 :1 (300 ml), and neutralized with 0.1m NaOH. The
suspension was filtered off and dried for three days under high vacuum: 6 (1.61 g, 97%). Green solid. 1H-NMR
(200 MHz, (D6)DMSO)2): 9.86 (s, 2 OH); 9.40 (br. d, 2 H, HÀC(8,8')); 9.00 (d, 3J ˆ 4.4, 2 H, HÀC(9,9')); 8.71
(br. d, 2 H, HÀC(4,4')); 8.4 (d, 3J ˆ 8.4, 2 H, HÀC(5,5'), or HÀC(6,6')); 8.0 (d, 3J ˆ 8.4, 2 H, HÀC(5,5) or
HÀC(6,6')); 7.83 (d, 3J ˆ 8.4, 4 Ho); 7.61 (d, 3J ˆ 4.5, 2 H, HÀC(8,8')); 7.23 (s, C6H4); 7.01 (d, 3J ˆ 8.4, 4 Hm); 3.05
‡
(m, 4 H, CH2CH2). FAB-MS: 675.2 ([6 ‡ H] ; calc. 674.2).
15,16,18,19,21,22,24,25,27,28,43,44,49,50-Tetradecahydro-10,13:30,33:45,48-trietheno-9,4,7:34,36,39-bis-
(methenonitrilomethyno)[1,4,7,10,13,16]hexaoxacyclohexatetracontino[26,27-c:37,36-c']dipyridine (12). Com-
pound 6 (1.5 g, 2.22 mmol) and 1,14-diiodo-3,6,9,12-tetraoxatetradecane (1.21 g, 2.66 mmol) were dissolved
under Ar in DMSO (50 ml) and DMF (110 ml), and the soln. was added at a controlled rate (0.1 drop sÀ1) via a
dropping funnel to a suspension of Cs2CO3 (2.9 g, 8.88 mmol) in DMF (300 ml) maintained at 608. Then the soln.
was further stirred and heated for 4 h. DMF was evaporated, the residue dissolved in CH2Cl2, the soln. washed
with H2O (7Â) to remove the remaining DMSO, the org. phase evaporated, and the residue purified by CC
(alumina, CH2Cl2/MeOH 98 :2): 12 (450 mg, 23%). White powder. 1H-NMR (400 MHz, CD2Cl2)2): 9.36 (d, 4J ˆ
2.3, 2 H, HÀC(9,9')); 9.08 (d, 3J ˆ 4.5, 2 H, HÀC(2,2')); 8.12 (d, 4J ˆ 2.3, 2 H, HÀC(7,7')); 7.67 (d, 3J ˆ 6.6, 4 Ho);
7.59 (d, 3J ˆ 4.5, 2 H, HÀC(3,3')); 7.41 (d, 3J ˆ 9.1, 2 H, HÀC(5,5')); 7.34 (d, 3J ˆ 9.1, 2 H, HÀC(6,6')); 7.05
(d, 3J ˆ 6.6, 4 Hm); 6.82 (s, CH2C6H4CH2); 4.10 (m, 4 H, Ha); 3.81 (m, 4 H, Hb); 3.70 (m, 12 H, Hg,d,e); 3.33
‡
(t, 3J ˆ 7.3, 4 H, HÀC(a,a')); 3.06 (t, 3J ˆ 7.3, 4 H, HÀC(b,b')). ES-MS: 877.6 ([12 ‡ H] ; calc. 876.3).
2,2'-[(1-Methylethylidene)bis(4,1-phenyleneoxyethane-2,1-diyloxyethane-2,1-diyloxy]bis[ethanol] (9). A
degassed soln. of 4,4'-(1-methylethylidene)bis[phenol] (1.22 g, 5.3 mmol) and Cs2CO3 (7 g, 21.5 mmol) in
anh. DMF (50 ml) washeated at 60 8. A soln. of 2-[2-(2-iodoethoxy)ethoxy]ethanol (7; 3.47 g, 13.4 mmol) in
DMF (5 ml) was added to this degassed soln. The mixture was stirred under Ar at 608 during 24 h. After
evaporation, the residue was extracted with CH2Cl2; the org. layer washed with H2O, dried (Na2CO3), and
evaporated, and the residue purified by CC (Al2O3, CH2Cl2/MeOH, 98 :2): 9 (2.31 g, 87%). White oil. 1H-NMR
(300 MHz, CDCl3)2): 7.1 (d, 3J ˆ 8.9, 4 Hm'); 6.8 (d, 3J ˆ 8.9, 4 Ho'); 4.09 (t, 3J ˆ 4.5, 4 Hl); 3.83 (t, 3J ˆ 4.5, 4 He);
3.68 (m, 12 H, Hb,g,d); 3.58 (t, 3J ˆ 4.1, 4 H, Ha); 1.61 (s, 2 Me).
2,2'-[(1-Methylethylidene)bis(4,1-phenyleneoxyethane-2,1-diyloxyethane-2,1-diyloxy]bis[ethanol] Di-
methanesulfonate (10). A soln. of 9 (2.32 g, 4.7 mmol) and freshly distilled Et3N (4 ml, 28 mmol) in freshly
distilled CH2Cl2 (50 ml) wascooled to À58 under Ar, and methanesulfonyl chloride (1.1 ml, 28 mmol) was
added slowly. After 4 h at À58, the mixture wasbrought to r.t., washed with H 2O, and dried (Na2SO4), and
evaporated: 10 (2.855 g, 93%). Oil. 1H-NMR (300 MHz, CDCl3)2): 7.1 (d, 3J ˆ 8.9, 4 Hm'); 6.8 (d, 3J ˆ 8.9, 4 Ho');
4.36 (t, 3J ˆ 2.8, 4 Ha); 4.08 (t, 3J ˆ 4.9, 4 Hl); 3.82 (t, 3J ˆ 4.5, 4 He); 3.77 (t, 3J ˆ 2.8, 4 Hb); 3.69 (m, 8 H, Hg,d),
3.03 (s, 2 MeS); 1.62 (s, 2 Me).
1,1'-(1-Methylethylidene)bis[4-{2-[2-(2-iodoethoxy)ethoxy]ethoxy}benzene] (11). The soln. of 10 (2.85 g,
4 mmol) in acetone (80 ml) was refluxed for 4 h in the presence of a large excess of LiBr (3.8 g, 44 mmol). After
evaporation, the crude mixture wastaken up in CH 2Cl2/H2O, the org. phase dried (Na2SO4) and evaporated, and
the residue purified CC (Al2O3, CH2Cl2): 11 (2.5 g, 92%). White oil. 1H-NMR (300 MHz, CDCl3)2): 7.1 (d, 3J ˆ
8.9, 4 Hm'); 6.8 (d, 3J ˆ 8.9, 4 Ho'); 4.12 (t, 3J ˆ 4.7, 4 Hl); 3.8 (m, 8 H, He,a); 3.72 (m, 8 H, Hg,d); 3.45 (t, 3J ˆ 6.3,
4 Hb); 1.61 (s, 2 Me).
15,16,18,19,21,22,34,35,37,38,40,41,56,57,62,63-Hexadecahydro-28,28-dimethyl-
10,13:24,27:29,32:43,46:58,61-pentaetheno-9,4,7:47,49,52-bis(methenonitrilomethyno)-28H-
[1,4,7,10,20,23,26,29]octaoxacyclononapentacontino[39,40-c:50,49-c']dipyridine (13). Asdescribed for 12, with 6
(0.4 g, 4 mmol), 11 (0.4 g, 6.5 mmol), DMSO (60 ml), DMF (40 ml), Cs2CO3 (2 g, 6 mmol), and DMF (200 ml).
1
CC (alumina, CH2Cl2/MeOH 99 :1) gave 13 (177 mg, 26%). Glassy solid. H-NMR (300 MHz, CDCl3)2): 9.36
(d, 4J ˆ 2.3, 2 H, HÀC(9,9')); 9.0 (d, 3J ˆ 4.5, 2 H, HÀC(2,2')); 8.20 (d, 4J ˆ 2.3, 2 H, HÀC(7,7')); 7.71 (d, 3J ˆ 9.1,
2 H, HÀC(5,5') or HÀC(6,6')); 7.61 (2d, 6 H, 4 Ho); 7.31 (d, 3J ˆ 4.5, 2 H, HÀC(3,3')); 7.11 6.99 (2d, 8 H, 3J ˆ
9.2, 4 Hm', 4 Ho'); 6.80 (d, s, CH2C6H4CH2, 4 Hm); 4.15 (m, 8 H, Ha,l), 3.84 (m, 8 H, Hb,e); 3.74 (s, 8 H, Hg,d); 3.46
‡
(t, 3J ˆ 6.9, 4 H, HÀC(a,a')); 3.00 (t, 3J ˆ 6.9, 4 H, HÀC(b,b')); 1.59 (s, 2 Me). FAB-MS: 1131.8 ([13 ‡ H] ; calc.
1131.5).
Bis(acetonitrile){15,16,18,19,21,22,24,25,27,28,43,44,49,50-tetradecahydro-10,13:30,33:45,48-trietheno-
9,4,7:34,36,3 9-bis(methenonitrilomethyno)[1,4,7,10,13,16]hexaoxacyclohexatetracontino[26,27-c:37,36-c']dipyri-

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Helvetica Chimica Acta Vol. 86 (2003)
dine-kN3,kN40,kN54,kN61}ruthenium(2‡) Bis[hexafluorophosphate(1 À )] ([14](PF6)2 and [15](PF6)2) Macro-
cycle 12 (126 mg, 0.143 mmol) was dissolved in 1,2-dichloroethane (70 ml) under Ar. [RuCl2(DMSO)4]
(0.143 mmol) was dissolved in 1,2-dichloroethane (70 ml) under Ar. The two solns. were simultaneously added
within 3 daysto refluxing 1,2-dichloroethane (650 ml) under Ar in a high-dilution device under vigourous
magnetic stirring. The crude of the reaction was then dissolved in a MeCN/H2O 80 :20 (100 ml). After 3 h of
heating, the purple mixture had turned to a yellow-orange soln. The reaction was stopped, and aq. sat. K(PF6)
osln. (50 ml) wasadded. The MeCN wasevaporated to afford a black precipitate which wasioslated by
filtration. This solid was purified by CC (silica gel, MeCN/H2O/sat. aq. KNO3 soln. 100 :5 :1). The first fraction
yielded, after anion exchange (PF6/NO3), the C2-isomer, [14](PF6)2 (42 mg, 21%). Red-orange solid. Crystals
i
for X-ray analysis were obtained by slow diffusion of Pr2O into a soln. of [14](PF6)2 in MeCN (see Table).
1H-NMR (300 MHz, MeCN)2): 9.54 (d, 4J ˆ 1.8, 2 H, HÀC(9,9')); 8.95 (d, 4J ˆ 1.8, 2 H, HÀC(7,7')); 8.4 8.2
(2d, 3J ˆ 9.1, 4 H, HÀC(5,5'), HÀC(6,6')); 7.86 (d, 3J ˆ 8.6, 4 Ho); 7.32 (d, 3J ˆ 8.6, 4 Hm); 7.24 (d, 3J ˆ 5.3, 2 H,
HÀC(2,2')); 6.94 (d, 3J ˆ 5.3, 2 H, HÀC(3,3')); 6.76 (d, 3J ˆ 8.1, 2 H, HÀC(c')); 6.36 (d, 3J ˆ 8.1, 2 H, HÀC(c));
4.59 (m, 2 H, Ha or Ha'); 4.31 (m, 2 H, Ha or Ha'); 4 3 (m, 24 H, Hb,g,d,e, HÀC(a,a',b,b')); 2.26 (s, 2 MeCN). ES-
‡
MS: 1205 ([14(PF6] , calc. 1204), 530.2 ([14]2‡, calc. 529.5), 489.1 ([14 À 2MeCN]2‡, calc. 488.5).
Table. X-Ray Experimental Data for [14] (PF6)2 and [15](PF6)2
[14](PF6)2
[15](PF6)2
Formula
C124H124F24N14O14P4Ru2
C62H63F12N7O7P2Ru
C120H116N12O12Ru2 ¥4PF6 ¥2 CH3CN ¥ 2 H2O C60H58N6O6Ru ¥ 2 PF6 ¥ CH3CN ¥ H2O
Mr
2816.45
1409.23
Crystal system
Space group
a [ä]
b [ä]
c [ä]
a [8]
b [8]
g [8]
V [ä3]
triclinic
P-1
17.0461(2)
18.0355(2)
24.1003(3)
102.988(5)
94.447(5)
101.215(5)
triclinic
P-1
15.2790(1)
15.9553(2)
15.9775(2)
94.990(5)
117.763(5)
109.815(5)
3099.1(3)
2
7024.7(1)
2
Z
Color
red
light red
Crystal dim. [mm]
0.12 Â 0.10 Â 0.10
0.10 Â 0.10 Â 0.06
Dcalc [gcmÀ3
F(000)
]
1.33
1.51
2884
0.353
1444
0.400
m [mmÀ1
]
Trans. min., max.
Temp. [K]
0.958, 0.965
173
0.9468, 1.0000
173
Wavelength [ä]
Radiation
Diffractometer
Scan mode
0.71073
0.71073
MoKa graphite monochromated
KappaCCD
f scans
MoKa graphite monochromated
KappaCCD
f scans
hkl limits
q limits[ 8]
Number of data measured
À 23.3, À25.24, À26.33
0.21, À22.21, À22.19
2.5, 30.07
18083
2.5, 30.03
56477
Number of data with I > 3s(I) 18135
13474
Number of variables1672
820
R
Rw
0.123
0.149
1.224
1.199
0.063
0.074
1.013
G.o.f.
Largest peak in final

Helvetica Chimica Acta Vol. 86 (2003)
4211
The second fraction yielded, after anion exchange, the C1-isomer [15](PF6)2 (51 mg, 26%). Red-orange
‡
solid. Crystals for X-ray analysis were obtained as for [14](PF6)2: Table. ES-MS: 1205.3 ([15(PF6)] ; calc.
1204),530.2 ([15]2‡, calc. 529.5), 489.2 ([15 À 2CH3CN]2‡; calc. 488.5).
Bis(acetonitrile){15,16,18,19,21,22,34,35,37,38,40,41,56,57,62,63-hexadecahydro-28,28-dimethyl-10,13:24,27:29,
32:43,46:58,61-pentaetheno-9,4,7:47,49,52-bis(methenonitrilomethyno)-28H-[1,4,7,10,20,23,26,29]octaoxacyclo-
nonapentacontino[39,40-c:50,49-c']dipyridine-kN3,kN53,kN67,kN78}ruthenium(2‡) Bis[hexafluorophosphate-
(1 À )] ([16)(PF6)2 and [17](PF6)2). Compound 13 (70 mg, 6.1 ¥ 10À5 mol) and [RuCl2(DMSO)4] (0.143 mmol)
were dissolved in 1,2-dichloromethane (280 ml). The soln. was degassed and refluxed under Ar for 4 h
(yellow ! dark violet). The dark violet soln. was evaporated and this crude was dissolved in (100 ml) of MeCN/
H2O 80 :20 (100 ml). After 2 h of heating, the purple mixture turned to a yellow-orange soln. The reaction was
stopped, and aq. sat. K(PF6) soln. (50 ml) wasadded. The MeCN wasevaporated to afford a precipitate, which
was isolated by filtration. This solid was purified by CC (silica gel, MeCN/H2O/sat. aq. KNO3 soln. 100 :5 :1).
The first fraction, after anion exchange, gave [16](PF6)2 (25 mg, 25%). Red-orange solid. 1H-NMR (300 MHz,
MeCN)2): d 9.81 (d, 4J ˆ 1.7, 2 H, HÀC(9,9')); 9.03 (d, 4J ˆ 1.7, 2 H, HÀC(7,7')); 8.4 8.3 (2d, 3J ˆ 9.1, 4 H,
HÀC(5,5'), HÀC(6,6')); 8.06 (d, 3J ˆ 8.7, 4 Ho); 7.32 (d, 3J ˆ 8.6, 4 Hm); 7.24 (d, 3J ˆ 5.5, 2 H, HÀC(2,2')); 6.94
(d, 3J ˆ 5.3, HÀC(3,3')); 6.82 (d, 3J ˆ 8.8, 4 Ho'); 6.66 (d, 3J ˆ 8.8, 6 H, 2 HÀC(c'), 4 Hm'); 6.36 (d, 3J ˆ 8.1, 2 H,
HÀC(c)); 4.41 (m, 4 Ha); 4 3 (m, 28 H, Hb,g,d,e,l, CCH2CH2C); 2.08 (s, MeCN); 1.31 (s, Me3CN). ES-MS:
‡
‡
1459.6 ([16(PF6)] ; calc. 1459), 657.4 ([16]2‡; calc. 657), 636.8 ([16(PF6) À CH3CN] ; calc. 636.5), 636.5 ([16 À
‡
2CH3CN] ; calc. 616).
Furthermore, the second fraction from the chromatography led to the C1-isomer (25 mg, [17](PF6)2 25%).
Red-orange solid.
6,6'-Bis{3-{2-[2-(tetrahydro-2H-pyran-2-yl)ethoxy]ethoxy}propyl}-2,2'-bipyridine (19). Under Ar, 1.7m
i
BuLi (5.75 ml, 9.76 mmol) was added dropwise to a soln. of Pr2NH (1.36 ml, 9.76 mmol) in distilled THF
(20 ml). A degassed soln. of 6,6'-dimethyl-2,2'-bipyridine (0.75 g, 4.07 mmol) in distilled THF (20 ml) was
cooled to À788, and the freshly prepared LDA soln. was added via cannula (yellow ! green). The mixture was
stirred during 2 h at À788, after which the mixture was stirred at r.t. during 2 min. The deep purple soln. was
cooled to À788 again. Meanwhile, a soln. of tetrahydro-2-{2-[2-(2-iodoethoxy)ethoxy]ethoxy}-2H-pyran (18)
(3.07 g, 8.95 mmol) in distilled THF (20 ml) was cooled to À788 and degassed. This soln. was then transferred
under Ar onto the 6,6'-dimethyl-2,2'-bipyridine soln. at À788 ( ! dark red). The soln. was stirred overnight. The
final soln. was hydrolyzed with H2O (80 ml). Some CH2Cl2 wasadded, the org. layer dried (MgSO 4), and
evaporated, and the product purified by CC (alumina, Et2O/MeOH 99 :1): 19 (798 mg, 31.8%). Yellow oil.
1H-NMR (200 MHz, CDCl3)2): 8.21 (d, 3J ˆ 7.6, 2 H, HÀC(3,3')); 7.65 (t, 3J ˆ 7.7, 2 H, H ÀC(4,4')); 7.12 (d, 3J ˆ
7.5, 2 H, HÀC(5,5')); 4.60 (t, 3J ˆ 3.0, 2 H of THP); 3.85 (m, 4 H of THP); 3.70 3.30 (m, 20 H, Hb f); 2.89
(t, 3J ˆ 8.0, 4 Ha'); 2.05 (m, 4 Ha); 1.8 1.3 (m, 12 H of THP).
2,2'-[2,2'-Bipyridine-6,6'-diylbis(propane-3,1-diyloxyethane-2,1-diyloxy)]bis[ethanol] (20). A soln. of 19
(840 mg, 1.19 mmol) in EtOH (150 ml) wasrefluxed, and five dropsof 37% HCl soln. were added. The reflux
was maintained for 16 h. After evaporation, the residue was dissolved in CH2Cl2 and neutralized with an aq.
NaHCO3 soln. (100 ml). The org. layer was dried and evaporated: 20 (507 mg, 95.5%), which wasused without
further purification. 1H-NMR (200 MHz, CDCl3)2): 8.22 (d, 3J ˆ 7.7, 2 H, H ÀC(3,3')); 7.69 (t, 3J ˆ 7.7, 2 H,
HÀC(4,4')); 7.14 (d, 3J ˆ 7.5, 2 H, HÀC(5,5')); 3.71 3.53 (m, 20 H, Hb,c,d,e,f); 2.92 (t, 3J ˆ 8.0, 4 Ha'); 2.05
(m, 4 Ha).
6,6'-Bis(4,7,10,13,16-pentaoxanonadec-18-en-1-yl)-2,2'-bipyridine (22). A soln. (10 ml) of DMF containing
NaH (120 mg, 0.234 mmol) and 20 (300 mg, 0.6 mmol) wasstirred for 1 h at 60 8. Then 21 (559 mg, 2.6 mmol) in
DMF (5 ml) wasadded dropwise, and heating wascontinued overnight. DMF wasevaporated, the crude taken
up with CH2Cl2, the soln. washed with H2O, dried (MgSO4), and evaporated, and the oily residue purified by CC
(silica gel, CH2Cl2/MeOH 97 :3): 22 (304 mg, 64%). Pale oil. 1H-NMR (300 MHz, CDCl3)2): 7.71 (d, 3J ˆ 7.7, 2 h,
HÀC(3,3')); 7.66 (t, 3J ˆ 7.7, 2 H, H ÀC(4,4')); 7.12 (d, 3J ˆ 7.7, 2 H, H ÀC(5,5')); 5.89 (m, 2 Hr); 5.18 (m, 4 H,
Hs,t); 3.98 (m, 2 Hq); 3.60 (m, 36 H, Hf,g,h,i,j,k,l,n,p); 2.92 (t, 3J ˆ 7.9, 4 Hd); 2.09 (m, 4 He).
[6,6'-Bis(4,7,10,13,16-pentaoxanonadec-18-en-1-yl)-2,2'-bipyridine-kN1,kN1']{15,16,18,19,21,22,24,25,27,28,
43,44,49,50-tetradecahydro-10,13:30,33:45,48-trietheno-9,4,7:34,36,39-bis(methenonitrilomethyno)[1,4,7,10,13,16]-
hexaoxacyclohexatetracontino[26,27-c:37,36-c']dipyridine-kN3,kN40,kN54,kN61}ruthenium(2‡) Bis[hexafluoro-
phosphate(1 À )] ([23](PF6)2). Complex [14](PF6)2 (38 mg, 2.7 ¥ 10À5 mol) and 22 (23 mg, 3.3 ¥ 10À5 mol) were
heated together in a degassed soln. of ethylene glycol (5 ml) for 2 h at 1408. After cooling, aq. sat. K(PF6) soln.
(5 ml) wasadded. The formed precipitate wasisolated by filtration, washed with H 2O, and purified by CC (silica
gel, MeCN/H2O/sat. aq. KNO3 soln. 100 :7:1). Anion exchange (NO3/PF6) yielded [23](PF6)2 (30 mg, 56%).
Orange solid. 1H-NMR (300 MHz, CD3CN)2): 8.80 (d, 4J ˆ 1.7, 2 H, HÀC(7,7')); 8.40 (d, 3J ˆ 9.0, 2 H,

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Helvetica Chimica Acta Vol. 86 (2003)
HÀC(5,5')); 8.29 (d, 4 H, HÀC(6,6'), HÀC(3,3')(bpy)); 8.11 (d, 4J ˆ 1.8, 2 H, HÀC(9,9')); 7.91 (t, 3J ˆ 8.2, 2 H,
HÀC(4,4')(bpy)); 7.32 (m, 6 H, 4 Ho, HÀC(2,2')); 7.24 (d, 3J ˆ 7.0, 2 H, HÀC(5,5')(bpy)); 7.11 (d, 3J ˆ 8.8,
4 Hm); 6.94 (m, 4 H, HÀC(3,3'), HÀC(c')); 6.50 (d, 3J ˆ 7.7, 2 H, H ÀC(c)); 5.85 (m, 2 Hr); 5.3 5.0 (m, 4 H,
Hs,t); 4.5 (m, 2 H, Ha or Ha1); 4.25 (m, 2 H, Ha or Ha1); 3.96 (m, 6 H, Hq, Hb'); 3.7 3 (m, 54 H, Hb,g,d,e, Hg,h,i,j,k,l,n,p
,
‡
H
a',b,a); 2.5 (m, 4 Hf); 1.3 (m, 6 H, Hd or Hd', He); 1.0 (m, 2 H, Hd or Hd'). FAB-MS: 1827.7 ([23(PF6)] ; calc.
1827.7), 1682.7 ([23]; calc. 1682.7), 841.3 ([23]2‡; calc. 841.3).
[6,6'-Bis(4,7,10,13,16-pentaoxanonadec-18-en-1-yl)-2,2'-bipyridine-kN1,kN1']{15,16,18,19,21,22,34,35,37,38,
40,41,56,57,62,63-hexadecahydro-28,28-dimethyl-10,13:24,27:29,32:43,46:58,61-pentaetheno-9,4,7:47,49,52-bis-
(methenonitrilomethyno)-28H-[1,4,7,10,20,23,26,29]octaoxacyclononapentacontino[39,40-c:50,49-c']dipyridine-
kN3,kN53,kN67,kN78}ruthenium(2‡) Bis[hexafluorophosphate(1 À )] ([24](PF6)2). Asdescribed for [ 23](PF6)2,
with [16]/(PF6)2 (25 mg, 1.5 ¥ 10À5 mol), 22 (17 mg, 2.4 ¥ 10À5 mol), ethylene glycol (3 ml), and aq. sat.K(PF6)
soln. (8 ml): [24](PF6)2 (16 mg, 46%). Orange solid. 1H-NMR (300 MHz, CD3CN)2): 8.88 (d, 4J ˆ 1.4, 2 H,
HÀC(7,7')); 8.43 8.29 (d and s, 3J ˆ 9.2, 6 H, HÀC(5,5'), HÀC(6,6'), HÀC(9,9')); 7.86 (d, 3J ˆ 7.86, 2 H,
HÀC(3,3')(bpy)); 7.86 (t, 4J ˆ 7.86, 2 H, HÀC(4,4')(bpy)); 7.59 (d, 3J ˆ 8.8, 4 Ho); 7.21 (m, 3J ˆ 8, 2 H,
HÀC(5,5')(bpy)); 7.16 (d, 3J ˆ 8.07, 4 Hm); 7.11 7.07 (2d, 3J ˆ 8.7, 6 H, 4 Ho', HÀC(2,2')); 6.94 (d, 3J ˆ 5.6,
2 H, HÀC(3,3')); 6.8 (d, 3J ˆ 8.7, 6 H, 4 Hm', HÀC(c')); 6.39 (d, 3J ˆ 7.8, 2 H, HÀC(c)); 5.9 (m, 2 Hr); 5.3 5.0
(m, 4 H, Hs,t); 4.3 (m, 2 H, Ha or Ha1); 4.25 (m, 2 H, Ha or Ha1); 3.96 (m, 6 H, Hq, Hb'); 3.7 3.0 (m, 58 H,
H
b,g,d,e,l, Hg,h,i,j,k,l,n,p, Ha,a',b); 2.5 (m, 4 Hf); 1.45 (s, 2 Me); 1.3 (m, 6 H, Hd or Hd', He); 1.2 (m, 2 H, Hd or Hd'). ES-
‡
MS: 2081.9 ([24(PF6)] ; calc. 2082.1), 968.5 ([24]2‡; calc. 968.5).
[24Z)-10,13,16,19,22,27,30,33,36,39-Decaoxa-47,48-diazatricyclo[41.3.1.12,6]octatetraconta-1(47),2,4,6(48),
24,43,45-heptaene-kN47,kN48]{15,16,18,19,21,22,24,25,27,28,43,44,49,50-tetradecahydro-10,13:30,33:45,48-triethe-
no-9,4,7:34,36,39-bis(methenonitrilomethyno)[1,4,7,10,13,16](hexaoxacyclohexatetracontino[26,27-c:37,36-c']di-
pyridine-kN3,kN40,kN54,kN61}ruthenium(2‡) Bis[hexafluorophosphate(1 À )] ([25](PF6)2). Complex
[23](PF6)2, (29 mg, 1.5 ¥ 10À5 mol) and [Ru(ˆCHPh)]Cl2(PCy3)2] (1 mg) were dissolved in freshly distilled
CH2Cl2 to yield a 0.01m soln. which was stirred at r.t. for several days. Each two days the reaction was stopped,
the mixture analyzed by 1H-NMR, and more ruthenium catalyst added. After one week, a total of 6 mg of the
Grubbs catalyst was added, and the reaction was finished. The mixture was submitted to CC (silica gel, MeCN/
H2O/sat. aq. KNO3 soln. 100 :10 :2) and then to anion exchange: [25](PF6)2 (20 mg, 68%). Orange crystalline
solid. UV/VIS (MeCN): 341 (4.39), 455 (3.99). 1H-NMR (500 MHz, CD3CN)2): 8.84 (d, 4J ˆ 1.8, 2 H,
HÀC(7,7')); 8.41 (d, 3J ˆ 9.1, 2 H, HÀC(5,5')); 8.31 (d, 3J ˆ 9.1, 2 H, HÀC(6,6')); 8.27 (d, 3J ˆ 8.0, 2 H,
HÀC(3,3')(bpy)); 8.13 (d, 4J ˆ 1.8, 2 H, HÀC(9,9')); 7.91 (dd, 3J ˆ 8.0, 2 H, HÀC(4,4')(bpy)); 7.34 (d, 3J ˆ 8.8,
4 Ho); 7.32 (d, 3J ˆ 5.6, 2 H, HÀC(2,2')); 7.24 (d, 3J ˆ 7.0, 2 H, HÀC(5,5')(bpy)); 7.12 (d, 3J ˆ 8.8, 4 Hm); 6.96
(d, 3J ˆ 5.6, 2 H, HÀC(3,3')); 6.94 (d, 3J ˆ 9.9, 2 H, HÀC(c')); 6.51 (d, 3J ˆ 9.9, 2 H, HÀC(c)); 5.78 (m, Hr, 88%
cis); 5.63 (m, Hr, 12% trans); 4.5 (m, 2 H, Ha or Ha1); 4.2 (m, 2 H, Ha or Ha1); 3.96 (m, 6 H, Hq and Hb'); 3.7 3.0
(m, 54 H, Hb,g,d,e, Hg,h,i,j,k,l,n,p, Hb,a,a'); 2.5 (m, 4 Hf); 1.3 (m, 6 H, Hd or Hd', and He); 1.0 (m, Hd or Hd'). 2D-ROESY
‡
NMR. ES-MS: 1799.7 ([25](PF6)] ; calc. 1799.7), 827.4 ([25]2‡; calc. 827.8).
[(24Z)-10,13,16,19,22,27,30,33,36,39-Decaoxa-47,48-diazatricyclo[41,3.1.12,6]octatetraconta-1(47),2,4,6,(48),
24,43,45-heptaene-kN47,kN48]{15,16,18,19,21,22,34,35,37,38,40,41,56,57,62,63-hexadecahydro-28,28-dimethyl-
10,13:24,27:29,32:43,46:58,61-pentaetheno-9,4,7:47,49,52-bis(methenonitrilomethyno)-28H-[1,4,7,10,20,23,26,29]-
octaoxacyclononapentacontino[39,40-c:50,49-c']dipyridine-kN3,kN53,kN67,kN78}ruthenium(2‡) Bis[hexa-
fluorophosphate(1 À )] ([26](PF6)2). Complex [24](PF6)2, (16 mg, 7.2 ¥ 10À6 mol) and [Ru(ˆCHPh)Cl2(PCy3)2
]
(1.2 mg, 20 mol-%) were dissolved at r.t. in freshly distilled CH2Cl2 to yield a 0.1m soln. which was stirred for
several days. After one day, the reaction was stopped, and more catalyst was added (2 mg). After three days, a
total of 4 mg of the Grubbs catalyst was added, and the reaction was finished. The mixture was submitted to CC
(silica gel, MeCN/H2O/sat. aq. KNO3 soln. 100 :7:1) and then to anion exchange [26](PF6)2 (12 mg, 76%).
Orange crystalline solid. UV/VIS (MeCN): 460 (4.1). 1H-NMR (400 MHz, CD3CN): 8.88 (d, 4J ˆ 1.7, 2 H,
HÀC(7,7')); 8.40 8.29 (d, 3J ˆ 9.2, 6 H, HÀC(5,5'), HÀC(6,6'), HÀC(9,9')); 8.12 (d, 3J ˆ 7.7, 2 H,
HÀC(3,3')(bpy)); 7.73 (t, 3J ˆ 7.7, 2 H, H ÀC(4,4')); 7.56 (d, 3J ˆ 8.7, 4 Ho); 7.15 (d, 3J ˆ 7.7, 2 H,
HÀC(5,5')(bpy)); 7.13 (d, 3J ˆ 8.8, 4 Hm); 7.07 7.0 (2d, 3J ˆ 8.8, 3J ˆ 5.4, 6 H, HÀC(2,2'), 4 Ho'); 7.99 (d, 3J ˆ
5.4, 2 H, HÀC(3,3')); 7.12 (2d, 3J ˆ 8.8, 6 H, 4 Hm', 2 HÀC(c')); 6.36 (d, 3J ˆ 9.2, 2 H, HÀC(c)); 5.78 (m, Hr);
4.25 (m, 4 Ha); 4.00 (m, 8 H, Hl, Hq); 3.79 (m, 4 Hb); 3.7 3 (m, 32 H, Hg,d,e, Hj,k,l,n,p); 3.47 (m, 4 Hi); 3.28
(m, 4 Hh); 3.05 (m, 4 Hg); 4.0-3.0 (m, 8 H, Ha,a',b,b'); 2.5 (m, 4 Hf); 1.3 (m, 6 H, Hd or Hd', He); 1.40 (s, 2 Me); 1.2
‡
(m, 2 H, Hd or Hd'). 2D-ROESY NMR. ES-MS: 2053.7 ([26](PF6)] , calc. 2053.1), 954.4 ([26]2‡; calc. 954.05).

Helvetica Chimica Acta Vol. 86 (2003)
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Received October 10, 2003