Metallomacrocycles with a difference: Macrocyclic complexes with exocyclic ruthenium(II)-containing domains

Article abstract of DOI:10.1002/chem.200901640

The templated synthesis of organic macrocycles containing rings of up to 96 atoms and three 2,2'-bipyridine (bpy) units is described. Starting with the bpy-centred ligands 5,5'-bis[3(1,4-dioxahept-6-enylphenyl)]-2,2'-bipyridine and 5,5'-bis[3-(1,4,7-triox

Full text of DOI:10.1002/chem.200901640

DOI: 10.1002/chem.200901640
Metallomacrocycles with a Difference: Macrocyclic Complexes with
Exocyclic Ruthenium(II)-Containing Domains
Edwin C. Constable,* Catherine E. Housecroft,* Markus Neuburger, Pirmin J. Rçsel,
Silvia Schaffner, and Jennifer A. Zampese[a]
Abstract: The templated synthesis of
organic macrocycles containing rings of
up to 96 atoms and three 2,2’-bipyri-
dine (bpy) units is described. Starting
with the bpy-centred ligands 5,5’-bis[3-
(1,4-dioxahept-6-enylphenyl)]-2,2’-bi-
pyridine and 5,5’-bis[3-(1,4,7-trioxadec-
9-enylphenyl)]-2,2’-bipyridine, we have
applied Grubbsꢀ methodology to
couple the terminal alkene units of the
coordinated ligands in [FeL3]2+ com-
plexes. Hydrogenation and demetalla-
tion of the iron(II)-containing macrocy-
clic complexes results in the isolation
of large organic macrocycles. The latter
bind {Ru(bpy)2} units to give macrocy-
to yield a macrocycle which retains the
exocyclic {Ru(bpy)2} unit. The poly-
G
ACHTUNGTRENNUNG
clic complexes with exocyclic rutheni-
um(II)-containing domains. The complex
(ethyleneoxy) domains in the latter
macrocycle readily scavenge sodium
ions, as proven by single-crystal X-ray
diffraction and atomic absorption spec-
troscopy data for the bulk sample. In
[RuACHTNUTGRNEUNG
(bpy)2(L)]2+ (isolated as the hexa-
fluorophosphate salt), in which L=
5,5’-bis[3-(1,4,7,10-tetraoxatridec-12-
enylphenyl)]-2,2’-bipyridine, undergoes
intramolecular ring-closing metathesis
addition to the new compounds,
a
series of model complexes have been
fully characterized, and representative
single-crystal X-ray structural data are
presented for iron(II) and ruthen-
ium(II) acyclic and macrocyclic species.
Keywords: chirality · heterocycles ·
macrocycles
·
ruthenium
·
supramolecular chemistry
Introduction
by chelating ligands. With the aim of developing general
routes for the preparation of mono- and polynuclear exo-
cyclic complexes, we have investigated the synthesis of
large-ring macrocycles containing one or more 2,2’-bipyri-
dine (bpy) metal-binding domains.
The assembly of topologically complex architectures has
become a realistic target for synthetic chemists.[6–10] For the
synthesis of large macrocycles,[11] Grubbsꢀ-catalysed ring-
closing metathesis (RCM) has proved to be a very efficient
strategy and operates under very mild reaction condi-
tions.[12,13] An elegant synthetic route devised by Sauvage
In the first decade of the 21st century, macrocyclic chemistry
can be considered a mature science.[1–4] However, the bulk
of synthetic systems that have been designed for metal-ion
binding are optimized for endocyclic bonding modes in
which the metal ion is coordinated within the cavity of the
macrocycle. In the case of macrocyclic ligands with soft
donor atoms such as sulfur, selection between endocyclic
and exocyclic bonding modes has been controlled by
anions.[5] An alternative method for enforcing an exocyclic
bonding mode is by the use of a kinetically inert centre in
which a certain number of coordination sites are occupied
first introduced the concept of using
a tetrahedral
{Cu
AHCTUNGTRENNUNG
plate the formation of a catenane.[14–16] Since this break-
through, metal-ion-templated syntheses have been applied
to control a variety of ring-closing steps, thus allowing the
assembly of catenanes, knots and rotaxanes.[17] Several
recent examples have focused on the formation of large or-
ganic macrocycles,[18–21] and, notably, Sauvage has made use
of octahedral ruthenium(II) as the templating metal
centre.[22–25] In 1973, Sokolov suggested the use of an octahe-
[a] Prof. Dr. E. C. Constable, Prof. Dr. C. E. Housecroft, M. Neuburger,
Dr. P. J. Rçsel, Dr. S. Schaffner, Dr. J. A. Zampese
Department of Chemistry
University of Basel
Spitalstrasse 51, 4056 Basel (Switzerland)
Fax : (+41)61-267-1018
E-mail: catherine.housecroft@unibas.ch
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.200901640. It contains details of
dral trisACTHNUTRGENUG(N chelate) template for the assembly of a trefoil
knot.[26] The Grubbsꢀ methodology provides an ideal oppor-
tunity for exploring this approach, starting with terminally
AAS determination of sodium content in [Ru
N
ACHTUGNTERN[NUNG PF6]2·
xNaACHTUNGTRENNUNG
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FULL PAPER
phenyl)-2,2’-bipyridine with 3-
(2-bromoethoxy)prop-1-ene in
the presence of Cs2CO3 in
DMF.[28] Ligands 3 and 4, con-
geners of
2 with additional
ethoxy spacers, were prepared
in an analogous manner to 2.
Both ligands were obtained in
high yield. The highest mass
(and base) peaks in the elec-
tron impact (EI) mass spectra
of 3 and 4 appeared at m/z
Scheme 1. Schematic representation of the synthesis of a trefoil knot or macrocycle templated by an octahe-
dral {Fe
(bpy)3}2+ unit.
ACHTUNGTRENNUNG
alkene-functionalized bpy li-
gands and an {Fe
(bpy)3}2+
AHCTUNGTRENNUNG
template. Under high dilution
conditions, RCM should pre-
dominate over alkene meta-
thesis between complex cat-
ions. By optimizing the length
of the spacers between the bpy
domain and the alkene func-
tionalities, in theory a three-
fold RCM should lead to
either a trefoil knot or an open
macrocycle (Scheme 1). In the
event, the non-knotted topo-
logical isomers were obtained, and we report here the tem-
plated synthesis of macrocycles containing rings with up to
596.3 and 685.4, respectively, and each was assigned to the
1
parent ion. The H and 13C NMR spectra were fully assigned
96 atoms and their reactions with cis-[Ru
macrocyclic complexes with exocyclic coordination domains.
(bpy)2Cl2] to form
by COSY, NOESY, HMQC and HMBC techniques and
were consistent with the symmetrical structures shown. The
aromatic regions of the 1H NMR spectra of CD2Cl2 solutions
of 3 and 4 are virtually superimposable, as are the spectro-
scopic signatures for the alkene protons (Hb1, Hb2 and Hb3).
The aliphatic regions in the 1H NMR spectra of the two
ligands are extremely similar, with the exception of addi-
tional signals for the extra methylene groups. For both li-
gands, the resonances for protons Ha1 appear as the highest-
frequency aliphatic signals, with the resonances for the
alkene-attached CH2 group (Ha5 for 3, Ha7 for 4) being at
the next highest frequency. The CD2Cl2 solution 13C NMR
spectra of 3 and 4 are also similar, the aromatic and alkene
regions being almost superimposable, and the aliphatic re-
gions differing only in the appearance of the additional CH2
13C signals on going from 3 to 4.
Results and Discussion
Ligand synthesis and characterization: We have previously
described the synthesis of ligand 1 (structures show the
Model complexes: Before proceeding to the formation of
macrocyclic ligands and their complexes, we describe the
synthesis and characterization of the model complexes
[Fe(1)3]
N
ACTHUNGNRET(NUGN bpy)2(1)]CAHTUNGTERNNGU[PF6]2, [RuAHCTNUGERTN(GNNU bpy)2(3)]ACHTUNGTRENN[UNG PF6]2 and
[Ru(bpy)2(4)]CAHTUNGTRENNUNG
E
bank for these systems proves helpful for the assignment of
spectra of the more complicated species encountered later
in the discussion. The reaction between ligand 1 and
FeCl2·4H2O in CH2Cl2/MeCN, followed by anion exchange
numbering and ring labelling scheme used for NMR spec-
troscopic assignments) and its deprotection to give 5,5’-
bis(3’-hydroxyphenyl)-2,2’-bipyridine.[27] We have also re-
ported the preparation of ligand 2 through caesium-directed
Williamsonꢀs methodology by reacting 5,5’-bis(3’-hydroxy-
and workup, led to the isolation of [Fe(1)3]
ACHTUGNTREN[UNNG PF6]2 in moder-
ate yield. The highest mass peak (also the base peak) at m/z
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11747

C. E. Housecroft, E. C. Constable et al.
580.5 in the electrospray ionization (ESI) mass spectrum
The complex [Ru
quantitative yield by the reaction of cis-[RuCAHTUNGTRENNNUG
ACHUTGTNNERNUG(bpy)2(1)]ACHTGNUTRENNUNG
was assigned to [Mꢀ2PF6]2+, and the isotope distribution
1
matched that calculated. Each of the H and 13C NMR spec-
ligand 1 under microwave conditions followed by anion ex-
change. The ESI mass spectrum exhibits peak envelopes
with characteristic ruthenium isotope distributions at m/z
927.1 and 391.2, assigned to [MꢀPF6]+ and [Mꢀ2PF6]+, re-
spectively. Figure 2 shows the aromatic region of the
tra was consistent with the formation of [Fe(1)3]2+ in which
each ligand is in a symmetrical environment. Compared to
the signals for the free ligand 1,[27] that assigned to proton
HA6 is the most significantly affected by coordination, shift-
ing from d=8.94 ppm (1 in CDCl3) to d=7.52 ppm (com-
plex in CD3CN). This is a characteristic indication that an
{MACHTUNGTRENNUNG(bpy)3} motif has been formed and occurs because of the
shielding experienced when HA6 lies over the p cloud of one
ring of an adjacent bpy ligand. Single crystals of [Fe(1)3]-
ACHTUNGTRENNUNG[PF6]2·3C2H4Cl2 suitable for X-ray diffraction study were
grown by layering diethyl ether over a 1,2-dichloroethane
solution of the complex. Figure 1 shows the structure of the
Figure 2. 500 MHz 1H NMR spectrum of
a
CD3CN solution of
[Ru(bpy)2(1)][PF6]2 at room temperature. See structure for atom labelling.
1H NMR spectrum of the complex. Coordination of ligand 1
1
to the {Ru
G
trum by the diagnostic shift of the signal for proton HA6
(from d=8.94[27] to 7.80 ppm, 1 being in CDCl3 and the com-
plex in CD3CN). In [Ru
chemically equivalent because each lies over a chemically
equivalent pyridine ring. However, in [Ru
(bpy)2(1)]2+, al-
(bpy)3]2+, all 6- and 6’-protons are
ACHTUNGTRENNUNG
Figure 1. Molecular structure of the [Fe(1)3]2+ cation in [Fe(1)3]-
ACHTUNGTRENNUNG[PF6]2·3C2H4Cl2 with ellipsoids plotted at the 30% probability level; hy-
though the pyridine rings in ligand 1 are chemically equiva-
lent, those in each bpy ligand are chemically inequivalent.
Proton HD6 points towards the p cloud of ring A, whereas
HC6 lies over the second ring C. Figure 2 illustrates the ob-
servation of two signals for HC6 and HD6, but we were
unable to unambiguously assign the signals to one or other
of these protons.
drogen atoms are omitted. Selected bond lengths [ꢂ] and angles [8]: Fe1–
N1 1.962(2), Fe1–N2 1.963(2), Fe1–N3 1.967(2), Fe1–N4 1.953(2), Fe1–
N5 1.974(2), Fe1–N6 1.961(2); N1-Fe1-N2 81.6(1), N3-Fe1-N4 81.5(1),
N5-Fe1-N6 82.3(1), N2-Fe1-N3 176.8(1), N1-Fe1-N5 173.7(1), N4-Fe1-N6
173.9(1).
[Fe(1)3]2+ cation. The compound crystallizes in the non-
chiral space group Pcab, and so both enantiomers of the
cation are present. Each ligand is significantly twisted, with
the angles between the least-squares planes of adjacent
rings being 33.7(2), 2.5(2) and 3.6(2)8 for the ligand contain-
ing atoms N1 and N2, 34.7(2), 10.7(2) and 16.7(2)8 for that
with atoms N3 and N4, and 29.8(2), 6.7(2) and 29.3(2)8 for
the ligand containing N5 and N6. The orientations of the
methoxy groups deserve comment. In the ligand containing
atoms O1 and O2, the methoxy substituents are in a transoid
arrangement, whereas in that containing O3 and O4, the
two substituents both point towards the iron atom. In the
third ligand, both methoxy groups (O5 and O6) are directed
away from the coordination centre. These variations are
The anion TRISPHAT[29,30] (tris(tetrachlorobenzenediola-
to)phosphate(V)) is a general NMR chiral resolving reagent
for chiral cationic species. Compared to the spectrum for
1
the [PF6]ꢀ salt, the H NMR spectrum of D-TRISPHAT salt
shows two sets of signals in roughly equal intensities arising
from the diastereoisomers [D-Ru
ACHTUNGTRENNUNG
and [L-RuACTHUNGTRENNNUG
mation).
X-ray-quality crystals of [RuACHTUNRGTNENG(U bpy)2(1)]ACHTUNGTERN[NUGN PF6]2·MeCN were
grown by layering Et2O over an MeCN solution of the com-
plex. The structure of the cation is shown in Figure 3. The
two bpy ligands deviate slightly from planarity (the angles
between the least-squares planes of the rings containing N51
and N61, and N71 and N81 are 2.8(2) and 9.8(2)8), and
ligand 1 is significantly twisted (the angles between the
planes of the four rings are 42.3(2), 7.9(2) and 34.1(2)8).
Both methoxy substituents point away from the rutheni-
um(II) centre, and one is involved in non-classical hydrogen
bonding to aromatic CH units of adjacent cations (see Sup-
porting Information).
ꢀ
most probably a result of non-classical O···H C hydrogen
bonds (see Supporting Information). Most importantly, the
structural determination confirmed that the {Fe(1)3} building
block can assemble with the peripheral methoxyphenyl units
and has significant flexibility by virtue of twisting about the
ꢀ
Cpyridine Cphenyl bonds.
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Ruthenium-Containing Macrocycles
FULL PAPER
ene and alkene protons. This was also true on going from
free ligand 4 to [RuACHTNUTRGENNUG(bpy)2(4)]ACHUTGNTREN[NUGN PF6]2.
With the spectroscopic signatures and structural proper-
ties of the model complexes established, we were in a posi-
tion to turn our attention to the use of ligands 2–4 and the
synthesis of large macrocyclic ligands containing bpy metal-
binding domains.
Templated synthesis of macrocyclic ligands: Our strategy for
the formation of macrocyclic ligands containing three bpy
metal-binding domains was to first prepare the iron(II) com-
plexes [Fe(2)3]2+, [Fe(3)3]2+ and [Fe(4)3]2+, apply Grubbsꢀ
methodology to couple the terminal alkene functionalities
of the coordinated ligands, and then carry out hydrogena-
tion and demetallation. The iron(II) complexes were pre-
Figure 3. Molecular structure of the [Ru
(bpy)2(1)][PF6]2·MeCN with ellipsoids plotted at the 30% probability
(bpy)2(1)]2+ cation in [Ru-
ACHTUNGTRENNUNG
U
ACHTUNGTRENNUNG
level; hydrogen atoms omitted. Selected bond lengths [ꢂ] and angles [8]:
Ru1–N31 2.052(3), Ru1–N71 2.055(3), Ru1–N51 2.056(3), Ru1–N81
2.060(3), Ru1–N11 2.063(3), Ru1–N61 2.070(3); N31-Ru1-N11 78.7(1),
N51-Ru1-N61 78.30(1), N71-Ru1-N81 78.9 (1), N31-Ru1-N51 175.0(1),
N81-Ru1-N11 171.4(1), N71-Ru1-N61 172.4(1).
pared by treating Fe
in MeCN at reflux for 3–4 days. [Fe(2)3]
[BF4]2 were isolated in near quantitative yields. The highest
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
mass peak in the ESI mass spectrum of each complex corre-
1
sponded to the [Mꢀ2BF4]2+ ion. The H and 13C NMR spec-
tra of the two complexes confirmed the presence of one,
symmetrical ligand environment in each case. The diagnostic
shift in the signal for protons HA6 from d=8.97 ppm in 2 to
d=7.54 ppm in [Fe(2)3]2+, and from d=8.93 ppm in 2 to d=
7.75 ppm in [Fe(3)3]2+, confirmed the formation of {Fe-
Ligands 3 and 4 react with cis-[Ru
wave conditions and, following anion exchange and chroma-
tographic workup, [Ru(bpy)2(3)][PF6]2 and [Ru(bpy)2(4)]-
[PF6]2 were isolated in ꢁ90% yield. The ESI mass spectrum
ACHTUNGTREN(NUNG bpy)2Cl2] under micro-
A
R
ACHTUNGTRENNUNG
A
(bpy)3}2+ units. Although the NMR spectroscopic data were
ACHTUNGTRENNUNG
consistent with the formation
of [Fe(4)3]2+ in the reaction of
Fe
an analytically pure sample of
[Fe(4)3][BF4]2 could not be ob-
ACHTNUGTRENN(UGN BF4)2·6H2O with ligand 4,
AHCTUNGTRENNUNG
tained, and we therefore fo-
cused our attention on the re-
activities of [Fe(2)3]2+ and
[Fe(3)3]2+
.
Scheme 2 summarizes the
approach taken to the forma-
tion of a macrocyclic ligand
beginning with the complex
[Fe(2)3]2+. A dichloromethane
solution of [Fe(2)3]ACTHNUTRGNENUG[BF4]2 was
stirred at room temperature in
the presence of Hoyveda–
of each complex showed molecular ions assigned to
Grubbs catalyst. The progress of the reaction was monitored
by H NMR spectroscopy and ESI mass spectrometry. The
1
[MꢀPF6]+ and [Mꢀ2PF6]2+, each peak envelope having the
1
expected isotope distributions. The H and 13C NMR spectra
1H NMR spectrum showed the disappearance of the termi-
nal alkene protons at d=5.18, 5.28 and 5.90 ppm, and the
appearance of new signals at d=5.93 and 5.74 ppm for the
newly formed HC=CH unit (Z and E isomers). After
40 days, >95% alkene metathesis had been achieved. The
crude product was demetallated by treating it with
Na2H2EDTA (EDTA: ethylenediaminetetraacetate) in the
presence of Na2CO3, the removal of FeII being monitored by
of the products were assigned by 2D techniques. In the
1H NMR spectra, the shift of the signal for proton HA6 from
d=8.93 ppm in 3 to d=7.81 ppm in [Ru
from d=8.94 ppm in 4 to d=7.65 ppm in [Ru
[PF6]2, was consistent with coordination of the ligands to the
ACHUTGTNNERNUG(bpy)2(3)]ACHTGNUTRENNUNG
AHCTUNGTRENNUNG
ACHTUNGTRENNUNG
metal ion. The appearance of two sets of signals for the bpy
ligand protons for each complex mimicked the scenario for
[Ru
(bpy)2(1)]
U
loss of the red colour typical of the {FeACTHNGURETNNU(G bpy)3} chromophore.
1
G
E
(Attempts to demetallate the complex with cyanide, or mix-
tures of H2O2 and NaOH, resulted in decomposition of the
RCM product.) After the organic product had been extract-
lar to that in the free ligand 3, which indicated that coordi-
nation of the bpy domain of 3 has little effect on the methyl-
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11749

C. E. Housecroft, E. C. Constable et al.
Ruthenium(II) complexes of li-
gands 5 and 6: Ligand 5 was
treated with two molar equiva-
lents of cis-[RuACHTUNTRGNEUNG(bpy)2Cl2] in
ethanol under microwave con-
ditions. After anion exchange
and chromatographic workup,
orange [{RuACHTUNGTRNENG(U bpy)2}2(5)]ACHTUNGTRENNUNG[PF6]4
was isolated in 46% yield. The
solution 1H NMR spectrum of
the product indicated a sym-
metrical structure, and re-
vealed one set of signals for
the bpy unit of ligand 5 and
two sets of signals for the pro-
Scheme 2. Schematic representation of the methodology used to prepare a macrocyclic ligand starting with
[Fe(2)3]2+: i) Hoyveda–Grubbs catalyst, CH2Cl2, 40 days, room temperature; ii) Na2H2EDTA, Na2CO3; iii) H2
(1 bar), Pd/C, CH2Cl2/EtOH. See text for n.
ed, it was hydrogenated (1 bar H2, Pd/C). Chromatographic
purification of the product proved difficult, but after a com-
bination of column and preparative thin-layer chromatogra-
phies (see Experimental Section) macrocycle 5 was ob-
1
tained. The H NMR spectrum of the product indicated that
1
it was approximately 80% pure. In the H NMR spectrum,
the appearance of a multiplet at d=1.68 ppm was consistent
with the presence of a methylene group not directly bonded
to an oxygen atom. This, along with the loss of signals in the
alkene region of the spectrum, supported the formation of
the final product shown in Scheme 2. The signals in the aro-
matic region of the spectrum were similar to those for
ligand 2, but each was shifted to a lower frequency by be-
tween 0.06 and 0.12 ppm. The highest mass and base peak in
the ESI mass spectrum of the product was observed at m/z
988.0 and corresponded to [M+Na]+ for a macrocycle with
n=2 in Scheme 2. Thus, although molecular modelling[31]
had indicated that the poly(ethyleneoxy) spacers were long
enough to allow coupling of all three ligands in [Fe(2)3]2+
,
in practice macrocycle 5 (n=2 in Scheme 2) was formed by
the coupling of only two coordinated ligands. This was con-
firmed from the structural characterization of the product of
the reaction of ligand 5 with cis-[RuACHTUNGRTENUNG(bpy)2Cl2] described
later.
The ring-closing strategy described above was also applied
to [Fe(3)3]2+. However, in this case, it was more efficient to
carry out the hydrogenation step before demetallation.
Careful chromatographic purification of the product result-
ed in the isolation of analytically pure macrocycle 6 in 26%
yield. A base peak at m/z 1734.6 in the ESI mass spectrum
confirmed the formulation of 6, the peak being assigned to
1
[M+Na]+. The H and 13C NMR spectra of 6 were consis-
tent with the symmetrical structure shown. The aromatic
1
region of the H NMR spectrum appeared very similar to
tons of each bpy ligand. By analogy with the discussion for
that of ligand 3, with signals shifted only 0.02 to 0.05 ppm to
lower frequency on going from 3 to 6. That complete hydro-
genation had been achieved was supported by the disappear-
ance of signals in the alkene region and the appearance of a
multiplet at d=1.62 ppm assigned to Ha6.
[RuACHTUNGTREN(NUG bpy)2(1)]ACHTUNGTRNEN[UNG PF6]2 above (see Figure 2), the data were con-
sistent with the structure shown. The dominant peak enve-
lopes in the ESI mass spectrum of the complex appeared at
m/z 1041.3, 646.0 and 448.2 and were assigned to
[Mꢀ2PF6]2+, [Mꢀ3PF6]3+ and [Mꢀ4PF6]4+, respectively.
The isotope distribution of each envelope matched that si-
mulated.
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Ruthenium-Containing Macrocycles
FULL PAPER
Single crystals of [{Ru
were grown by layering ethyl acetate over a 1,2-dichloro-
ethane solution of [{Ru(bpy)2}2(5)][PF6]4. The complex crys-
ACHUTTGNERN(NUG bpy)2}2(5)]CAHTUNGTRNEN[UNG PF6]4·C2H4Cl2·2.5EtOAc
A
ACHTUNGTRENNUNG
¯
tallizes in the centrosymmetric P1 space group and was ob-
tained in the homochiral form (Figure 4) with the unit cell
Figure 5. Space-filling representation of the [{RuACTHNUTRGNEUNG
(bpy)2}2(5)]4+ cation in
[{RuACTHNUTRGENNG(U bpy)2}2(5)]HCAUTNTGNER[NUGN PF6]4·C2H4Cl2·2.5EtOAc showing the ethyl acetate mole-
cule (visible above in the front half of the cavity) and [PF6]ꢀ ion hosted
within the macrocyclic cavity.
Figure 4. Molecular structure of the [{Ru
(bpy)2}2(5)][PF6]4·C2H4Cl2·2.5EtOAc with ellipsoids plotted at the 30%
(bpy)2}2(5)]4+ cation in [{Ru-
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
probability level; hydrogen atoms omitted. For each of the disordered C
and O atoms in the macrocycle, one position only is shown. Selected
bond lengths [ꢂ] and angles [8]: Ru1–N1 2.052(4), Ru1–N2 2.054(3),
Ru1–N3 2.060(3), Ru1–N4 2.050(3), Ru1–N5 2.047(3), Ru1–N6 2.063(4),
Ru2–N7 2.056(4), Ru2–N8 2.069(4), Ru2–N9 2.074(3), Ru2–N10 2.055(4),
Ru2–N11 2.057(4), Ru2–N12 2.063(4); N1-Ru1-N2 79.3(1), N3-Ru1-N4
79.2(1), N5-Ru1-N6 78.8(1), N2-Ru1-N4 171.8(2), N3-Ru1-N5 174.4(1),
N1-Ru1-N6 172.3(1), N8-Ru2-N10 78.7(2), N7-Ru2-N9 79.1(2), N11-Ru2-
N12 79.3(2), N8-Ru2-N9 174.1(2), N10-Ru2-N11 173.4(2), N7-Ru2-N12
168.2(2).
containing one DD and one LL isomer. Both {RuACTHUNRGTNEUNG(bpy)2}
units are directed towards the outside of the macrocycle,
and bond parameters within the coordination sphere of each
ruthenium ion are unexceptional. Both poly(ethyleneoxy)
chains, two [PF6]ꢀ ions and the 1,2-dichloroethane solvent
molecules suffer from disorder, and have been modelled
using multiple positions and appropriate restraints. The
Ru1···Ru2 separation across the macrocyclic cavity is
10.012(1) ꢂ, and the aromatic rings are too far apart for
there to be any intramolecular p stacking. The cavity of the
1H and 13C NMR spectra was consistent with the symmetri-
cal structure shown. The diagnostic shift of protons HA6
upon coordination, and the appearance of one set of signals
for the bpy unit of 6 and two sets of signals for the protons
of each bpy ligand, provided confirmation that each bpy
[{RuACHTUNGTRENNUNG
(bpy)2}2(5)]4+ cation hosts one disordered [PF6]ꢀ ion
and one ethyl acetate solvent molecule, each sandwiched be-
tween pairs of aromatic rings (Figure 5).
Ligand 6 was treated with three molar equivalents of cis-
[Ru
N
domain in ligand 6 had bound a {Ru
ence of three stereogenic ruthenium(II) centres in [{Ru-
(bpy)2}3(6)]6+ leads to the possibility of a pair of homochiral
LLL/DDD stereoisomers and three pairs of heterochiral
LLD/DDL stereoisomers (Figure 6). The addition of ap-
proximately six equivalents of [Et4N][D-TRISPHAT] (see
ACHTUNGRTEN(NUGN bpy)2} unit. The pres-
anion exchange, orange [{Ru
G
ACHTUNGTRENNUNG
in 92% yield. Analytically pure material was obtained with-
out the need for chromatographic purification. The highest
mass peak in the ESI mass spectrum was observed at m/z
1765.7 and was assigned to [Mꢀ2PF6]2+. A series of peak
envelopes at m/z 1128.5, 811.1, 619.8 and 492.4 arose from
sequential loss of [PF6]ꢀ, and all peaks exhibited the correct
isotopic distributions. The number of signals in each of the
ACHTUNGTRENNUNG
Supporting Information) to a CD2Cl2 solution of [{Ru-
1
G
N
ing far more complex, which can be attributed to the pres-
Chem. Eur. J. 2009, 15, 11746 – 11757
ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
11751

C. E. Housecroft, E. C. Constable et al.
cross peak to Ha8) was observed at d=2.30 ppm, significant-
ly shifted to lower frequency when compared with the sig-
nals for the other OCH2 protons (d=3.38 to 3.98 ppm). In
the solid-state structure (see below), the poly(ethyleneoxy)
chain wraps around the {Ru
ACHTUNGERTN(NUNG bpy)3} unit. Assuming that this
same arrangement is maintained in solution, then the O-
AHCTUNGTREN(GNUN CH2)4O unit lies within the cleft between the two bpy li-
gands, the Ha7 protons being close to the bpy p clouds.
Elemental analytical data for the orange product did not,
however, correspond to [RuACHTUNRGTENN(UG bpy)2(7)]ACHTUNGTRNEN[UGN PF6]2, but we were
fortunate in being able to grow X-ray-quality crystals from
an MeCN solution of the complex layered with Et2O. The
X-ray diffraction study revealed the crystalline sample to be
[RuCATHNUGTENR(UNGN bpy)2(7)]ACHTUGNTERN[NUG NaRuACHUTNGERTG(NUNN bpy)2(7)]ACHTNGUTREN[NUGN PF6]5. The source of the
Figure 6. Schematic representation of the stereoisomers possible for [{Ru-
(bpy)2}3(6)]6+
G
.
sodium ions is not clear, and we can only assume that they
are extracted by the macrocyclic ligand during chromato-
graphic workup. Attempts to prepare sodium-free samples
of the complex failed. The sodium content of the bulk
sample was determined by atomic absorption spectroscopy
(AAS; see Supporting Information) and the results indicat-
ence of [DDD-{Ru
(bpy)2}3(6)][D-TRISPHAT]6, [LLD-{Ru
SPHAT]6 and [DDL-{Ru(bpy)2}3(6)][D-TRISPHAT]6. How-
ever, we were unable to unambiguously assign the spectrum.
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
ed that (35ꢂ10)% of the [Ru
(bpy)2(7)]2+ cations contained
ACHTUNGTRENNUNG
Na+. The role of the sodium ions in the complex was re-
vealed from the results of the single-crystal X-ray diffraction
RCM with [RuACHTUNGTRENNUNG
(bpy)2(4)]2+: Because we were unable to pro-
ceed with the use of [Fe(4)3]2+ for RCM, we decided instead
study. The complex crystallizes in the P1 space group and
the asymmetric unit contains one [Ru
¯
to apply Grubbsꢀ methodology (Scheme 2) to [Ru-
(bpy)2(7)]2+ and one
ACHTUNGTRENNUNG
A
E
N
[NaRu
ACHTUNGTRENNUNG
treated with Hoyveda–Grubbs catalyst at room temperature
and the reaction was monitored periodically with H NMR
countered from disordered solvent molecules that fill the
void space between the cations. As these solvent molecules
were not important to the overall structure, they were re-
moved by the program SQUEEZE.[32] The flexibility of the
poly(ethyleneoxy) chains in both cations led to varying de-
grees of disorder and, understandably, some of the atom po-
sitions in the chains are poorly defined. Figure 7a shows the
1
spectroscopy and ESI mass spectrometry. After 17 days, the
1
diagnostic H NMR signals for the alkene protons in [Ru-
ACHTUNGTRENNUNG
(bpy)2(4)]2+ had disappeared. Hydrogenation of the unsatu-
rated intermediate, followed by chromatographic purifica-
tion, resulted in the isolation of an orange solid. The ESI
mass spectrum of the latter exhibited peaks at m/z 1217.6
structure of the [RuACTHNUTRGNEUNG
(bpy)2(7)]2+ cation. Each of the atoms
and 536.2, consistent with intramolecular RCM in [Ru-
in the chain from O1 to O9 is disordered and each has been
modelled over two positions with fractional occupancies of
0.5/0.5. One phenyl ring is also disordered. Bond parameters
within the ruthenium(II) coordination sphere are unexcep-
1
G
N
tional. The {Ru
clic cavity, with the O
two bpy ligands (Figure 7b). As in [Ru
(bpy)2} unit in the [NaRu
(bpy)2(7)]3+ cation points towards
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG
the macrocyclic cavity; the sodium ion lies on the opposite
side of the macrocycle. The Na+ ion is coordinated by three
O donor atoms (O51–Na1 2.686(4), O54–Na1 2.306(4),
O57–Na1 2.619(5) ꢂ) and by two [PF6]ꢀ ions (Na1–F34
2.429(5), Na1–F32 2.473(6), Na1–F56 2.488(5), Na1–F54
ꢀ
2.507(7), Na1–F55 2.532(6) ꢂ). Figure 8 shows the close C
H···F contacts between the centrosymmetric pair of [NaRu-
AHCTUNGTRENNUNG
(bpy)2(7)]3+ cations in the unit cell. The non-sodium-bound
[PF6]ꢀ ions are also involved in extensive C H···F interac-
ꢀ
tions, which dominate the cation–anion packing.
and 13C NMR spectra were also consistent with this formula-
tion. The methylene protons Ha8 gave rise to a signal at d=
1.58 ppm, which is similar to the non-oxygen-attached CH2
groups in the macrocycles described above. However, the
signal for Ha7 (the assignment being confirmed by a COSY
Absorption, emission and electrochemical properties of the
ruthenium(II) complexes: The absorption spectra of CH2Cl2
solutions of the model complex [Ru
N
ACHTUNGTRENNUNG
each of the macrocyclic complexes [Ru
N
ACHTUNGTRENNUNG
11752
www.chemeurj.org
ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2009, 15, 11746 – 11757

Ruthenium-Containing Macrocycles
FULL PAPER
Figure 8. Centrosymmetric pair of [NaRuACTHUNGTRENNUNG
ciated with two [PF6]ꢀ anions in [Ru
G
E
N
ACHTUNGTRENNUNG
Symmetry code i=2ꢀx, ꢀy, 1ꢀz.
Table 1. Redox potentials for [Ru
[{Ru(bpy)2}2(5)][PF6]4 and [{Ru(bpy)2}3(6)]
ferrocene/ferrocenium).
G
ACTHUGNNERT[GNUN PF6]2, [RuACHTNURGTEG(NNUN bpy)2(7)]ACHTUNGTRENNUNG[PF6]2,
R
G
N
ACHTUNGTRENNUNG
Cation
E(Ru2+
/
Ligand-based reductions [V][a]
Ru3+) [V]
[Ru
[Ru
[{Ru
N
0.903
0.904
ꢀ1.60, ꢀ1.87, ꢀ2.10, ꢀ2.41
Figure 7. a) Molecular structure of the [Ru
(bpy)2(7)][NaRu(bpy)2(7)][PF6]5; hydrogen atoms omitted. Ellipsoids are
(bpy)2(7)]2+ cation in [Ru-
ACHTUNGTRENNUNG
ꢀ1.60
ꢀ1.48
ꢀ2.15
ꢀ1.57
ꢀ2.42
G
E
G
G
ACHTUNGTRENNUNG
N
A
U
ACHTUNGTRENNUNG
plotted at 30% probability level. For disordered atoms (see text), only
one position for each atom is shown. Selected bond lengths [ꢂ] and
angles [8]: Ru1–N11a 2.058(3), Ru1–N11b 2.060(3), Ru1–N21a 2.064(3),
Ru1–N21c 2.064(3), Ru1–N21b 2.067(3), Ru1–N11c 2.071(3); N11a-Ru1-
N21a 78.3(1), N11b-Ru1-N21b 79.0(1), N21c-Ru1-N11c 78.9(1), N11b-
Ru1-N21c 174.0(1), N11a-Ru1-N21b 173.0(1), N21a-Ru1-N11c 173.1(1).
A
ACHTUNGTRENNUNG
[{Ru
(bpy)2}3(6)]6+ 0.927
A
U
AHCTUNGTRENNUNG
[a] Reversible unless otherwise stated; irr: irreversible.
b) Space-filling diagram of the [Ru
thyleneoxy) chain, pale grey; aromatic rings, dark grey).
(bpy)2(7)]2+ cation (Ru, black; poly(e-
ACHTUNGTRENNUNG
Conclusions
By using bpy-centred ligands with terminal alkene function-
alities, we have illustrated the application of Grubbsꢀ meth-
odology to couple the alkene units of the coordinated li-
gands in [FeL3]2+ complexes (L=2 or 3). Hydrogenation
and demetallation of the iron(II)-containing macrocyclic
complexes results in the isolation of organic macrocycles
containing up to 96 atoms and three bpy units. The latter
[{RuACHTUNGTRENNUNG(bpy)2}2(5)]ACHTUNGTRENNUNG[PF6]4 and [{RuAHCTNUGERTNN(GUN bpy)2}3(6)]ACTHNGUTRENN[UNG PF6]6 exhibit a
metal-to-ligand charge transfer band at 457 nm in addition
to a series of higher-energy intense absorptions originating
!
from ligand-based p* p transitions. Excitation of each
complex at around 350 nm (see Experimental Section) led
to a single emission (616 nm for [Ru
[Ru
(bpy)2(7)]2+, 617 nm for [{Ru(bpy)2}2(5)]4+ and 621 nm
for [{Ru
(bpy)2}3(6)]6+).
(bpy)2(1)]2+, 641 nm for
ACHTUNGTRENNUNG
A
U
bind {RuACTHGNUTRENNU(G bpy)2} units to give macrocyclic complexes with
exocyclic ruthenium(II)-containing domains. For ligand 4
A
The electrochemical properties of the complexes were
studied by cyclic and square-wave voltammetry and are
summarized in Table 1. Each complex undergoes a single,
reversible metal-centred oxidation at slightly higher poten-
(which contains the longest poly(ethyleneoxy) chains in our
study), intramolecular RCM starting from [Ru
ACHTUNGTRENNUNG
leads to a macrocycle which retains the exocyclic {RuACHTUNGTRENNUNG
unit. The poly(ethyleneoxy) domains in the latter macrocy-
cle are capable of scavenging sodium ions, as proven by
single-crystal X-ray diffraction and by AAS data for the
bulk sample. The ligands presented herein were the result of
an attempt to prepare a trefoil knot through the Sokolov ap-
proach at a single metal centre. In the event, the non-knot-
ted topological isomers were obtained but the exquisite con-
tial than [RuACHTUNGTRENNUNG
(bpy)3]2+ (0.89 V under the same experimental
conditions as for the complexes studied here). Each complex
undergoes a series of ligand-based reductions which, for the
di- and trinuclear complexes, are irreversible, but tend to be
reversible for the mononuclear species.
Chem. Eur. J. 2009, 15, 11746 – 11757
ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
11753

C. E. Housecroft, E. C. Constable et al.
13C NMR (126 MHz, CD3CN) d=161.4 (CB3), 158.3 (CD2), 158.0 (CC2),
156.5 (CA2), 153.1 (CA6), 150.0 (CC6+D6), 140.6 (CB1), 138.9 (CC4/D4), 138.85
(CC4/D4), 137.2 (CA5), 136.8 (CA4), 131.6 (CB5), 128.7 (CC5), 128.6 (CD5),
125.5 (CA3/C3/D3), 125.33 (CA3/C3/D3), 125.32 (CA3/C3/D3), 120.4 (CB4/B6), 116.3
(CB4/B6), 113.3 (CB2), 56.2 ppm (OMe); 19F NMR (376 MHz, CD3CN) d=
ꢀ74.1 ppm (d, J=706 Hz); IR (solid): n˜ =3088w, 2934w, 1601w, 1578w,
1464m, 1447m, 1427m, 1285w, 1215w, 1171w, 1051w, 1028w, 878w, 829s,
791m, 762m, 731m, 698w cmꢀ1; UV/Vis (CH2Cl2): lmax (e)=457 (15000),
trol over the stoichiometry of the reaction through the chain
length of the spacer prompted us to study these systems in
detail.
Experimental Section
318 sh (46500), 289 nm (85900 molꢀ1 dm3 cmꢀ1); emission (CH2Cl2, lexc
=
General: 1H and 13C NMR spectra were recorded (ꢃ295 K) on Bruker
Avance DRX-600, DRX-500 and DPX-400 MHz spectrometers; chemical
shifts were relative to residual solvent peaks with TMS d=0 ppm for 1H
350 nm): lmax =616 nm; ESIMS: m/z 391.2 [Mꢀ2PF6]2+ (calcd 391.1),
927.1 [MꢀPF6]+ (calcd 927.2); elemental analysis calcd (%) for
C44H36F12N6O2P2Ru: C 49.31, H 3.39, N 7.86; found C 49.20, H 3.39, N
7.70.
ACTHNUTRGNEUNG
and 13C, and relative to CF(35Cl)3 in CDCl3 for 19F (external reference).
NMR spectra were assigned by using distortionless enhancement by po-
larization transfer (DEPT) and 2D techniques (COSY, NOESY, HMQC
and HMBC). Infrared spectra were recorded on a Shimadzu FTIR-8400S
spectrophotometer (solid samples, Golden Gate diamond attenuated
total reflectance accessory). ESI mass spectra were recorded with Finni-
gan MAT LCQ or Bruker Esquire 3000plus instruments, and EI mass spec-
tra with a VG 70-250 instrument. Electronic absorption and emission
spectra were recorded on a Varian Cary 5000 spectrophotometer and a
Shimadzu RF-5301 PC spectrofluorometer, respectively. Microwave reac-
tions were carried out in a Biotage Initiator 8 reactor. Solvents were dis-
tilled before use, and reactions were carried out under N2. Electrochemi-
cal measurements were performed by using an Eco Chemie Autolab
PGSTAT 20 apparatus with a glassy carbon working electrode, platinum
mesh for counter electrode, and silver wire as reference electrode. Com-
pounds were dissolved and measured in dry and argon-purged MeCN
5,5’-Bis[3-(1,4,7-trioxadec-9-enylphenyl)]-2,2’-bipyridine (3): 5,5’-Bis(3’-
hydroxyphenyl)-2,2’-bipyridine (2.40 g, 7.05 mmol), 1-bromo-3,6-dioxa-
non-8-ene (3.24 g, 15.5 mmol) and Cs2CO3 (8.00 g, 24.5 mmol) were dis-
solved in dry DMF (200 mL). The reaction mixture was heated for 4 days
at 1208C. Removal of DMF, column chromatography (SiO2, CH2Cl2/
MeOH 49:1) and filtration over Al2O3 yielded 3 as a colourless crystal-
line solid (3.33 g, 5.58 mmol, 79%). M.p. 73–758C; 1H NMR (500 MHz,
CD2Cl2): d=8.93 (s, 2H; HA6), 8.55 (d, J=8.2 Hz, 2H; HA3), 8.06 (dd, J=
2.2, 8.3 Hz, 2H; HA4), 7.43 (t, J=7.9 Hz, 2H; HB5), 7.29 (d, J=7.7 Hz,
2H; HB6), 7.24 (m, 2H; HB2), 6.99 (dd, J=2.1, 8.2 Hz, 2H; HB4), 5.92 (m,
2H; Hb1), 5.27 (dd, J=1.6, 17.2 Hz, 2H; Hb3), 5.16 (dd, J=1.5, 10.4 Hz,
2H; Hb2), 4.21 (m, 4H; Ha1), 4.01 (m, 4H; Ha5), 3.88 (m, 4H; Ha2), 3.71
(m, 4H; Ha3), 3.62 ppm (m, 4H; Ha4); 13C NMR (126 MHz, CD2Cl2) d=
160.0 (CB3), 155.2 (CA2), 148.2 (CA6), 139.6 (CB1), 136.8 (CA5), 135.8 (CA4),
135.6 (Cb1), 130.73 (CB5), 121.3 (CA3), 120.1 (CB6), 117.0 (Cb2/3), 114.7
(CB4), 113.9 (CB2), 72.6 (Ca5), 71.4 (Ca3), 70.2 (Ca2), 70.1 (Ca4), 68.2 ppm
(Ca1); IR (solid): n˜ =3010w, 2872m, 1724w, 1605m, 1578s, 1460s, 1441m,
1362w, 1298m, 1277m, 1231w, 1202m, 1119m, 1099m, 1059m, 1018w,
933m, 841s, 777s, 744w, 692m, 611m cmꢀ1; EI-MS: m/z 596.3 [M]+ (calcd
596.3); elemental analysis calcd (%) for C36H40N2O6 C: 72.46, H 6.76, N
4.69; found C 72.26, H 6.66, N 4.49.
with 0.1m [nBu4N]ACHTUNGTRENNUNG[PF6] as supporting electrolyte. The scan rate was
100 mVsꢀ1 and ferrocene was added as an internal standard at the end of
every experiment. AAS measurements: see the Supporting Information.
cis-[RuACHTUNGTRENNUNG
(bpy)2Cl2],[33] 5,5’-bis(3’-hydroxyphenyl)-2,2’-bipyridine[27] and li-
gands 1[27] and 2[28] were prepared as previously reported. Second-genera-
tion Hoyveda–Grubbs catalyst and [Et4N][D-TRISPHAT] were pur-
chased from Aldrich and Pd/C from Avocado, and were used as received.
[Ru
procedure as for [Ru
and cis-[Ru(bpy)2Cl2] (58.8 mg, 121 mmol). Column chromatography
(SiO2, CH2Cl2/MeOH 20:1) yielded [Ru(bpy)2(3)][PF6]2 (141 mg,
ACHUTGTNNERNUG(bpy)2(3)]ACHTGNUTRENNUNG
[Fe(1)3]ACHTUNGTRENNUNG[PF6]2: Ligand 1 (249 mg, 676 mmol) was dissolved in CH2Cl2
A
ACHTUNGTRENNUNG
(2 mL) and MeCN (10 mL). An aqueous solution containing an excess of
FeCl2·4H2O (45.0 mg, 355 mmol) was added causing an immediate colour
change to red. The reaction mixture was heated at reflux for 2 days, and
then the organic solvents were removed in vacuo. An excess of aqueous
NH4PF6 was added. The aqueous phase was extracted with CH2Cl2 (3ꢃ
50 mL) and the combined organic layers were dried over MgSO4. Re-
moval of solvent and recrystallization from CH2Cl2/Et2O yielded [Fe(1)3]-
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG
108 mmol, 90%) as an orange solid. M.p. 99–1028C; 1H NMR (500 MHz,
CD3CN): d=8.58 (d, J=8.6 Hz, 2H; HA3), 8.52 (m, 4H; HC3+D3), 8.33
(dd, J=2.0, 8.5 Hz, 2H; HA4), 8.09 (m, 4H; HC4+D4), 7.89 (d, J=5.5 Hz,
2H; HC6), 7.82 (d, J=5.6 Hz, 2H; HD6), 7.81 (d, J=1.7 Hz, 2H; HA6),
7.44 (m, 4H; HC5+D5), 7.35 (t, J=8.0 Hz, 2H; HB5), 7.00 (m, 4H; HB4+B6),
6.93 (s, 2H; HB2), 5.90 (m, 2H; Hb1), 5.25 (dd, J=3.3, 17.3 Hz, 2H; Hb3),
5.12 (dd, J=1.4, 10.4 Hz, 2H; Hb2), 4.07 (dd, J=5.3, 9.7 Hz, 4H; Ha1),
3.97 (dd, J=1.2, 4.2 Hz, 4H; Ha5), 3.80 (m, 4H; Ha2), 3.65 (dd, J=3.5,
5.7 Hz, 4H; Ha3/a4), 3.57 ppm (dd, J=3.5, 5.6 Hz, 4H; Ha3/a4); 13C NMR
(126 MHz, CD3CN): d=160.5 (CB3), 158.3 (CA2), 158.0 (CD2), 156.5 (CC2),
153.1 (CC3+D3), 150.0 (CA6), 140.6 (CA5), 138.9 (CC4/D4), 138.85 (CC4/D4),
137.2 (CB1), 136.77 (CA4), 136.3 (Cb1), 131.7 (CB5), 128.7 (CC5/D5), 128.6
(CC5/D5), 125.5 (CA3), 125.3 (2 CC5+D5), 120.5 (CB6), 117.0 (Cb2/3), 116.95
(CB4), 113.8 (CB2), 72.5 (Ca5), 71.45 (Ca3/a4), 70.4 (Ca3/a4), 70.2 (Ca2),
68.8 ppm (Ca1); 19F NMR (376 MHz, CD3CN): d=ꢀ74.1 ppm (d, J=
706 Hz); IR (solid): n˜ =3077w, 2934w, 2881w, 1601w, 1595w, 1463m,
1445m, 1422m, 1301w, 1242w, 1206m, 1051w, 1028w, 825s, 762m,
695w cmꢀ1; UV/Vis (MeCN): lmax (e)=456 (15900), 316 (46300), 288 nm
(79000 molꢀ1 dm3 cmꢀ1); emission (MeCN, lexc =355 nm): lmax =642 nm;
ESIMS: m/z 1155.4 [MꢀPF6]+ (calcd 1155.3), 505.2 [Mꢀ2PF6]2+ (calcd
505.2); elemental analysis calcd (%) for C56H56F12N6O6P2Ru: C 51.74, H
4.34, N 6.46; found C 51.78, H 4.25, N 6.24.
ACHTUNGTRENNUNG
[PF6]2 (131 mg, 90 mmol, 35%). M.p. 179–1828C; 1H NMR (400 MHz,
CDCl3): d=8.52 (d, J=8.3 Hz, 6H; HA3), 8.25 (d, J=8.4 Hz, 6H; HA4),
7.52 (s, 6H; HA6), 7.18 (t, J=8.0 Hz, 6H; HB5), 6.81 (d, J=8.2 Hz, 6H;
HB6), 6.76 (d, J=7.4 Hz, 6H; HB4), 6.69 (s, 6H; HB2), 3.57 ppm (s, 18H;
HMe); 13C NMR (101 MHz, CDCl3): d=159.8 (CB3), 156.8 (CA2), 151.3
(CA6), 139.3 (CA5), 136.6 (CA4), 135.0 (CB1), 130.2 (CB5), 123.6 (CA3), 118.6
(CB6), 114.8 (CB4), 111.8 (CB2), 54.8 ppm (CMe); IR (solid): n˜ =2935w,
2833w, 1717w, 1601m, 1582m, 1504m, 1470s, 1448m, 1433m, 1371m,
1304w, 1288m, 1246w, 1219m, 1173w, 1153m, 1051m, 1024m, 995m, 822s,
777m, 729m, 687w, 667m, 619m, 606m, 555m cmꢀ1; ESIMS: m/z 580.5
[Mꢀ2PF6]2+ (calcd 580.2); elemental analysis calcd (%) for
C72H60F12FeN6O6P2: C 59.60, H 4.17, N 5.79; found C 59.30, H 4.36, N
5.55.
[Ru
ACHTUNGTRENNUNG(bpy)2(1)]ACHTUNGTRENNUNG
235 mmol) and cis-[RuACHTUNGTRENNUNG
EtOH (5 mL). The reaction mixture was heated in a microwave reactor
for 40 min at 1408C. An excess of aqueous NH4PF6 (ꢃ4 mmol, 100 mL)
was added to the orange solution. An orange precipitate formed which
was isolated by filtration and washed with water (50 mL) and ether
5,5’-Bis[3-(1,4,7,10-tetraoxatridec-12-enylphenyl)]-2,2’-bipyridine
(4):
Ligand 4 was prepared by the same method as 3 starting with 5,5’-bis(3’-
hydroxyphenyl)-2,2’-bipyridine (1.11 g, 3.26 mmol), 1-bromo-3,6,9-trioxa-
undec-11-ene (2.06 g, 8.15 mmol) and Cs2CO3 (4.25 g, 13.0 mmol). Ligand
4 was isolated as a colourless solid (2.01 g, 2.93 mmol, 90%). M.p. 57–
588C; 1H NMR (500 MHz, CD2Cl2): d=8.94 (d, J=1.8 Hz, 2H; HA6),
8.56 (d, J=8.2 Hz, 2H; HA3), 8.07 (dd, J=2.1, 8.3 Hz, 2H; HA4), 7.43 (t,
J=7.9 Hz, 2H; HB5), 7.29 (d, J=7.7 Hz, 2H; HB6), 7.25 (d, J=1.9 Hz,
(50 mL) to yield [RuACHTUNGTRENNUNG(bpy)2(1)]ACHTUGNTERN[NUGN PF6]2 (234 mg, 218 mmol, 93%) as an
orange powder. M.p. 327–3298C; 1H NMR (500 MHz, CD3CN): d=8.58
(d, J=8.5 Hz, 2H; HA3), 8.51 (m, 4H; HC3+D3), 8.33 (dd, J=2.0, 8.5 Hz,
2H; HA4), 8.07 (td, J=1.3, 8.0 Hz, 4H; HC4+D4), 7.89 (d, J=5.3 Hz, 2H;
HC6/D6), 7.82 (d, J=5.3 Hz, 2H; HD6/C6), 7.80 (d, J=1.8 Hz, 2H; HA6),
7.44 (m, 4H; HC5+D5), 7.36 (t, J=8.0 Hz, 2H; HB5), 7.00 (dd, J=2.0,
8.0 Hz, 4H; HB4+B6), 6.92 (t, J=2.0 Hz, 2H; HB2), 3.77 ppm (s, 6H; HMe);
11754
www.chemeurj.org
ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2009, 15, 11746 – 11757

Ruthenium-Containing Macrocycles
FULL PAPER
2H; HB2), 6.99 (dd, J=2.1, 8.2 Hz, 2H; HB4), 5.90 (m, 2H; Hb1), 5.26 (dd,
J=1.6, 17.2 Hz, 2H; Hb3), 5.15 (dd, J=1.3, 10.4 Hz, 2H; Hb2), 4.21 (m,
4H; Ha1), 3.99 (d, J=5.6 Hz, 4H; Ha7), 3.87 (m, 4H; Ha2), 3.70 (m, 4H;
Ha3), 3.63 (m, 8H), 3.57 ppm (m, 4H); 13C NMR (126 MHz, CD2Cl2): d=
160.0 (CB3), 155.2 (CA2), 148.1 (CA6), 139.6 (CB1), 136.7 (CA5), 135.7 (CA4),
135.6 (Cb1), 130.7 (CB5), 121.3 (CA3), 120.1 (CB6), 116.9 (Cb2/3), 114.6 (CB2),
113.9 (CB4), 72.5, 71.3, 71.1 (2C), 70.2, 70.1, 68.2 ppm (Ca1); IR (solid):
n˜ =2868m, 1599m, 1582m, 1464s, 1364m, 1300m, 1232w, 1209m, 1126m,
1107m, 1067m, 932m, 633w cmꢀ1; EI-MS: m/z 685.4 [M]+ (calcd 685.4);
elemental analysis calcd (%) for C40H48N2O8: C 70.16, H 7.06, N 4.09;
found C 70.03, H 7.06, N 4.00.
30 min, the red colour had disappeared. The solvent volume was reduced
and the solution was extracted with CH2Cl2 (3ꢃ100 mL). The combined
organic layers were dried over MgSO4, filtered and the solvent was re-
moved in vacuo to yield a brown oil. The crude product was dissolved in
CH2Cl2 (50 mL) and EtOH (50 mL) and the reaction mixture was stirred
under an atmosphere of H2 (1 bar) at room temperature for 2 days in the
presence of Pd/C (100 mg, 30 mol% Pd). After column chromatography
(SiO2, CH2Cl2, NEt3 (1–3%)) followed by preparative thin-layer chroma-
tography (Al2O3, CH2Cl2/MeOH (1%), twice; Al2O3, CH2Cl2/MeOH
(0.6%), once), ligand 5 was isolated as a colourless solid (10.5 mg, 7%,
ꢃ80% pure). 1H NMR (400 MHz, CD2Cl2): d=8.85 (m, 4H; HA6), 8.45
(d, J=8.3 Hz, 4H; HA3), 7.97 (dd, J=2.3, 8.3 Hz, 4H; HA4), 7.38 (t, J=
7.9 Hz, 4H; HB5), 7.22 (m, 8H; HB2+B6), 6.96 (m, 4H; HB4), 4.17 (m, 8H;
Ha1), 3.78 (m, 8H; Ha2/a3), 3.57 (m, 8H; Ha2/a3), 1.68 ppm (m, 8H; Ha4);
ESIMS: m/z 988.0 [M+Na]+ (calcd 988.1). The ligand was used in the
next step without further purification.
[Ru
procedure as for [Ru
raoxatridec-12-enylphenyl)]-2,2’-bipyridine (420 mg, 613 mmol) and cis-
[Ru(bpy)2Cl2] (300 mg, 619 mmol). After column chromatography (SiO2,
CH2Cl2/MeOH 20:1), [Ru(bpy)2(4)][PF6]2 was isolated as an orange solid
ACHTUNGTRENNUNG(bpy)2(4)]ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
(793 mg, 571 mmol, 93%). M.p. 77–798C; 1H NMR (500 MHz, CDCl3):
d=8.50 (d, J=8.6 Hz, 2H; HA3), 8.44 (m, 4H; HC3+D3), 8.13 (d, J=
8.3 Hz, 2H; HA4), 7.99 (t, J=8.0 Hz, 2H; HC4/D4), 7.95 (t, J=7.9 Hz, 2H;
HC4/D4), 7.79 (d, J=4.1 Hz, 4H; HC6+D6), 7.65 (s, 2H; HA6), 7.47 (m, 4H;
HC5+D5), 7.22 (t, J=8.0 Hz, 2H; HB5), 6.83 (m, 6H; HB2+B4+B6), 5.84 (m,
2H; Hb1), 5.20 (dd, J=1.4, 17.2 Hz, 2H; Hb3), 5.09 (d, J=10.4 Hz, 2H;
Hb2), 4.05 (m, 4H; Ha1), 3.95 (d, J=5.6 Hz, 4H; Ha6), 3.81 (m, 4H; Ha2),
3.69 (m, 4H; Ha3/a4), 3.64 (m, 8H; Ha3/a4+a5), 3.56 ppm (m, 4H; Ha7);
13C NMR (126 MHz, CDCl3): d=159.6 (CB3), 156.8 (CC2/D2), 156.3 (CC2/D2),
155.1 (CA2), 151.7 (CC6/D6), 151.4 (CC6/D6), 148.1 (CA6), 140.5 (CA5), 138.3
(CC4/D4), 138.25 (CC4/D4), 136.3 (CA4), 135.7 (CB1), 134.7 (Cb1), 130.8 (CB5),
128.6 (CC5/D5), 128.3 (CC5/D5), 124.6 (CC3/D3), 124.5 (CC3/D3), 124.3 (CA3),
119.6 (CB6), 117.1 (Cb2/3), 116.5 (CB4), 112.7 (CB2), 72.1 (Ca7), 70.7 (Ca3/a4),
70.6 (Ca3/a4), 69.5 (Ca2), 69.4 (Ca6), 67.6 ppm (Ca1); 19F NMR (376 MHz,
CD3CN): d=ꢀ74.09 ppm (d, J=706 Hz); IR (solid): n˜ =3080w, 2864m,
1601m, 1580m, 1464w, 1445w, 1423w, 1369m, 1302m, 1217m, 1095m,
1063m, 945w, 827s, 764m, 731m, 698w cmꢀ1; UV/Vis (MeCN): lmax (e)=
[{Ru
dure as [Ru
and cis-[Ru(bpy)2Cl2] (10.8 mg, 22.4 mmol). Preparative thick-layer chro-
matography (Al2O3, CH2Cl2/MeOH 20:1) gave [{Ru(bpy)2}2(5)][PF6]4 as
G
ACHTUNGTRENNUNG
R
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
G
ACHTUNGTRENNUNG
an orange solid (12.1 mg, 5.1 mmol, 46%). M.p. 192–1968C; 1H NMR
(600 MHz, CD3CN): d=8.48 (m, 8H; HC3+D3), 8.41 (dd, J=2.7, 8.5 Hz,
4H; HA3), 8.16 (m, 4H; HA4), 8.01 (m, 8H; HC4+D4), 7.86 (m, 4H; HC6),
7.78 (m, 8H; HA6+D6), 7.39 (m, 8H; HC5+D5), 7.32 (t, J=8.1 Hz, 4H;
HB5), 6.98 (dd, J=2.0, 8.7 Hz, 4H; HB4), 6.91 (m, 8H; HB2+B6), 4.04 (m,
8H; Ha1), 3.71 (m, 8H; Ha2), 3.48 (m, 8H; Ha3), 1.57 ppm (m, 8H; Ha4);
13C NMR (151 MHz, CD3CN): d=160.0 (CB3), 157.6 (CC2), 157.3 (CD2),
155.7 (CA2), 152.4 (CC6+D6), 149.3 (CA6), 139.9 (CA5), 138.2 (CD4), 136.4
(CB1), 136.0 (CA4), 131.0 (CB5), 128.1 (CC5), 128.0 (CD5), 124.9 (CD3), 124.7
(CC3), 124.6 (CA3), 119.7 (CB6), 116.2 (CB4), 113.7 (CB2), 71.1 (Ca3), 69.3
(Ca2), 68.2 (Ca1), 26.64 ppm (Ca4); 19F NMR (376 MHz, CD3CN): d=
ꢀ74.09 ppm (d, J=706 Hz); ESIMS: m/z 1041.3 [Mꢀ2PF6]2+ (calcd
1041.2), 646.0 [Mꢀ3PF6]3+ (calcd 645.8), 448.2 [Mꢀ4PF6]4+ (calcd 448.1);
IR (solid): n˜ =3086w, 2922m, 2853m, 1601m, 1582m, 1464m, 1445m,
1369w, 1301w, 1211m, 1119m, 1055w, 825s, 761m cmꢀ1; UV/Vis (CH2Cl2):
lmax (e)=457 (19700), 316 sh (61800), 290 nm (114300 molꢀ1 dm3 cmꢀ1);
emission (CH2Cl2, lexc =450 nm): lmax =617 nm; elemental analysis calcd
(%) for C100H92F24N12O8P4Ru2: C 50.64, H 3.91, N 7.09; found C 50.58, H
4.12, N 7.13.
456 (16200), 318 nm (56900 molꢀ1 dm3 cmꢀ1); emission (CH2Cl2, lexc
=
350 nm): lmax =636 nm; ESIMS: m/z 1243.2 [MꢀPF6]+ (calcd 1243.3),
549.1 [Mꢀ2PF6]2+ (calcd 549.2); elemental analysis calcd (%) for
C60H64F12N6O8P2Ru: C 51.91, H 4.65, N 6.05; found C 51.93, H 4.68, N
5.87.
[Fe(2)3]
ACHTUNGTRENNUNG
(40 mL) and an aqueous solution (40 mL) of Fe
N
[Fe(3)3]ACTHUGNTREN[NUG BF4]2: Ligand 3 (1.84 g, 3.08 mmol) and FeACTHUGNTREN(NUNG BF4)2·6H2O (1.04 g,
1.45 mmol) was added. The solution immediately turned red and was
heated at reflux for 12 h. A 1H NMR spectrum of the crude product
3.08 mmol) were dissolved in MeCN (300 mL) and the solution was
heated at reflux for 3 days. Filtration over Al2O3 and removal of the sol-
1
showed ꢃ10% of unreacted ligand; Fe
N
vent yielded [Fe(3)3]
N
(500 MHz, CD3CN): d=8.66 (d, J=8.5 Hz, 6H; HA3), 8.44 (dd, J=1.8,
8.5 Hz, 6H; HA4), 7.75 (d, J=1.3 Hz, 6H; HA6), 7.33 (t, J=8.0 Hz, 6H;
HB5), 7.06 (d, J=7.7, 6H; HB6), 6.96 (dd, J=2.1, 8.3 Hz, 6H; HB4), 6.89
(s, 6H; HB2), 5.86 (m, 6H; Hb1), 5.22 (dd, J=1.7, 17.3 Hz, 6H; Hb3), 5.10
(dd, J=1.5, 10.4 Hz, 6H; Hb2), 3.95 (m, 24H; Ha1+a5), 3.68 (m, 12H; Ha2),
3.58 (m, 12H; Ha3), 3.53 ppm (m, 12H; Ha4); 13C NMR (126 MHz,
CD3CN): d=160.5 (CB3), 158.8 (CA2), 153.5 (CA6), 140.0 (CA5), 137.7
(CA4), 137.1 (CB1), 136.3 (Cb1), 131.7 (CB5), 125.3 (CA3), 120.6 (CB6), 117.2
(CB4), 117.0 (Cb2,b3), 113.4 (CB2), 72.5 (Ca5), 71.4 (Ca3), 70.4 (Ca4), 70.2
(Ca2), 68.7 ppm (Ca1); 19F NMR (376 MHz, CDCl3): d=ꢀ153.1 ppm (s);
ESIMS: m/z 923.2 [Mꢀ2BF4]2+ (calcd 922.9); UV/Vis (MeCN): lmax (e)=
from the filtrate, [Fe(2)3]ACHTNUTRGNE[UGN BF4]2 was isolated as a red solid which was
dried in vacuo (848 mg, 483 mmol, 100%). 1H NMR (400 MHz, CDCl3):
d=8.91 (d, J=8.3 Hz, 6H; HA3), 8.36 (d, J=7.7 Hz, 6H; HA4), 7.54 (s,
6H; HA6), 7.27 (t, J=8.0, 6H; HB5), 6.93 (d, J=8.4 Hz, 6H; HB6), 6.79
(m, 12H; HB2+B4), 5.90 (m, 6H; Hb1), 5.28 (m, 6H; Hb3), 5.18 (dd, J=1.4,
10.4 Hz, 6H; Hb2), 4.03 (m, 24H), 3.74 ppm (m, 12H; Ha1+a2+a3);
13C NMR (101 MHz, CDCl3); d=159.8, 157.5, 150.6, 140.5, 137.8, 135.2,
134.4, 131.0, 125.4, 119.2, 117.4, 116.5, 112.8, 72.3, 68.3, 67.7 ppm;
ESIMS: m/z 790.8 [Mꢀ2BF4]2+ (calcd 790.3); elemental analysis calcd
(%) for C96H96B2F8FeN6O12: C 65.69, H 5.51, N 4.79; found C 65.37, H
5.54, N 4.72.
336 (102700), 544 nm (8960 molꢀ1 dm3 cmꢀ1); emission (MeCN, lexc
=
340 nm):
108H120N6O18B2F8Fe·2H2O: C 63.10, H 6.08, N 4.09; found C 63.10, H
6.10, N 4.24.
Ligand 6: [Fe(3)3]CATHNUGTNRE[NUG BF4]2 (1.93 g, 955 mmol) and second-generation Hoyve-
lmax =406 nm;
elemental
analysis
calcd
(%)
for
C
Ligand 5: [Fe(2)3]ACHTUNGTRENNUNG[BF4]2 (267 mg, 152 mmol) and second-generation Hoy-
veda–Grubbs catalyst (19.0 mg, 30.4 mmol) were dissolved in CH2Cl2
(250 mL). The solution was stirred at room temperature for 40 days.
During this time, additional catalyst was added (10 mg after 10 days, and
5 mg after 25 days). The reaction was quenched with ethyl vinyl ether
(5 mL) and the solvent was removed in vacuo to yield a red solid. The
1H NMR and ESI mass spectra of the product confirmed that >95%
alkene metathesis had been achieved; the compound was used in the
next step without purification. The crude product was dissolved in MeCN
(100 mL) and an aqueous solution (30 mL) of Na2H2EDTA (283 mg,
760 mmol) and Na2CO3 (80.5 mg, 760 mmol) was added. The reaction mix-
ture was heated to 508C and stirred at that temperature for 1 h. After
da–Grubbs catalyst (75.0 mg, 120 mmol) were dissolved in CH2Cl2
(955 mL). The solution was stirred at room temperature for 30 days.
During this time, additional catalyst was added (75 mg after 8 days, and
30 mg after 20 days). The reaction was quenched with ethyl vinyl ether
(5 mL) and the solvent was removed in vacuo to give a red solid.
1H NMR and ESIMS confirmed that>95% alkene metathesis had been
achieved, and the compound was used further without purification. The
crude product was dissolved in a mixture of EtOH (150 mL) and CH2Cl2
(150 mL), and Pd/C (500 mg, 25 mol% Pd) was added. The reaction mix-
Chem. Eur. J. 2009, 15, 11746 – 11757
ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
11755

C. E. Housecroft, E. C. Constable et al.
ture was stirred under an atmosphere of H2 (1 bar) at room temperature
for 12 h. The 1H NMR and ESI mass spectra of the product confirmed
complete hydrogenation. The crude product (ꢃ955 mmol) was dissolved
in MeCN (200 mL) and an aqueous solution (20 mL) of Na2H2EDTA
(1.86 g, 5.00 mmol) and Na2CO3 (1.06 g, 10.0 mmol) was added. The reac-
tion mixture was stirred at 508C for 3 h; the red colour disappeared after
30 min. The organic solvent was removed in vacuo and the aqueous resi-
due was extracted with CH2Cl2 (5ꢃ50 mL). The combined organic layers
were dried over MgSO4, filtered and the solvent removed in vacuo to
yield a brown oil (1.65 g). Part of the residue (440 mg) was purified by
preparative thin-layer chromatography (Al2O3, CH2Cl2/MeOH (1.1%),
6 h elution) on eight plates and ligand 6 was isolated as a colourless oil
(113 mg, 66.0 mmol, 26%). 1H NMR (500 MHz, CD2Cl2): d=8.90 (d, J=
1.8, 6H; HA6), 8.50 (d, J=8.3 Hz, 6H; HA3), 8.01 (dd, J=2.2, 8.3 Hz, 6H;
HA4), 7.39 (t, J=7.9 Hz, 6H; HB5), 7.24 (d, J=7.9 Hz, 6H; HB6), 7.22 (d,
J=1.8 Hz, 6H; HB2), 6.96 (dd, J=2.1, 8.2 Hz, 6H; HB4), 4.17 (m, 12H;
Ha1), 3.83 (m, 12H; Ha2), 3.67 (m, 12H; Ha3), 3.57 (m, 12H; Ha4), 3.46
(m, 12H; Ha5), 1.62 ppm (m, 12H; Ha6); 13C NMR (126 MHz, CD2Cl2):
d=160.0 (CB3), 155.2 (CA2), 148.1 (CA6), 139.5 (CB1), 136.6 (CA5), 135.6
(CA4), 130.7 (CB5), 121.3 (CA3), 120.0 (CB6), 114.6 (CB4), 113.9 (CB2), 71.6
(Ca1), 71.4 (Ca2), 70.7 (Ca3), 70.2 (Ca4), 68.2 (Ca5), 27.0 ppm (Ca6); IR
(solid): n˜ =2920m, 2862m, 1722w, 1682m, 1597m, 1580m, 1462s, 1439m,
1362w, 1298m, 1281w, 1231w, 1205m, 1103s, 1063m, 1018m, 995s, 937w,
839s, 779s, 744m, 694m, 652w, 604m cmꢀ1; ESIMS: m/z 1734.6 [M+Na]+
(calcd 1734.8); elemental analysis calcd (%) for C102H114N6O18·2H2O: C
70.08, H 6.80, N 4.81; found C 70.18, H 6.94, N 4.92.
CH2Cl2 (20 mL) in the presence of a catalytic amount of Pd/C (30 mg).
The solvent was removed in vacuo, and the product re-dissolved in the
minimum amount of CH2Cl2. [RuACHTUNRGTENNUG(bpy)2(7)]CAHUTNGTRENN[UGN PF6]2 was purified by prepa-
rative thick-layer chromatography (SiO2, CH2Cl2/MeOH 25:1) and was
isolated as an orange solid (20.2 mg, 14.8 mmol, 10%; see text). 1H NMR
(500 MHz, CD3CN): d=8.63 (d, J=8.1 Hz, 2H; HD3), 8.56 (t, J=8.0 Hz,
4H; HC3A3), 8.35 (dd, J=2.0, 8.5 Hz, 2H; HA4), 8.22 (td, J=1.2, 7.9 Hz,
2H; HD4), 8.06 (m, 2H; HC4), 7.90 (d, J=5.0 Hz, 2H; HC6), 7.84 (d, J=
5.5 Hz, 2H; HD6), 7.82 (d, J=1.8 Hz, 2H; HA6), 7.55 (m, 2H; HD5), 7.42
(t, J=6.6 Hz, 2H; HC5), 7.38 (t, J=8.0 Hz, 2H; HB5), 7.27 (d, J=7.8 Hz,
2H; HB6), 6.96 (dd, J=2.2, 8.2 Hz, 2H; HB4), 6.72 (m, 2H; HB2), 3.98 (t,
J=6.1 Hz, 4H; Ha1), 3.76 (t, J=6.0 Hz, 4H; Ha2), 3.72–3.45 (m, 8H), 3.38
(m, 4H), 2.30 (m, 4H; Ha7), 1.58 ppm (m, 4H; Ha8); 13C NMR (126 MHz,
CD3CN): d=160.8 (CB3), 158.3 (CC2/D2), 158.2 (CC2/D2), 156.7 (CA2), 153.5
(CA6), 150.3 (CC2+D2), 140.3 (CB1), 140.1 (CD4), 139.2 (CC4), 137.0 (CA5),
136.3 (CA4), 132.1 (CB5), 129.5 (CD5), 129.0 (CC5), 126.0 (CC3/D3A3), 125.9
(CC3/D3A3), 125.6 (CC3/D3A3), 120.9 (CB6), 118.9 (CB4), 113.0 (CB2), 71.9,
71.8, 71.6, 71.2, 70.1 (Ca2), 68.7 (Ca1), 34.6 (Ca7), 27.0 ppm (Ca8); 19F NMR
(376 MHz, CD3CN): d=ꢀ74.1 ppm (d, J=706 Hz); IR (solid): n˜ =
2921m, 2892w, 2853m, 1728m, 1717m, 1601m, 1585w, 1464m, 1446m,
1423m, 1372w, 1352w, 1302w, 1275m, 1243m, 1215m, 1121m, 1093m,
1055m, 1032m, 940w, 876w, 829s, 792m, 767s, 740w, 732m, 695m, 690m,
660m cmꢀ1; UV/Vis (CH2Cl2): l(e)=457 (14700), 354 sh (39200), 321 sh
(45700), 290 nm (86800 molꢀ1 dm3 cmꢀ1); emission (MeCN, lexc =350 nm):
lmax =641 nm; ESIMS: m/z 1217.6 [MꢀPF6]+ (calcd 1217.3), 536.2
[Mꢀ2PF6]2+ (calcd 536.2). Satisfactory elemental analysis could not be
obtained, presumably because of the sodium content (see text).
[{Ru
dure as [Ru
and cis-[Ru(bpy)2Cl2] (23.6 mg, 48.6 mmol) suspended in EtOH (5 mL).
A
ACHTUNGTRENNUNG
A
ACHTUNGTRENNUNG
Crystal structure determination: Data were collected on
a Bruker–
ACHTUNGTRENNUNG
Nonius Kappa CCD or Stoe IPDS instrument; data reduction, solution
and refinement used the programs COLLECT,[34] SIR92,[35] DENZO/
SCALEPACK[36] and CRYSTALS,[37] or Stoe IPDS software[38] and
SHELXL97.[39] Structures were analysed by using Mercury v.2.2.[40]
The reaction mixture was heated in a microwave reactor at 1208C for
40 min. An excess of aqueous NH4PF6 (ꢃ1 mmol, 50 mL) was added to
the orange solution. The orange precipitate that formed was collected by
filtration and washed with water (30 mL) and diethyl ether (30 mL).
[Fe(1)3]
plate; orthorhombic; space group Pcab, a=22.5632(1), b=25.4589(2), c=
28.8665(2) ꢂ; U=16581.9(2) ꢂ3; Z=8; 1calcd =1.400 Mgmꢀ3; m
(MoKa)=
CATHUNGTREN[NUNG PF6]2·3C2H4Cl2: C78H82Cl6F12FeN6O6P2; M=1747.95; purple
[{RuACHTUNGTRENNUNG(bpy)2}3(6)]ACHTUNGTRENNUNG[PF6]6 was isolated as an orange solid (56.2 mg,
14.7 mmol, 92%). Attempts to separate the two diastereoisomers (see
text) by chromatography were unsuccessful. M.p. 170–1768C; 1H NMR
(500 MHz, CD3CN): d=8.55 (d, J=8.6 Hz, 6H; HA3), 8.50 (t, J=7.5 Hz,
12H; HC3+D3), 8.29 (d, J=8.5 Hz, 6H; HA4), 8.06 (m, 12H; HC4+D4), 7.88
(d, J=5.3 Hz, 6H; HC6), 7.81 (d, J=5.4 Hz, 6H; HD6), 7.79 (d, J=1.5 Hz,
6H; HA6), 7.43 (m, 12H; HC5+D5), 7.30 (t, J=7.9 Hz, 6H; HB5), 6.95 (m,
18H; HB2+B4+B6), 4.05 (m, 12H; Ha1), 3.75 (m, 12H; Ha2), 3.59 (m, 12H;
Ha3/a4), 3.52 (m, 12H; Ha3/a4), 3.37 (m, 12H; Ha5), 1.52 ppm (m, 12H;
Ha6); 13C NMR (126 MHz, CD3CN): d=160.5 (CB3), 158.3 (CD2), 158.0
(CC2), 156.5 (CA2), 153.1 (CC6+D6), 150.0 (CA6), 140.6 (CB1), 139.0 (CC4/D4),
138.9 (CC4/D4), 137.2 (CA5), 136.8 (CA4), 131.7 (CB5), 128.7 (CD5), 128.65
(CC5), 125.5 (CC3/D3), 125.3 (CC3/D3), 120.5 (CB4/B6), 117.0 (CB4/B6), 113.9
(CB2), 71.6 (Ca5), 71.5 (Ca3/a4), 70.9 (Ca3/a4), 70.2 (Ca2), 68.8 (Ca1), 27.3 ppm
(Ca6); IR (solid): n˜ =3061w, 2929m, 2864m, 1738m, 1728m, 1601m,
1582m, 1464m, 1447m, 1369w, 1302w, 1217m, 1099m, 1059w, 827s,
761m cmꢀ1; UV/Vis (CH2Cl2): lmax (e)=457 (31200), 355 sh (77000), 318
ACHTUNGTRENNUNG
0.495 mmꢀ1; T=173(2) K; 113362 reflections collected (19770 unique);
merging r=0.049; refinement of 11198 reflections (1081 parameters)
with I>2.5s(I) converged at final R1=0.0704 (R1 all data=0.1038),
wR2=0.0813 (wR2 all data=0.0960); goodness of fit (gof)=1.050.
[RuACTHNURTGNNEG(U bpy)2(1)]ACHTUTGNRNEN[GUN PF6]2·MeCN: C46H39F12N7O2P2Ru; M=1112.85; red
¯
needle; triclinic; space group P1, a=12.449(3), b=13.757(3), c=
14.219(3) ꢂ; a=76.49(3), b=74.54(3), g=83.29(3)8; U=2278.2(8) ꢂ3;
ACTHNUTRGNEUNG
Z=2; 1calcd =1.618 Mgmꢀ3; m(MoKa)=0.512 mmꢀ1; T=173(2) K; 33505
reflections collected (8048 unique); merging r=0.1257; refinement of
7300 reflections (669 parameters) with I>2.0s(I) converged at final R1=
0.0572 (R1 all data=0.0629), wR2=0.1435 (wR2 all data=0.1493); gof=
1.096.
[{RuACTHNUTRGENNU(G bpy)}2(5)]HCAUTTGNRNE[NNGU PF6]4·C2H4Cl2·2.5EtOAc: C112H116F24N12O13P4Ru2; M=
¯
2691.12; red plate; triclinic; space group P1, a=114.116(1), b=20.075(2),
c=23.409(2) ꢂ; a=77.354(5), b=73.193(5), g=85.179(5)8; U=
sh (100100), 290 nm (181000 molꢀ1 dm3 cmꢀ1); emission (CH2Cl2, lexc
=
350 nm): lmax =621 nm; ESIMS: m/z 1765.7 [Mꢀ2PF6]2+ (calcd 1766.4),
1128.5 [Mꢀ3PF6]3+ (calcd 1129.28), 811.1 [Mꢀ4PF6]4+ (calcd 810.7),
619.8 [Mꢀ5PF6]5+ (calcd 619.6), 492.4 [Mꢀ6PF6]6+ (calcd 492.2); elemen-
tal analysis calcd (%) for C162H162F36N18O18P6Ru3: C 50.91, H 4.27, N
6.60; found C 50.63, H 4.19, N 6.20.
6194.7(11) ꢂ3; Z=2; 1calcd =1.443 Mgmꢀ3
(MoKa)=0.437 mmꢀ1
; mACHTUNGTRENNUNG ; T=
173(2) K; 386895 reflections collected (48568 unique); merging r=0.050;
refinement of 18510 reflections (1825 parameters) with I>1.9s(I) con-
verged at final R1=0.0679 (R1 all data=0.1455), wR2=0.0723 (wR2 all
data=0.1851); gof=1.0375.
[RuACHTUNGTRENNUNG(bpy)2(7)]ACHTUNGTRENNUNG[PF6]2: Complex [RuACHUTNREGTG(NNUN bpy)2(4)]CATHNUGTREN[NUGN PF6]2 (193 mg, 139 mmol)
[RuACTHUNGTERN(UNNG bpy)2(7)]CAHUTGTNRNENUG[NaRuACHTUNGETRG(NNNU bpy)2(7)]ACTHUNGNERT[UNGN PF6]5: C116H124F30N12NaO16P5Ru2; M=
and second-generation Hoyveda–Grubbs catalyst (6.0 mg, 9.6 mmol) were
dissolved in CH2Cl2 (14 mL) and stirred at room temperature for 5 days.
The 1H NMR and ESI mass spectra of the reaction mixture indicated
about 40% conversion of starting material to product. Further catalyst
(16 mg) was added to the reaction mixture, which was stirred for a fur-
ther 7 days. The 1H NMR spectrum of the mixture showed that the reac-
tion was not complete, and further catalyst (8.0 mg) was added. After
5 days of stirring under ambient conditions, the starting material had
been consumed. The crude, unsaturated product was passed through a
short chromatography column (Al2O3, CH2Cl2/MeOH 40:1) and the sol-
vent was removed in vacuo. The intermediate product was then hydro-
genated with molecular H2 (1 atm) in a mixture of EtOH (20 mL) and
¯
2892.26; red block; triclinic; space group P1, a=15.154(3), b=17.614(4),
c=26.892(5) ꢂ; a=86.54(3), b=82.28(3), g=84.31(3)8; U=7070(3) ꢂ3;
ACTHNUTRGNEUNG
Z=2; 1calcd =1.359 Mgmꢀ3; m(MoKa)=0.372 mmꢀ1; T=173(2) K; 89634
reflections collected (24992 unique); merging r=0.0834; refinement of
21321 reflections (1741 parameters) with I>2.0s(I) converged at final
R1=0.0658 (R1 all data=0.0763), wR2=0.1683 (wR2 all data=0.1755);
gof=1.054.
CCDC-736161, 736162, 736163 and 736164 contain the supplementary
crystallographic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
11756
www.chemeurj.org
ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2009, 15, 11746 – 11757

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Received: June 16, 2009
Published online: September 16, 2009
Chem. Eur. J. 2009, 15, 11746 – 11757
ꢁ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
11757