A noncovalently assembled porphyrinic catenane consisting of two interlocking [43]-membered rings

Article abstract of DOI:10.1039/c1nj20294d

A new macrocycle and the corresponding [2]catenane were prepared quantitatively from relatively large organic fragments using coordination chemistry bonds only (Zn-N bonds for the ring and Cu-N bonds for the catenane). The two constitutive macrorings of t

Full text of DOI:10.1039/c1nj20294d

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PAPER
A noncovalently assembled porphyrinic catenane consisting of two
interlocking [43]-membered ringsw
´
Maryline Beyler, Valerie Heitz* and Jean-Pierre Sauvage*
Received (in Montpellier, France) 4th April 2011, Accepted 2nd May 2011
DOI: 10.1039/c1nj20294d
A new macrocycle and the corresponding [2]catenane were prepared quantitatively from
relatively large organic fragments using coordination chemistry bonds only (Zn–N bonds for the
ring and Cu–N bonds for the catenane). The two constitutive macrorings of the [2]catenane
are 43-membered rings. The organic components consist of a bis-Zn porphyrin and a
1,10-phenanthroline derivative, both fragments being significantly larger than those previously
used for making related compounds. The catenane was assembled in two steps from a bis-Zn
porphyrin and a 2,9-di(400-pyridyl-40-phenyl)-1,10-phenanthroline. In a first step the entwined
copper(I) complex of the phenanthroline derivative was formed via Cu(I)–N interactions.
Subsequently, a double ring closing reaction was performed by coordination of two
equivalents of bis-Zn porphyrin to the entwined copper(I) complex. The tetraporphyrinic
[2]catenane was thus obtained thanks to the formation of four Zn(II)–pyridine bonds. It has a
high association constant, 4 ꢀ 1010
M
ꢁ2, due to the good geometrical fit between the
constituents.
family of molecules and it is particularly interesting to con-
Introduction
struct such compounds under thermodynamic control using
coordination bonds. A few such molecules have recently been
reported, which consist of rather short fragments and thus
leading to relatively small rings, unable to undergo further
copper-directed threading reactions.1 We would now like to
report the synthesis of a new catenane containing larger cycles
than those of the previous compounds as well as the data of an
equilibrium study in solution. The thermodynamic parameters
obtained show that the coordination chemistry-assembled
catenane and its constitutive rings are slightly less stable than
their smaller homologues, in agreement with entropy
considerations.
Since the early work of Schill and co-workers, the field of
catenanes, rotaxanes and knots has undergone a real revolution.2
The introduction of templated strategies has profoundly modified
the way molecular chemists look at catenanes, mostly due to
the accessibility of these compounds after the templated
approaches were described. Since these species could be made
at a real preparative scale, their use as components of ‘‘mole-
cular machines’’3 or in relation to novel materials4 and energy
or electron transfer processes5 has experienced a spectacular
development. The preparation of such compounds under
thermodynamic control based on labile covalent bonds6 or
non-covalent bonds such as hydrogen or coordination bonds
is particularly promising.7 The synthesis of transition metal-
incorporating catenanes for which the ring-forming step involves
the formation of a coordination bond has been pioneered by
Fujita and his co-workers.8 By combining copper(I)–1,
10-phenanthroline interactions and palladium(II)–pyridine inter-
actions, several catenanes assembled via coordination chemistry
have also been made in collaborative work with Fujita and his
team.9 Porphyrin-incorporating catenanes represent a promising
Results and discussion
Synthesis of the ligands
The bis-zinc(II)porphyrin
4 was obtained in two steps
from the bis-triflate naphthalene derivative 11 and the zinc(II)
meso-iodophenyl porphyrin 310 as depicted in Scheme 1.
The first step was the conversion of the two triflate functions
of 1 into boronic ester functions. 2 was obtained by using the
approach of Miyaura with bis(pinacolato)diboron as the
transmetalating reagent.11 In addition to PdCl2(dppf) as a
catalyst and KOAc as a base, free dppf was required. In fact,
its addition allowed the re-activation of the catalyst that was
poisoned by the liberation of triflate. After purification of the
crude product by chromatography, 2 was isolated as a white
solid in 30–40% yield. Pd-catalysed cross-coupling reaction of
´
Laboratoire de Chimie Organo-Minerale, Institut de Chimie,
Universite de Strasbourg-CNRS/UMR7177, 4 rue Blaise Pascal,
´
67070 Strasbourg Cedex, France. E-mail: sauvage@chimie.u-strasbg.fr,
v.heitz@unistra.fr; Fax: +33 3 6885 1368; Tel: +33 3 6885 1361
w Electronic supplementary information (ESI) available. See DOI:
10.1039/c1nj20294d
c
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Scheme 1 Synthesis of the bis-Zn porphyrin 4. (i) PdCl2(dppf), dppf, KOAc, dioxane, 85 1C, 30–40%; (ii) Pd(PPh3)4, Na2CO3, toluene/EtOH/
H2O, 90 1C, 50%.
Scheme 2 Synthesis of the bis(pyridine)phenanthroline derivative 7.
(i) Pd(PPh3)4, Na2CO3, toluene/EtOH/H2O, 90 1C, 51%.
2 with 3 (2 equiv.) gave the desired purple bis-Zn porphyrin
Scheme 3 Formation of the noncovalently assembled macrocycle 8.
4 in 50% yield by using conditions analogous to those
previously described by Sanders and co-workers.12
The bis(pyridine) 7 was obtained thanks to a double Suzuki
coupling reaction between the 2,9-bis(para-bromophenyl)-
1,10-phenanthroline 59c and the commercially available
pyridine-4-boronic acid 6 (Scheme 2).
particularly the signals opy and mpy of the pyridine moieties
(Dd: ꢁ1.51 and ꢁ4.92 ppm, respectively) that lie in the shielding
field of a porphyrin. Moreover these signals are broad because
of the dissociation equilibrium in which 7 is involved.1,13
The constituents 4 and 7 of the macrocycle are perfectly
complementary in terms of angles (see Scheme 3). In fact, the
sum of the four angles in an hypothetical quadrangle whose 4
edges are co-linear to the two Zn–N coordination axes and the
two C–C bonds connecting the porphyrins to the di(40-phenyl)-
2,7-naphthalene fragments is 3601. This should lead to a high
association constant.
This reaction was performed under classical conditions to
afford
7 in 51% yield after purification by column
chromatography.
Noncovalently assembled ring and [2]catenane
Macrocycle 8 was obtained in one step from 4 and 7 thanks
to two non-covalent Zn(II)–N interactions. The reaction is
depicted in Scheme 3.
In order to evaluate the stability of the ring, UV-vis titra-
tions were carried out. To a solution of bis-Zn porphyrin 4 in
toluene (c = 1.09 ꢀ 10ꢁ6 M), constant aliquots of a solution of
bis(pyridine) 7 in toluene (c = 3.26 ꢀ 10ꢁ5 M) were gradually
added, and UV-vis spectra were recorded after each addition.
As expected, upon axial coordination of the pyridyl ligands
to the zinc(II) porphyrins, the absorption bands of zinc(II)
porphyrins displayed a small bathochromic shift13,14 and the
presence of an isosbestic point indicated that only one species
was formed. The UV-vis absorption spectra obtained during
the titration of 4 with increasing amounts of 7 are reported in
Fig. 2.
4 and 7 in stoichiometric proportions (c = 1 ꢀ 10ꢁ3 M)
were dissolved in chloroform. The solution was stirred at room
temperature under argon. Macrocycle 8 was obtained quanti-
tatively and characterized by 1H NMR (Fig. 1) including
COSY (Fig. S1 and S2, ESIw) and ROESY (Fig. S3–S5, ESIw).
As shown in Fig. 1, the protons of the bis-Zn porphyrin 4
are only slightly affected by formation of ring 8, contrary to
the protons of the bis(pyridine) ligand 7. In fact, these protons
are strongly upfield shifted upon coordination with 4,
c
1752 New J. Chem., 2011, 35, 1751–1757
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1
Fig. 1 Partial H NMR spectrum (300 MHz, CDCl3, 298 K) of (a) 4, (b) 7 and (c) 8.
Fig. 2 Absorption spectra (Soret band) in toluene containing 4 (c =
1.09 ꢀ 10ꢁ6 M, 3 mL) after additions of constant aliquots (10 mL) of 7
(c = 3.26 ꢀ 10ꢁ5 M).
Scheme 4 Chemical structures and number of internal atoms of (a) a
related non-covalent macrocycle,1b (b) macrocycle 8.
size is needed to be able to construct a [2]catenane with four
bulky porphyrins surrounding the central copper bis-phenan-
throline core. Previous attempts to synthesize a [2]catenane
from a central copper(I) complex coordinated to two di-2,9-
di(40-pyridyl)-1,10-phenanthroline chelate failed.1 In these
experiments, the small distances between the pyridyl groups
belonging to two chelates prevented the coordination to the
porphyrins perpendicularly to their planes, mostly owing to
the presence of very bulky groups attached at the periphery of
the porphyrin backbones.
The association constant of the following equilibrium was
calculated:
4 + 7 " 8
½8ꢂ
Kass
¼
½4ꢂ ꢀ ½7ꢂ
The data were analysed (Fig. S6, ESIw) and a stability constant
of Kass = 2 ꢀ 105 ꢃ 0.2 Mꢁ1 was obtained.
A higher value was obtained for a related non-covalent
porphyrinic macrocycle.1b In this previously reported macro-
cycle, represented in Scheme 4, the number of internal atoms
was smaller and equal to 38 compared to 43 for 8.
From the new ligands 4 and 7, a [2]catenane was formed in
two steps as described in Scheme 5.
In a first step, the entwined precursor complex 9ꢄPF6 was
formed. A solution of [Cu(CH3CN)4]ꢄPF6 (1 equiv.) in aceto-
nitrile was added to a solution of 7 (2 equiv.) in chloroform.
After 3 h, the solvents were pumped off to lead quantitatively to
The Zn–N bond strength being of the same order for each
macrocycle, it is expected that formation of a smaller macro-
cycle is favoured in terms of entropy. Nevertheless, a large ring
c
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Scheme 5 Synthesis of noncovalently assembled catenane 10+. (i) [Cu(CH3CN)4]ꢄPF6, CHCl3, CH3CN, rt, 100%; (ii) 4 (2 equiv.), CHCl3,
CH3CN, rt, 100%.
the desired complex 9ꢄPF6, obtained as a red solid. 9ꢄPF6 was
characterized by 1H NMR and by mass spectrometry ES-MS.
Then, 9ꢄPF6 (1 equiv., c = 1 ꢀ 10ꢁ3 M) was dissolved in
acetonitrile and reacted with 4 (2 equiv., c = 5 ꢀ 10ꢁ4 M) in
The protons of ligand 7 are very upfield shifted in 10ꢄPF6
compared to the same protons in 8 because 7 is involved in the
copper(I) entwined complex. The signals of the protons o0 and
m0 are remarkably upfield shifted (Dd: ꢁ1.51 and ꢁ1.27 ppm
respectively) proving that an intertwined complex is formed.
In fact the entwining places the phenyl of one chelate above
the shielding cone of the 1,10-phenanthroline unit of the
second chelate.
1
CHCl3. After 3 h, the solvents were removed and H NMR
showed the formation of catenane 10ꢄPF6 as the only product
of the reaction (Fig. 3). The different signals could be assigned
thanks to COSY (Fig. S7 and S8, ESIw) and ROESY (Fig. S9
and S10, ESIw) experiments.
The association constant of the [2]catenane 10ꢄPF6 was also
determined by absorption titrations. The same protocol as
previously was used. To a solution of bis-Zn porphyrin 4 in
The 1H NMR spectra of the macrocycle 8 and of the
[2]catenane 10ꢄPF6 are compared with one another in Fig. 3.
1
Fig. 3 Partial H NMR spectrum (300 MHz, CDCl3, 298 K) of (a) 8 and (b) 10ꢄPF6.
c
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toluene (c = 1.09 ꢀ 10ꢁ6 M), constant aliquots of 9ꢄPF6
in toluene (c = 3.26 ꢀ 10ꢁ5 M) were gradually added, and
UV-vis spectra were recorded after each addition. The asso-
ciation constant Kass of the following equilibrium was
calculated:
Starting materials
All chemicals were of best commercially available grade and
used without further purification (unless mentioned).
Spectral and equilibrium constant measurements
2(4) + 9+ " 10+
½10þꢂ
UV-visible spectra were recorded with a Kontron Instruments
UVIKON 860 spectrometer at 25 1C with a 1 cm path cell.
All measurements were made in toluene solutions, c E 10ꢁ6 M
in bis-zinc(II)porphyrin 4. Dipyridyl derivatives 7 or 9ꢄPF6
toluene solutions (c E 10ꢁ5 M) were added to the bis-
zinc(II)porphyrin 4 sample in 10 mL aliquots via a 100 mL
Hamilton syringe. UV-visible spectrophotometric titrations were
analyzed by fitting the series of spectra at 1 nm intervals by using
the SPECFIT/32 3.0 (Spectrum Software Associates), which
takes into account the changes in volume during the titration.
Kass
¼
2
½4ꢂ ꢀ ½7ꢂ
The data were analysed (Fig. S11, ESIw) and an association
constant of Kass = 4 ꢀ 1010 ꢃ 0.1 Mꢁ2 was obtained. This
corresponds to the square value of the one found for macro-
cycle 8. There is thus no cooperative effect upon coordination
of a second bis(porphyrin) 4 to 9+.
Conclusions
Compound 2
A macrocycle and a [2]catenane were obtained quantitatively
under thermodynamic control via the formation of zinc(II)–
pyridine interactions. These assemblies are stable as attested
by the high association constants determined by UV-Vis spectro-
scopy experiments. The optimized geometrical fit between the
constituents and the relatively strong zinc(II)–pyridine interaction
enables to obtain in a two step reaction, a tetraporphyrinic
[2]catenane.
A round-bottom flask was charged with methanesulfonic
acid 1,1,1-trifluoro-1,10-(2,7-naphtalenedidyl) ester 1 (278 mg,
0.94 mmol), bis(pinacolato)diboron (665 mg, 3.78 mmol),
KOAc (384 mg, 5.64 mmol), 1,10-bis(diphenylphosphino)-
ferrocene (52 mg, 0.094 mmol), Pd(dppf)Cl2 (53.2 mg,
0.094 mmol) and 5 mL of commercial anhydrous dioxane.
The mixture was degassed by three vacuum–argon cycles,
and stirred at 80 1C under an atmosphere of argon overnight.
The solvent was removed under reduced pressure; the crude
product was taken up in CH2Cl2 and washed with water (3 ꢀ
10 mL). The crude product was then purified by a fast column
chromatography on silica eluted with CH2Cl2/pentane (90/10),
to yield 30–40% of a white solid 2.
1H NMR (300 MHz, CDCl3, 298 K): d (ppm) 8.41 (s, 2H, 1),
7.87 (dd, 2H, 3J = 8.2 Hz, 4J = 1.0 Hz, 3), 7.80 (d, 2H, 3J =
8.2 Hz, 4), 1.39 (s, 24H, OMe).
13C NMR (75 MHz, CDCl3, 298 K): d (ppm) 179.54, 137.12,
131.54, 126.79, 83.88, 24.94.
The large size of the two constitutive rings of the [2]catenane
provides the system with empty cavities which will be utilised
in the future for coordinating additional species to the free
1,10-phenanthroline fragments so as to lead to more complex
threaded species. The present systems pave the way to the
stepwise synthesis of large sophisticated assemblies like
[2]polycatenanes. Since the cavity of ring 8 appears to be large
enough to undergo threading reactions, it could thus be
imagined that successive threading steps and coordination-
directed ring closing reactions could progressively lead to the
construction of a [2]polycatenane.
Compound 4
Experimental section
A round-bottom flask containing meso iodophenyl porphyrin
3 (105 mg, 0.046 mmol), Na2CO3 (9.8 mg, 0.092 mmol) and
Pd(PPh3)4 (10.6 mg, 10 mol%) was degassed by three vacuum–
General methods
Dry solvents were distilled from suitable drying agents (toluene
from sodium/benzophenone, dichloromethane from calcium
hydride and chloroform from potassium carbonate). Thin
layer chromatography was carried out using pre-coated polymeric
sheets of silica gel (Macheray-Nagel, POLYGRAM, SIL
G/UV254). Preparative column chromatography was carried
out using silica gel (Merck Kieselgel, silica gel 60, 0.063–
0.200 mm). Nuclear Magnetic Resonance (NMR) spectra for
1H were acquired on Bruker AVANCE 400 or 300 spectro-
meters. The spectra were referenced to residual proton–solvent
references (1H: CD3CN at 1.94 ppm, CD2Cl2 at 5.32 ppm,
CDCl3 at 7.26 ppm; 13C: CDCl3 at 77.36 ppm). In the assign-
ments, the chemical shift (in ppm) is given first, followed, in
brackets, by the multiplicity of the signal (s: singlet, d: doublet,
t: triplet, m: multiplet, bd: broad doublet), the number of
protons implied, the value of the coupling constants in Hertz if
applicable, and finally the assignment. Mass spectra were
obtained by using a Bruker MicroTOF spectrometer (ES-MS).
argon cycles. The mixture was dissolved in a degassed biphasic
mixture of freshly distilled toluene (2 mL), ethanol (0.8 mL)
and deionised water (0.6 mL). The reaction mixture was
heated at 90 1C overnight under argon. The solvents were
evaporated under reduced pressure and the crude product was
taken up in CH2Cl2 and washed with water (3 ꢀ 30 mL). The
resulting material was purified by column chromatographies
on silica eluted with pentane/CH2Cl2 (100/0 to 50/50) to yield
a purple solid 4 (50 mg, 50%).
1H NMR (300 MHz, CD2Cl2, 298 K): d (ppm) 9.16 (d, 4H,
3J = 4.6 Hz, py1), 9.09 (d, 4H, 3J = 4.6 Hz, py2), 9.05 (bs, 8H,
py3 + py4), 8.68 (s, 2H, 1), 8.46 (d, 4H, 3J = 8.1 Hz, m), 8.30
(d, 4H, 3J = 8.1 Hz, o), 8.25 (bs, 4H, 3 + 4), 8.17 (d, 8H, 4J =
1.8 Hz, opx), 8.15 (d, 4H, 4J = 1.8 Hz, opz), 7.90 (m, 6H, 4J =
1.6 Hz, ppx + ppz), 1.59 (s, 108H, tBux + tBuz).
ES/MS: m/z 2154.36 [4
+
H+], calcd 2154.68 for
C
146H156N8Zn2H.
c
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UV-vis (toluene): lmax (log e) = 427 (5.85), 551 (4.52), 591
(3.29) nm.
1H NMR (400 MHz, CD3CN, 298 K: d (ppm) 8.64 (d, 8H,
3J = 5.7 Hz, mpy), 8.56 (d, 4H, 3J = 8.4 Hz, 4, 7), 8.02 (d, 4H,
3J = 8.4 Hz, 3, 8), 7.94 (s, 4H, 5, 6), 7.70 (d, 8H, 3J = 8.4 Hz,
o), 7.21 (d, 8H, 3J = 6.0 Hz, opy), 6.96 (d, 8H, 3J = 8.4 Hz, m).
ES/MS: m/z 1035.277 [9+], calcd 1035.298 for C68H44N8Cu.
Compound 7
A
round-bottom flask was charged with 2,9-bis(para-
bromophenyl)-1,10-phenanthroline 5 (200 mg, 0.41 mmol),
and Pd(PPh3)4 (28.6 mg, 6 mol%), and degassed by three
vacuum–argon cycles. The mixture was dissolved in 8 mL of
freshly distilled and degassed toluene. Then were added,
respectively, a degassed solution of pyridine-4-boronic acid
(152 mg, 1.24 mmol) in EtOH (10 mL) and a degassed solution
of Na2CO3 (219 mg, 2 mmol) in deionised water (1.5 mL).
The mixture was heated at 90 1C overnight under argon. The
solvents were evaporated under reduced pressure and the
crude product taken up in CH2Cl2 and washed with water
(3 ꢀ 30 mL). The organic layers were combined and dried
with MgSO4. The resulting material was purified by column
chromatography on silica eluted with CHCl3/MeOH (100/0 to
98/2) to afford a white solid 7 (102 mg, 51%).
Compound 10ꢄPF6
In a round-bottom flask, 9ꢄPF6 (3.2 mg, 0.0027 mmol) was
dissolved in 1 mL of degassed CH3CN. In a round-bottom
flask, 4 (11.7 mg, 0.0054 mmol) was dissolved in 5 mL of
freshly distilled and degassed CHCl3. This solution was added
dropwise via canula to the solution of 9ꢄPF6 in CH3CN. The
solution turned immediately purple-green. The mixture was
allowed to react for four hours at room temperature under
argon. The solvents were removed under reduced pressure to
yield quantitatively the desired complex 10ꢄPF6 as a purple
greenish solid (14.9 mg).
1H NMR (300 MHz, CD2Cl2, 298 K): d (ppm) 9.02 (d, 8H,
3J = 4.5 Hz, py1), 8.97 (s, 16H, py3 + py4), 8.96 (d, 8H,
3J = 4.5 Hz, py2), 8.55 (bs, 4H, 1), 8.34 (d, 4H, J = 7.5 Hz,
3
1H NMR (300 MHz, CDCl3, 298 K): d (ppm) 8.66 (d, 4H,
4), 8.17 (d, 4H, 3J = 7.9 Hz, 3), 8.14 (d, 8H, J = 7.6 Hz, o),
3
3
3J = 6.2 Hz, mpy), 8.59 (d, 4H, J = 8.5 Hz, o), 8.37 (d, 2H,
4
4
3J = 8.5 Hz, 4, 7), 8.22 (d, 2H, 3J = 8.5 Hz, 3, 8), 7.90 (d, 4H,
3J = 8.5 Hz, m), 7.84 (s, 2H, 5, 6), 7.64 (d, 4H, 3J = 6.3 Hz, opy).
ES/MS: m/z 487.19 [7 + H+], calcd 487.19 for C34H22N4H.
8.07 (m, 24H, J = 1.7 Hz, opZ), 7.79 (t, 4H, J = 1.7 Hz,
opx), 7.77 (m, 20H, 4J = 1.7 Hz, ppx + ppz + m), 7.72
(bd, 4H, 3J = 8.7 Hz, 40, 70), 7.14 (bd, 4H, 3J = 7.5 Hz, 30, 80),
3
6.81 (bs, 4H, 50, 60), 6.58 (bd, 8H, J = 6.3 Hz, o0), 5.74 (bd,
3
8H, J = 6.7 Hz, m0), 5.45 (bs, 8H, mpy), 3.56 (vbs, 8H, opy).
Compound 8
ES/MS: m/z 5346.7 [10+], calcd for 5346.5
In a round-bottom flask, 4 (8.8 mg, 0.004 mmol) was dissolved
in 1 mL of freshly distilled and degassed CHCl3. In another
round-bottom flask, 7 (6.7 mg) was dissolved in 15 mL of
freshly distilled and degassed CHCl3. 4.5 mL (0.004 mmol) of
this solution were added dropwise to the solution of 4 in
CHCl3. The solution turned immediately purple-green. The
mixture was allowed to react overnight at room temperature
under argon. The solvent was removed under reduced pressure
to give quantitatively complex 8 as a purple greenish solid
(7.4 mg).
C
360H356N24CuZn4.
UV-vis (toluene): lmax (log e) = 428 (5.85), 552 (4.52), 592
(3.29) nm.
Acknowledgements
We gratefully acknowledge the French Ministry of Education
for a fellowship (M.B.).
Notes and references
1H NMR (400 MHz, CDCl3, 298 K): d (ppm) 9.04 (d, 4H,
3J = 4.7 Hz, py1), 9.01 (bs, 8H, py3 + py4), 9.01 (d, 4H, 3J =
4.7 Hz, py2), 8.55 (s, 2H, 1), 8.30 (bs, 2H, 4), 8.13 (d, 8H, 4J =
1 (a) M. Beyler, V. Heitz and J.-P. Sauvage, Chem. Commun., 2008,
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Chem. Soc., 2010, 132, 4409–4417.
2 (a) G. Schill, Catenanes, Rotaxanes and Knots, Organic Chemistry,
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4
1.8 Hz, opx), 8.11 (d, 4H, J = 1.6 Hz, opz), 8.09 (m, 10H,
3
o0 + 40, 70 + m + 3 + o), 7.87 (d, 6H, J = 8.5 Hz, 30, 80),
7.80 (t, 4J = 1.6 Hz, ppx + ppz), 7.61 (s, 2H, 50, 60), 7.01
(d, 4H, 3J = 8.4 Hz, m0), 6.12 (d, 4H, 3J = 5.5 Hz, mpy), 3.70
(bs, 4H, opy), 1.54 (s, 72H, tBux), 1.53 (s, 36H, tBuz).
UV-vis (toluene): lmax (log e) = 428 (5.85), 551 (4.52), 591
(3.29) nm.
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In a round-bottom flask, 7 (10.0 mg, 0.02 mmol) was dissolved
in 20 mL of freshly distilled CHCl3. The solution was degassed
by three vacuum–argon cycles. In a Schlenk, Cu(CH3CN)4ꢄ
PF6 (7.7 mg, 0.02 mmol) was dissolved in 3 mL of degassed
CH3CN. 1.5 mL (0.01 mmol) of this solution was added
dropwise to the solution of 7 in CHCl3. The solution turned
immediately red. The mixture was allowed to react for 5 hours
at room temperature under argon. The solvents were removed
under reduced pressure to give quantitatively the desired
complex 9ꢄPF6 as a brown solid (10.4 mg).
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