[40]Nonaphyrin(1.1.1.1.1.1.1.1.1) and its heterometallic complexes with palladium-carbon bonds

Article abstract of DOI:10.1002/chem.200601304

meso-Pentafluorophenyl-substituted [40]nonaphyrin-(1.1.1.1.1.1.1.1.1) 3 has been prepared by using a stepwise ring-size-selective synthesis, and has been reduced with NaBH₄ to [42]nonaphyr-in(1.1.1.1.1.1.1.1.1) 5. Structurally, 3 is characteriz

Full text of DOI:10.1002/chem.200601304

DOI: 10.1002/chem.200601304
[40]Nonaphyrin(1.1.1.1.1.1.1.1.1) and Its Heterometallic Complexes with
Palladium–Carbon Bonds
Yiho Kamimura, Soji Shimizu, and Atsuhiro Osuka*[a]
Abstract:
substituted
(1.1.1.1.1.1.1.1.1) 3 has been prepared
by using a stepwise ring-size-selective
synthesis, and has been reduced with
NaBH4
in(1.1.1.1.1.1.1.1.1) 5. Structurally, 3 is
characterized by figure-of-eight
shape, consisting of a porphyrin-like
tetrapyrrolic segment and a hexaphyr-
in-like hexapyrrolic segment, whereas 5
has been found to adopt a distorted
nonplanar butterfly-like shape. In the
mono-metal complexes 6 and 7, a ZnII
or CuII ion is bound by the porphyrin-
meso-Pentafluorophenyl-
like tetrapyrrolic segment, maintaining
the overall structure of 3. Similarly to
3, complexes 6 and 7 are interconverti-
ble with the corresponding complexes
9 and 10 through two-electron reduc-
tion with NaBH4 and oxidation with
DDQ. The metal-free hexaphyrin-like
segments of 6 and 7 have been shown
to serve as a suitable platform for the
complexation of two palladium ions,
providing hetero-trinuclear metal com-
plexes 11 (ZnII–PdII–PdII) and 13 (CuII–
PdII–PdII) in high yields, in which the
Zn or Cu ion resides at the same por-
phyrin-like segment, and one Pd ion is
bound in an NNCC fashion through
[40]nonaphyrin-
to
[42]nonaphyr-
À
a
double C H bond activation while the
other is bound in an NNC fashion with
À
single C H bond activation. Multi-
metal complexes 11, 12, and 13 exhibit
small electrochemical HOMO–LUMO
gaps (<0.6 eV), despite their nonpla-
nar conformations.
Keywords: conjugation
metallic complexes
·
hetero-
HOMO–
A
·
LUMO gap · macrocyclic ligands ·
porphyrinoids
Introduction
ins on the basis of the reaction of pyrrole and pentafluoro-
benzaldehyde under modified Rothemund–Lindsey condi-
tions (concentrations 67mm each; BF3·OEt2 in CH2Cl2, and
2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ)).[2] These
meso-aryl-substituted expanded porphyrins can be regarded
as real homologues of porphyrin, in view of the alternating
arrangement of pyrroles and methine carbons. In the course
of our studies on the metalation of these expanded porphyr-
ins, we have elucidated their novel reactivities and proper-
ties, which are different for each expanded porphyrin, de-
pending on their structural and electronic demands.[4] Rep-
resentative examples are the oxidation-induced “rhodium-
walk” of an RhI complex of N-fused pentaphyr-
in(1.1.1.1.1),[5] gable-type bis-CuII–hexaphyrins and their an-
tiferromagnetic interactions,[6] a CuI-ion-induced double-pyr-
rolic rearrangement of a [26]hexaphyrin(1.1.1.1.1.1) to a
doubly N-confused hexaphyrin,[7] aromatic and anti-aromatic
switching of AuIII-metalated planar hexaphyrin(1.1.1.1.1.1),[8]
sequential multiple N-fusion reactions of [32]heptaphyr-
in(1.1.1.1.1.1.1) and a boron complex of quadruply N-fused
heptaphyrin,[9] a quantitative thermal splitting reaction of
bis-CuII [36]octaphyrin(1.1.1.1.1.1.1.1.1) into two CuII–por-
phyrin molecules,[10] and partial hydrolytic cleavage of the
pyrrole ring of perfluorinated [36]octaphyrin upon CuII ion
Expanded porphyrins incorporating more than four pyrrole
units have been extensively studied because of their unique
optical and electrochemical properties and complexation be-
haviors, which depend on ring size, ring connectivity, and
the number of conjugated p electrons of the macrocycle.[1,2]
One of the most fascinating functions of expanded porphyr-
ins is that they can coordinate multiple metal ions within
their large cavities, in contrast to porphyrins, which can ac-
commodate most metal ions in only a 1:1 manner. Despite
this coordination potential, only a limited number of homo-
bis-metalated complexes of expanded porphyrins have hith-
erto been reported.[3] Recently, we have explored the syn-
thesis of a series of meso-aryl-substituted expanded porphyr-
[a] Y. Kamimura, S. Shimizu, Prof. A. Osuka
Department of Chemistry, Graduate School of Science
Kyoto University, and Core Research for Evolutional Science and
Technology (CREST), Japan Science and Technology Agency
Sakyo-ku, Kyoto 606-8502(Japan)
Fax : (+81)75-753-3970
E-mail: osuka@kuchem.kyoto-u.ac.jp
Supporting information for this article is available on the WWW
under http://www.chemeurj.org/ or from the author.
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FULL PAPER
metalation.[11] Another attractive feature of the expanded
porphyrins is that they can adopt more than two stable oxi-
dation states, which are interconvertible through two-elec-
tron oxidation and reduction.[5,8] In addition, they are also
of interest by virtue of their large two-photon absorption
(TPA) cross sections.[12] Enhanced TPA properties are ex-
pected for larger expanded porphyrins, but their chemistry,
especially their metal complexation behavior, has been only
poorly studied, except for rare examples.[13] This is particu-
larly the case for structures larger than octaphyrins, due in
part to the increasing synthetic difficulty with increasing
size. In the course of our investigations, we have elucidated
the structure of the trifluoroacetic acid (TFA)-stabilized
complex of [42]nonaphyrin(1.1.1.1.1.1.1.1.1) 5,[2b] but the
structure and properties of the corresponding free-base non-
aphyrin were unknown. Thus, we have investigated the syn-
thesis, redox behavior, and complexation chemistry of meso-
pentafluorophenyl nonaphyrin(1.1.1.1.1.1.1.1.1), and we
present our findings herein. In the metalation of [40]nona-
phyrin 3, positive heteroallosterism was employed to allow
the effective formation of hetero-trinuclear metal complexes
11 and 13.
reaction mixture was separated by using column chromatog-
raphy on silica gel, eluting with a CH2Cl2/hexane mixture. A
bright-green fraction containing 3 was collected and the
product was recrystallized from CH2Cl2/hexane to give
violet crystals. This method allowed us to prepare 3 on a
large scale (ca. 280 mg) in one batch synthesis. High-resolu-
tion electrospray ionization time-of-flight (HR-ESI-TOF)
mass measurement revealed the parent ion peak of 3 at m/z
2192.1369 ([M+H]+; calcd for C99H23F45N9: 2192.1352). X-
ray crystal structure analysis of 3 revealed a twisted asym-
metric structure consisting of a helically arranged porphy-
rin-like tetrapyrrolic core (pyrroles A, B, H, and I) and a
hexapyrrolic core (pyrroles C, D, E, F, G, and H), with two
inverted pyrroles E and H (Figure 1). In accordance with
this nonsymmetric structure, the 1H NMR spectrum dis-
played eighteen peaks due to the b-CH protons in the range
d=10.17–5.67 ppm and four peaks due to the NH protons at
d=16.41, 14.44, 13.82, and 12.35 ppm. Reduction of 3 with
NaBH4 gave [42]nonaphyrin(1.1.1.1.1.1.1.1.1) 5, the parent
ion peak of which was observed in the HR-ESI-TOF mass
spectrum at m/z 2194.1522 ([M+H]+; calcd for C99H25F45N9:
2194.1509), in accordance with its formulation as [42]nona-
phyrin. Solutions of 5 were dark green, but the product was
purple in the solid state. It was found that the nonaphyrin 5
could be quantitatively oxidized to 3 by treatment with
DDQ. The UV/Vis absorption spectrum of 5 showed a red-
shift of approximately l=30 nm from that of 3 (Figure 2).
Results and Discussion
Synthesis, structural characterization, and redox behavior of
[40]nonaphyrin(1.1.1.1.1.1.1.1.1) (3): The nonaphyrin 3 was
prepared in 15% yield along with hexaphyrin 2 (30%) and
dodecaphyrin 4 (2%) by following our ring-size-selective
synthetic protocol using tripyrrane 1 and pentafluorobenzal-
dehyde (22.2 mm each; at 08C in CH2Cl2; 0.25 equiv metha-
nesulfonic acid, and subsequent oxidation with 2,3-dichloro-
5,6-dicyano-1,4-benzoquinone (DDQ))[2c] (Scheme 1). The
1
The H NMR spectrum of 5 featured six peaks due to NH
protons at d=15.31, 15.09, 14.88, 14.62, 13.65, and
13.10 ppm, and eighteen peaks due to b-CH protons in the
range d=9.36–5.26 ppm as the major peaks, thus indicating
the non-aromaticity of 5. In addition, sets of peaks attributa-
ble to the corresponding protons of the minor conformer
could also be detected. X-ray diffraction analysis of 5 re-
Scheme 1. Ring-size-selective synthesis of nonaphyrin 3.
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A. Osuka et al.
lar hydrogen bonding is ob-
served between each adjacent
amine NH and imine N of the
pyrrole rings (A, B, and C; D
and E; and F, G, and H).
Metalation behavior of 3: To in-
vestigate the coordination prop-
erties of nonaphyrin, we at-
tempted metalations with ZnII
and CuII salts. Treatment of a
solution of 3 in a 1:1 mixture of
CH2Cl2 and methanol with an
excess of Zn(OAc)2·2H2O in
G
the presence of sodium acetate
provided the mono-ZnII com-
plex 6 in 75% yield, the parent
ion peak of which was detected
at m/z 2253.0460 ([M]À; calcd
for C99H20F45N9Zn: 2253.0420)
in the HR-ESI-TOF mass spec-
trum. Even under more forcing
conditions, no further zincation
was observed. The solid-state
Figure 1. X-ray crystal structure of 3: a) top view and b) side view. Peripheral substituents at the meso-position
and hydrogen atoms at the b-positions have been omitted for clarity. c) Formal structure of 3.
structure of 6 has been determined by using X-ray diffrac-
tion analysis to have a twisted conformation similar to that
of 3 (Figure 4a). The ZnII ion is coordinated within the heli-
cally arranged porphyrin-like core consisting of the pyrroles
A, B, H, and I with an average coordination bond length of
2.01 Š. The pyrroles A, B, and I are almost coplanar, with
mean plane deviations of 0.18 Š, while pyrrole H is tilted
with a dihedral angle of 52.28. The metal-free portion of 6
forms a meso-aryl-substituted hexaphyrin-like rectangular
segment consisting of the pyrroles C, D, E, F, G, and H. Of
these, pyrroles D, E, F, and G are arranged in an almost co-
planar manner, with a mean plane deviation of 0.15 Š. In
accordance with the X-ray crystal structure, the 1H NMR
spectrum of 6 features eighteen signals due to the b-CH
protons in the range d=12.99–4.92 ppm and two signals due
Figure 2. UV/Vis spectra of 3, 5, 9, and 10 in CH2Cl2.
vealed a distorted asymmetric butterfly-like conformation
(Figure 3), which is similar to that of the TFA-stabilized
complex of [42]nonaphyrin(1.1.1.1.1.1.1.1.1).[2b] Intramolecu-
Figure 3. X-ray crystal structure of 5: a) top view and b) side view. Peripheral substituents at the meso-position and hydrogen atoms at the b-positions
have been omitted for clarity. c) Formal structure of 5.
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[40]Nonaphyrin and Its Metal Complexes
FULL PAPER
stability. Upon standing in solu-
tion exposed to air, 8 was con-
verted to its oxygenated prod-
uct, as judged from the mass
spectrum.
Reduction of mono-metal com-
plexes 6 and 7: Reductions of
the mono-metal complexes
6
and 7 were also examined. Sim-
ilarly to the free base 3, com-
plexes 6 and 7 were smoothly
reduced with NaBH4 to the
mono-ZnII complex 9 and the
mono-CuII complex 10 without
Figure 4. X-ray crystal structures of a) 6 and b) 7. Peripheral substituents at the meso-position and hydrogen
À
À
atoms at the b-positions have been omitted for clarity; selected bond lengths [Š] 6: Zn N1 2.014, Zn N2
À
À
À
À
À
À
2.008, Zn N3 2.024, Zn N8 1.984; 7: Cu N1 1.966, Cu N21.994, Cu N3 1.996, Cu N8 1.950.
to the NH protons at d=19.91 and 17.98 ppm. The UV/Vis
absorption spectrum of 6 exhibits absorption bands at l=
457 and 741 nm, which are red-shifted relative to those of 3
(Figure 5).
demetalation. These two complexes can be formulated as
[42]nonaphyrins. Low-energy absorption bands were ob-
served at l=819 and 818 nm for 9 and 10, respectively. Al-
though the X-ray crystal structures of 9 and 10 have yet to
be determined, these complexes may be considered to adopt
similar conformations as in the case of 5, in view of the simi-
larity of their absorption spectra. Complexes 9 and 10 could
be quantitatively oxidized back to 6 and 7 by treating them
with DDQ or MnO2. Metalation of 5 with ZnII ions gave
complex 9 in 78% yield, whereas metalation of 5 with CuII
ions afforded the complexes 7 and 8 in yields of just 42%
and 25%, respectively, probably as a result of instantaneous
oxidation of 5 to 3 by CuII ions (Scheme 2).
Figure 5. UV/Vis spectra of 6, 7, 11, 12, and 13 in CH2Cl2.
Under similar conditions, 3 was reacted with Cu(OAc)2 to
G
afford a mono-CuII complex (7) and a bis-CuII complex (8).
The resulting mixture was separated by using column chro-
matography on silica gel, eluting with a CH2Cl2/hexane mix-
ture. The first indigo-blue fraction contained 8 (12.5 mg,
27% yield) and the second yellow-green fraction contained
7 (15.7 mg, 35% yield). In the mass spectrum of complex 7,
the parent ion peak was seen at m/z 2252.0408 ([M]À; calcd
for C99H20F45N9Cu: 2252.0425). The structure of 7 has been
explicitly determined by using X-ray analysis, which re-
vealed a twisted conformation similar to those of 3 and 6
(Figure 4b). In 7, the CuII ion is bound within the porphyrin-
like core with an average coordination bond length of
1.97 Š, which is similar to that in related porphyrins (1.99 Š
in the case of CuTFPP).[14] In the porphyrin-like core, pyr-
roles A, B, and I are almost coplanar with a mean plane de-
viation of 0.16 Š, while pyrrole H is tilted with a dihedral
angle of 44.38. The absorption spectrum of 7 features bands
at l=453 and 737 nm (Figure 5). In the mass spectrum of
complex 8, the parent ion peak was observed at m/z
2311.9511 ([MÀH]À; calcd for C99H17F45N9Cu2: 2311.9486),
which indicates the coordination of two Cu ions. Structural
characterization of 8, however, has been hampered by its in-
Scheme 2. Redox behavior of nonaphyrins.
Trinuclear metal complexes: Since the mono-metalated
complexes 6 and 7 possess planar hexaphyrin-like moieties
that may accommodate additional metal ions, further metal-
ations were attempted with various metal salts. After many
attempts, we found that the metalation of 6 with Pd(OAc)2
G
in a mixture of CH2Cl2 and MeOH (1:10) in the presence of
NaOAc at room temperature quantitatively afforded the
brown trinuclear (Zn–Pd–Pd) complex 11. In the mass spec-
trum of 11, the parent ion peak was seen at m/z 2459.8140
([MÀH]À; calcd for C99H15N9F45ZnPd2: 2459.8129). Prelimi-
nary X-ray analysis of 11 indicated a distorted nonplanar
structure, in which the ZnII ion resides within the porphyrin-
like tetrapyrrolic core and the two PdII ions are effectively
accommodated within the remaining hexaphyrin-like seg-
1
ment. In the H NMR spectrum of 11, fourteen signals due
to b-protons appear in the range d=10.60–3.46 ppm; proton
H(1) gives rise to a singlet at d=4.63 ppm (for the designa-
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1623

A. Osuka et al.
tion of H(1), cf. the similar proton in Figure 6a) and the
signal of the outer NH proton is seen at d=5.89 ppm.
Under similar conditions, in the absence of sodium ace-
tion spectra of 11, 12, and 13 are similar to one another, and
are considerably broader than those of 6 and 7 (Figure 5).
It is important to note that the quantitative formation of
11 or 13 is only possible by using 6 or 7 as starting sub-
strates. Attempted metalations
tate, metalation of 7 with Pd(OAc)2 provided the CuPd1
A
of 3 in the presence of both
CuII and PdII ions or with PdII
ions alone under various condi-
tions gave very complicated in-
tractable mixtures, underscoring
the importance of the pre-coor-
dination of the CuII or ZnII ion
for the clean formation of 11
and 13. It is probable that the
pre-coordination fixes the por-
phyrin-like tetrapyrrolic seg-
ment, thereby imposing a some-
what constrained structure on
the hemi-hexaphyrin-like seg-
ment, which facilitates the sub-
sequent mono- and bis-pallada-
tions. As has recently been ex-
plored, expanded porphyrins
represent a class of promising
multi-metal ligands, but, with
increasing size of the macrocy-
Figure 6. X-ray crystal structures of 13; a) top view and b) side view. Peripheral substituents at the meso-posi-
tion and hydrogen atoms at the b-positions (except H1) have been omitted for clarity; selected bond lengths
cles, their metalation behavior
becomes ever more difficult to
control, mainly due to the in-
creasing diversity of possible
conformations. In this respect,
À
À
À
À
À
À
À
[Š]: Cu N1 1.975, Cu N22.014, Cu N8 2.011, Cu N9 1.951, Pd1 N6 2.075, Pd1 N7 2.058, Pd1 C23 1.955,
À
À
À
À
Pd1 C37 1.970, Pd2 N3 2.071, Pd2 N4 2.038, Pd2 C22 1.932, Pd2···C38 2.226. c) Formal structure of 13.
complex 12 and the CuPd2 complex 13 in yields of 16% and
46%, respectively. More forcing metalation conditions
(reflux in the presence of sodium acetate) led to quantita-
tive conversion to 13, suggesting the stepwise formation of
12 and 13 from 7. The parent ion peaks were observed in
the HR-ESI-TOF mass spectra at m/z 2354.9250 ([MÀH]À;
calcd for C99H17N9F45CuPd: 2354.9253) for 12 and at m/z
2458.8181 ([MÀH]À; calcd for C99H15N9F45CuPd2: 2458.8138)
for 13. While only a preliminary crystal structure was ob-
tained for 12 (Supporting Information), the structure of 13
has been determined by using X-ray diffraction analysis
(Figure 6). In the latter, the Cu ion resides in the familiar
porphyrin-like core consisting of pyrroles A, B, H, and I, the
Pd1 ion is bound by C23, N6, N7, and C37 in an NNCC
fashion analogous to doubly N-confused porphyrin-like co-
ordination,[15] and the Pd2 ion is bound by N3, N4, and C22.
Interestingly, the distance between Pd2 and C38 is 2.23 Š,
our stepwise metalation protocol based on positive hetero-
or homoallosterism may be useful for controlled metalation.
Cyclic voltammograms of 3, 6, 7, 11, 12, and 13: Additional
attractive attributes of the multinuclear complexes 11, 12,
and 13 are their small electrochemical HOMO–LUMO gaps
(Figure 7). Cyclic voltammetry (Pt working electrode, scan
rate 0.1 VsÀ1, in CH2Cl2 containing 0.1m tetrabutylammoni-
um hexafluorophosphate, versus ferrocene/ferrocenium ion)
has revealed that 3 undergoes a reversible oxidation at
0.35 V and two reversible reductions at À0.52and À0.77 V,
and that complexes 6 and 7 display two reversible oxidations
at 0.22 and 0.53 V and at 0.25 and 0.57 V, respectively, and
two reversible reductions at À0.45 and À0.75 V and at À0.48
and À0.80 V, respectively. Thus, the electrochemical
HOMO–LUMO gaps are rather small, at 0.87, 0.67, and
0.73 V for 3, 6, and 7, respectively. Curiously, the trinuclear
complexes 11 and 13 exhibit two reversible oxidations at
0.17 and 0.54 V and at 0.16 and 0.53 V, respectively, and two
reversible reductions at À0.42and À0.79 V and at À0.42and
À0.80 V, respectively. The electrochemical HOMO–LUMO
gaps for 11 and 13 are thus 0.59 and 0.58 V, which are dis-
tinctly smaller than those of related octaphyrins[3d] and com-
parable to that (0.60 V) of cyclo[8]pyrrole,[17] which, to the
best of our knowledge, has been the smallest gap hitherto
reported for a metal complex of an expanded porphyrin.
À
which is distinctly longer than a normal C Pd bond length,
but is exactly what one would expect for an agostic interac-
tion, thus suggesting an agostic interaction between Pd2and
[16]
À
the C H bond of pyrrole H. As a consequence of the co-
ordination of the two palladium ions, the tetrapyrrolic seg-
ment consisting of pyrroles D, E, F, and G becomes more
coplanar in 13, with a mean plane deviation of 0.12Š, while
pyrrole H is tilted at a dihedral angle of 33.68. The absorp-
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[40]Nonaphyrin and Its Metal Complexes
FULL PAPER
in(1.1.1.1.1.1.1.1.1) 5. The structure of 3 has been identified
as having a figure-of-eight shape consisting of a porphyrin-
like tetrapyrrolic segment and a hexaphyrin-like hexapyrrol-
ic segment, while the structure of 5 has been characterized
as having a distorted butterfly-like shape. The nonaphyrin 3
has been converted into the mono-ZnII complex 6 and the
mono-CuII complex 7, in which the respective metal ions are
bound within the porphyrin-like core. Complexes 6 and 7
have been shown to serve as suitable precursors for the as-
sembly of the trinuclear metal complexes 11 (ZnII–PdII–PdII)
and 13 (CuII–PdII–PdII). Complex 13 has been found to
adopt a distorted nonplanar structure, in which the Pd1 ion
is bound in an NNCC fashion as in a doubly N-confused
porphyrin and the Pd2ion is bound in an NNC fashion with
an agostic interaction with the bridgehead pyrrole H. Curi-
ously, the metal complexes 6, 7, 11, 12, and 13 display small
electrochemical HOMO–LUMO gaps despite their distorted
nonplanar structures.
Experimental Section
General procedures: All reagents and solvents were of commercial re-
agent grade and were used without further purification except where
noted. Dry CH2Cl2 was obtained by distillation over CaH2. 1H and 19F
NMR spectra were recorded on a JEOL ECA-600 spectrometer (operat-
ing at 600.17 MHz for 1H and at 564.73 MHz for 19F) using the residual
1
solvent signal as an internal reference for H (d=7.260 ppm for CHCl3 in
CDCl3) and hexafluorobenzene as an external reference for 19F (d=
À162.9 ppm). Spectroscopic grade CH2Cl2 was used as solvent for all
UV/Vis spectroscopic studies. UV/Vis absorption spectra were recorded
on a Shimadzu UV-3100 spectrophotometer. Mass spectra were recorded
on either a JEOL HX-110 spectrometer, operating in the positive FAB
ionization mode with an accelerating voltage of 10 kV and 3-nitrobenzyl
alcohol as the matrix; a Shimadzu/KRATOS KOMPACT MALDI 4 spec-
trometer operating in the positive MALDI ionization mode; or
a
BRUKER microTOF spectrometer operating in positive- and negative-
ion modes with acetonitrile as solvent. Preparative separations were per-
formed by using flash column chromatography on silica gel (Merck Kie-
selgel 60H Art. 7736) or by using gravity column chromatography on
silica gel (Wako gel C-200, C-300, and C-400) or alumina (Sumitomo
Chemical KC-1525).
Crystallographic data collections and structure refinement: Crystallo-
graphic data for compounds 3, 5, and 13 were collected at À1508C on a
Rigaku RAXIS-RAPID apparatus using graphite-monochromated MoKa
radiation (l=0.71069 Š). Data for compounds 6 and 7 were collected at
T=À1838C on a Bruker SMART APEX apparatus, also using graphite-
monochromated MoKa radiation (l=0.71069 Š). Details of the crystal
structure determinations are listed in Table 1. The structures were solved
by using direct methods (SIR-97[18] or SHELXS-97[19]) and refined by ap-
plying Rigaku CrystalStructure software or by full-matrix least-squares
techniques (SHELXL-97).[19] CCDC-622794 (3), -620155 (5), -620156 (6),
-620157 (7), and -620158 (13) 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.au.uk/data_
request/cif.
Figure 7. Cyclic voltammograms of a) 3, b) 6, c) 7, d) 12, e) 11, and f) 13
in CH2Cl2 containing 0.1m TBAPF6 obtained at a Pt working electrode
(scan rate 0.1 VsÀ1).
The small HOMO–LUMO gap of cyclo[8]pyrrole has been
attributed to its large 30p electronic system, which is almost
planar. Interestingly, the electrochemical HOMO–LUMO
gap of complex 12 is even smaller, amounting to just 0.55 V.
The very small HOMO–LUMO gaps of these complexes are
remarkable, considering their distorted nonplanar figure-of-
eight conformations.
meso-Pentafluorophenyl-substituted [40]nonaphyrin (3): A solution of
5,10-bis(pentafluorophenyl)tripyrrane (1) (1.39 g, 2.5 mmol) and penta-
fluorobenzaldehyde (0.3 mL, 2.5 mmol) in CH2Cl2 (110 mL) (22.2 mm)
was stirred for 2h under N 2 with protection from light at 08C. Thereafter,
2.5m methanesulfonic acid (MSA) in CH2Cl2 (125 mL, 0.125 equiv) was
added to the solution. After a further 2h, 2,3-dichloro-5,6-dicyano-1,4-
benzoquinone (DDQ) (2.83 g, 12.5 mmol, 5 equiv) was added, and the re-
sulting solution was stirred overnight at room temperature. The reaction
Conclusion
In summary, the [40]nonaphyrin(1.1.1.1.1.1.1.1.1) 3 has been
prepared by using a stepwise ring-size-selective synthesis
and has been reduced with NaBH4 to the [42]nonaphyr-
Chem. Eur. J. 2007, 13, 1620 – 1628
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
1625

A. Osuka et al.
Table 1. Crystal data and structure refinement of 3, 5, 6, 7, and 13.
3
5
6
7
13
formula
Mr
T [K]
C
117H46F45N9
C100H26Cl2F45N9O
2298.09
123
C99H20F45N9OZn
2271.61
90
C111H34CuF45N9O2
2444.01
90
C111H23CuF45N9Pd2
2613.72
123
2426.62
123
crystal system
space group
a [Š]
b [Š]
c [Š]
orthorhombic
triclinic
P1 (no. 2)
15.059(4)
15.745(4)
19.371(6)
86.836(11)
79.811(10)
80.680(11)
4459(2)
2
1.712
0.227
2275
0.50”0.15”0.10
54.7
monoclinic
P21/c (no. 14)
14.5361(12)
22.0518(18)
26.669(2)
90
95.5350(10)
90
8508.8(12)
orthorhombic
Pbca (no. 61)
27.128(11)
20.317(8)
37.640(15)
90
triclinic
Pbca
A
P1 (no. 2)
13.731(3)
17.300(5)
22.157(7)
72.651(10)
85.300(11)
78.057(9)
4914(2)
27.235(5)
20.325(3)
38.101(5)
90
90
90
21090(6)
8
1.528
0.147
9704
0.60”0.20”0.05
56.255.2 56.4
18299
124048
1607
a [8]
b [8]
90
90
g [8]
V [Š3]
Z
20746(14)
4
8
2
1calcd [gcmÀ3
]
1.773
0.448
4480
0.45”0.35”0.20
50.0
20179
98955
1415
1.565
0.348
9704
0.45”0.20”0.10
1.766
0.720
2556
0.20”0.10”0.05
m [mmÀ1
(000)
]
F
A
crystal size [mm3]
2qmax [8]
observed reflns
total reflns
parameters
20366
45507
1515
24185
123426
1545
17024
38249
1469
absorpn correction
R1 [I>2s(I)]
wR2 (all data)
GoF
none
none
0.07620.609
0.2412
none
empirical
none
0.0883
0.2805
1.017
0.0742 0.0832
0.1792
1.024
0.2398
0.971
0.2677
1.030
1.024
was ultimately quenched by passing the mixture through a column of alu-
mina. The eluate was concentrated and then separated by using column
chromatography on silica gel (Wako gel C-400) to give [26]hexaphyr-
and the resulting mixture was stirred for 30 min. The reaction was then
quenched by the addition of water. The organic layer was washed with
brine and dried over Na2SO4. Removal of the solvent gave 5 almost
quantitatively. Crystals of 5 suitable for X-ray crystallographic analysis
were grown by means of vapor diffusion of hexane into a solution of the
in(1.1.1.1.1.1)
2
(510 mg,
0.35 mmol,
30%),
[40]nonaphyr-
in(1.1.1.1.1.1.1.1.1)
3
(280 mg, 0.13 mmol, 15%), and dodecaphyr-
1
in(1.1.1.1.1.1.1.1.1.1.1.1) 4 (35 mg, 12 mmol, 2%). At this scale of reaction,
we also observed the formation of porphyrin and other expanded por-
phyrins, including pentaphyrin, heptaphyrin, octaphyrin, decaphyrin, and
undecaphyrin, by means of TLC and MALDI TOF-MS analyses. Crystals
of 3 suitable for X-ray crystallographic analysis were grown by means of
vapor diffusion of heptane into a solution of the compound in CH2Cl2.
1H NMR (600 MHz, CDCl3, 298 K): d=16.41 (s, 1H; NH), 14.44 (s, 1H;
NH), 13.82(s, 1H; NH), 12.35 (s, 1H; NH), 10.17 (d, J=4.1 Hz, 1H; b-
H), 9.81 (d, J=4.0 Hz, 1H; b-H), 9.76 (d, J=4.1 Hz, 1H; b-H), 7.99 (d,
J=4.7 Hz, 1H; b-H), 7.95 (d, J=4.6 Hz, 1H; b-H), 6.78 (d, J=4.6 Hz,
1H; b-H), 6.77 (s, 1H; b-H), 6.73 (s, 1H; b-H), 6.65 (s, 1H; b-H), 6.53 (d,
J=4.1 Hz, 1H; b-H), 6.40 (s, 1H; b-H), 6.24 (d, J=4.1 Hz, 1H; b-H),
6.19 (d, J=4.2Hz, 1H; b-H), 6.15 (d, J=4.0 Hz, 1H; b-H), 6.08 (d, J=
4.1 Hz, 1H; b-H), 6.05 (d, J=4.6 Hz, 1H; b-H), 5.92(d, J=3.7 Hz, 1H;
b-H), 5.67 ppm (d, J=3.8 Hz, 1H; b-H); 19F NMR (565 MHz, CDCl3,
298 K): d=À133.6 (d, J=20.7 Hz, 1F; o-Ar), À134.1 (d, J=19.0 Hz, 1F;
o-Ar), À134.5 (d, J=20.7 Hz, 1F; o-Ar), À135.0 (m, 1F; o-Ar), À135.5
(m, 2F; o-Ar), À136.5 (m, 3F; o-Ar), À137.9 (d, J=20.7 Hz, 1F; o-Ar),
À138.0 (d, J=17.3 Hz, 1F; o-Ar), À138.3 (m, 1F; o-Ar), À138.9 (m, 1F;
o-Ar), À139.2(d, J=22.4 Hz, 1F; o-Ar), À139.6 (m, 2F; o-Ar), À139.9
(m, 1F; o-Ar), À140.2(m, 1F; o-Ar), À151.4 (q, J=20.7 Hz, 1F; p-Ar),
À151.6 (q, J=22.4 Hz, 1F; p-Ar), À152.1 (m, 2F; p-Ar), À152.7 (m, 3F;
p-Ar), À154.3 (t, J=20.7 Hz, 1F; p-Ar), À154.9 (t, J=20.7 Hz, 1F; p-
Ar), À158.0 (m, 1F; m-Ar), À159.1 (m, 1F; m-Ar), À160.6 (t, J=
19.0 Hz, 1F; m-Ar), À160.8 (t, J=20.7 Hz, 1F; m-Ar), À161.2(m, 7F;
m-Ar), À161.6 (t, J=20.7 Hz, 1F; m-Ar), À161.8 (t, J=20.7 Hz, 1F; m-
Ar), À162.0 (q, J=22.4 Hz, 1F; m-Ar), À163.3 (t, J=18.9 Hz, 1F; m-
Ar), À163.5 (t, J=20.7 Hz, 1F; m-Ar), À164.6 (t, J=20.7 Hz, 1F; m-Ar),
À165.1 ppm (t, J=21.5 Hz, 1F; m-Ar); UV/Vis (CH2Cl2): lmax (e)=342
(50000), 442(72000), 705 nm (90000); HR-ESI-TOF-MS: m/z: calcd for
C99H23F45N9: 2192.1352; found: 2192.1369 [M+H]+.
compound in CH2Cl2. H NMR (600 MHz, CDCl3, 298 K) (major peaks):
d=15.31 (s, 1H; NH), 15.09 (brs, 1H; NH), 14.88 (s, 1H; NH), 14.62
(brs, 1H; NH), 13.65 (s, 1H; NH), 13.10 (s, 1H; NH), 9.36 (d, J=2.9 Hz,
1H; b-H), 7.54 (d, J=4.5 Hz, 1H; b-H), 7.47 (d, J=3.8 Hz, 1H; b-H),
7.37 (s, 1H; b-H), 7.05 (s, 1H; b-H), 6.91 (d, J=4.4 Hz, 1H; b-H), 6.54
(s, 2H; b-H), 6.35 (d, J=4.8 Hz, 1H; b-H), 6.25 (d, J=3.5 Hz, 1H; b-H),
6.10 (d, J=3.8 Hz, 1H; b-H), 6.03 (d, J=4.2Hz, 1H; b-H), 6.01 (d, J=
4.1 Hz, 1H; b-H), 5.80 (s, 1H; b-H), 5.72(d, J=3.8 Hz, 1H; b-H), 5.69
(d, J=3.2Hz, 1H; b-H), 5.56 (d, J=2.9 Hz, 1H; b-H), 5.26 ppm (s, 1H;
b-H); 19F NMR (565 MHz, CDCl3, 298 K): d=À131.5 (dd, J=56.9 Hz,
J=17.3 Hz, 1F; o-Ar), À134.1 (d, J=22.4 Hz, 1F; o-Ar), À134.3 (m, 2F;
o-Ar), À135.1 (dd, J=55.2Hz, J=13.8 Hz, 1F; o-Ar), À135.8 (d, J=
20.7 Hz, 1F; o-Ar), À136.6 (m, 1F; o-Ar), À137.1 (d, J=22.4 Hz, 1F; o-
Ar), À137.9 (d, J=20.7 Hz, 1F; o-Ar), À138.2(m, 4F; o-Ar), À138.6 (m,
4F; o-Ar), À140.5 (m, 1F; o-Ar), À147.7 (t, J=20.7 Hz, 1F; p-Ar),
À149.9 (m, 1F; p-Ar), À151.7 (t, J=21.5 Hz, 1F; p-Ar), À151.9 (m, 1F;
p-Ar), À152.1 (m, 1F; p-Ar), À152.5 (m, 1F; p-Ar), À152.7 (m, 1F; p-
Ar), À153.0 (m, 2F; p-Ar), À156.0 (m, 1F; m-Ar), À157.1 (t, J=19.8 Hz,
1F; m-Ar), À158.1 (m, 2F; m-Ar), À158.9 (m, 1F; m-Ar), À160.1 (m,
1F; m-Ar), À160.3 (m, 1F; m-Ar), À160.5 (m, 3F; m-Ar), À160.8 (m,
4F; m-Ar), À161.0 ppm (m, 4F; m-Ar) (beside these signals, sets of
minor peaks were observed, suggesting the presence of minor conformers
of
5 in solution); UV/Vis (CH2Cl2): lmax (e)=469 (70000), 739 nm
(111000); HR-ESI-TOF-MS: m/z: calcd for C99H25F45N9: 2194.1509;
found: 2194.1522 [M+H]+.
ZnII complex of [40]nonaphyrin (6): A solution of 3 (43.8 mg, 20 mmol)
and NaOAc (3.3 mg, 40 mmol, 2equiv) in a 1:1 mixture of CH 2Cl2 and
methanol was stirred under N2 at room temperature. Zn(OAc)2·2H2O
G
(43.9 mg, 0.2mmol, 10 equiv) was then added, and after 15–30 min the
reaction mixture was washed with brine, dried with Na2SO4, and the sol-
vent was removed. The residual mixture was separated by using column
meso-Pentafluorophenyl-substituted [42]nonaphyrin (5): NaBH4 (7.6 mg,
0.2mmol, 10 equiv) was carefully added in small portions to a stirred so-
lution of 3 (43.8 mg, 20 mmol) in a 1:1 mixture of CH2Cl2 and methanol
chromatography on silica gel (Wako gel C-400) to give complex 6
(33.6 mg, 15 mmol, 75%). Crystals of 6 suitable for X-ray crystallographic
analysis were grown by means of vapor diffusion of hexane into a solu-
1626
www.chemeurj.org
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2007, 13, 1620 – 1628

[40]Nonaphyrin and Its Metal Complexes
FULL PAPER
1
tion of the compound in CH2Cl2. H NMR (600 MHz, CDCl3, 298 K): d=
À154.1 (q, J=20.7 Hz, 1F; p-Ar), À158.5 (m, 3F; m-Ar), À159.9 (m, 1F;
m-Ar), À160.0 (t, J=20.8 Hz, 1F; m-Ar), À160.3 (t, J=20.7 Hz, 1F; m-
Ar), À160.4 (t, J=20.7 Hz, 1F; m-Ar), À160.5 (t, J=20.7 Hz, 1F; m-Ar),
À160.7 (t, J=20.7 Hz, 1F; m-Ar), À161.1 (t, J=22.5 Hz, 1F; m-Ar),
À161.2(t, J=21.6 Hz, 1F; m-Ar), À161.3 (t, J=22.4 Hz, 1F; m-Ar),
À161.6 (t, J=20.7 Hz, 2F; m-Ar), À161.7 (t, J=22.5 Hz, 1F; m-Ar),
À161.8 (m, 1F; m-Ar), À163.1 (m, 1F; m-Ar), À164.8 ppm (t, J=
24.2 Hz, 1F; m-Ar); UV/Vis (CH2Cl2): lmax (e)=339 (41000), 466
(90000), 819 nm (93000); FAB-MS: m/z: calcd for C99H22F45N9Zn:
2255.06; found: 2254.94 [M]+.
CuII complex of [42]nonaphyrin (10): NaBH4 (3.8 mg, 0.1 mmol,
10 equiv) was carefully added in small portions to a stirred solution of 7
(22.5 mg, 10 mmol) in a 1:1 mixture of CH2Cl2 and methanol and stirring
was continued for a further 30 min. The reaction was then quenched with
water and the mixture was washed with brine and dried over Na2SO4.
Removal of the solvent left a quantitative yield of the mono-Cu complex
of [42]nonaphyrin 10. UV/Vis (CH2Cl2): lmax (e)=332(41000), 467
(84000), 818 nm (85000); FAB-MS: m/z: calcd for C99H22F45N9Cu:
2254.06; found: 2253.94 [M]+.
19.91 (s, 1H; NH), 17.98 (s, 1H; NH), 12.99 (s, 1H; b-H), 12.47 (s, 1H;
b-H), 12.32 (s, 1H; b-H), 9.60 (s, 1H; b-H), 7.52(s, 1H; b-H), 7.16 (s,
1H; b-H), 7.02(s, 1H; b-H), 6.46 (s, 1H; b-H), 6.41 (s, 1H; b-H), 6.26 (s,
2H; b-H), 6.04 (s, 1H; b-H), 5.70 (s, 1H; b-H), 5.63 (s, 1H; b-H), 5.39 (s,
1H; b-H), 5.34 (s, 1H; b-H), 5.12(s, 1H; b-H), 4.92ppm (s, 1H; b-H);
19F NMR (565 MHz, CDCl3, 298 K): d=À127.5 (brs, 1F; o-Ar), À128.6
(m, 1F; o-Ar), À130.8 (d, J=23.3 Hz, 1F; o-Ar), À132.0 (d, J=21.6 Hz,
1F; o-Ar), À132.6 (d, J=19.0 Hz, 1F; o-Ar), À134.2(m, 1F; o-Ar),
À134.7 (d, J=23.3 Hz, 1F; o-Ar), À134.9 (d, J=21.1 Hz, 1F; o-Ar),
À136.2(d, J=20.7 Hz, 1F; o-Ar), À136.4 (d, J=17.3 Hz, 2F; o-Ar),
À137.0 (m, 3F; o-Ar), À137.3 (d, J=21.6 Hz, 1F; o-Ar), À138.0 (m, 1F;
o-Ar), À139.5 (m, 2F; o-Ar), À148.8 (m, 1F; p-Ar), À149.5 (t, J=
21.6 Hz, 1F; p-Ar), À150.4 (t, J=20.7 Hz, 1F; p-Ar), À151.3 (t, J=
20.7 Hz, 1F; p-Ar), À151.6 (dd, J=55.0 Hz, J=20.7 Hz, 2F; p-Ar),
À152.2 (t, J=20.7 Hz, 1F; p-Ar), À153.4 (t, J=20.7 Hz, 1F; p-Ar),
À153.6 (t, J=21.2 Hz, 1F; p-Ar), À156.1 (m, 1F; m-Ar), À156.5 (m, 1F;
m-Ar), À159.3 (t, J=23.3 Hz, 1F; m-Ar), À159.5 (m, 2F; m-Ar), À159.8
(m, 3F; m-Ar), À160.0 (m, 1F; m-Ar), À160.1 (m, 2F; m-Ar), À160.3 (t,
J=22.0 Hz, 1F; m-Ar), À160.4 (t, J=21.6 Hz, 1F; m-Ar), À160.5 (t, J=
21.6 Hz, 1F; m-Ar), À162.3 (m, 2F; m-Ar), À163.6 (t, J=21.6 Hz, 1F;
m-Ar), À164.1 ppm (t, J=22.0 Hz, 1F; m-Ar); UV/Vis (CH2Cl2): lmax
(e)=350 (55000), 457 (84000), 741 nm (89000); HR-ESI-TOF-MS: m/z:
calcd for C99H20F45N9Zn: 2253.0420; found: 2253.0460 [M]À.
ZnII–PdII complex and ZnII–PdII–PdII complex (11) of [40]nonaphyrin:
Pd(OAc)2 (22.4 mg, 0.1 mmol, 10 equiv) was added to a stirred solution
A
of 6 (22.6 mg, 0.01 mmol) in a 1:10 mixture of CH2Cl2 and methanol at
room temperature. After 2h, the reaction mixture was washed with brine
and dried over Na2SO4, and the solvent was removed. The residual mix-
ture was separated by using column chromatography on silica gel (Wako
gel C-400) to give the ZnPd complex (3.6 mg, 1.5 mmol, 15%) and the
ZnPd2 complex 11 (5.2mg, 2.1 mmol, 21%). When the metalation was
performed in the presence of sodium acetate, complex 11 was formed
almost quantitatively.
CuII complexes of [40]nonaphyrin (7) and (8): A solution of 3 (43.8 mg,
20 mmol) and NaOAc (3.3 mg, 40 mmol) in a 1:1 mixture of CH2Cl2 and
methanol was stirred under N2 at room temperature. Cu(OAc)2 (24.5 mg,
A
0.2mmol, 10 equiv) was then added, and after 15–30 min the reaction
mixture was washed with brine, dried with Na2SO4, and the solvent was
removed. The residual mixture was separated by using column chroma-
tography on silica gel (Wako gel C-400) to give mono-CuII complex 7
(15.7 mg, 6.9 mmol, 35%) and bis-CuII complex 8 (12.5 mg, 5.4 mmol,
27%). Crystals of 7 suitable for X-ray crystallographic analysis were
grown by means of vapor diffusion of hexane into a solution of the com-
pound in CH2Cl2.
Mono-CuII complex of [40]nonaphyrin (7): UV/Vis (CH2Cl2): lmax (e)=
351 (52000), 453 (80000), 737 nm (87000); HR-ESI-TOF-MS: m/z: calcd
for C99H20F45N9Cu: 2252.0425; found: 2252.0408 [M]À.
ZnII–PdII–PdII complex of [40]nonaphyrin (11): 1H NMR (600 MHz,
CDCl3, 298 K): d=10.60 (d, J=4.1 Hz, 1H; b-H), 8.53 (d, J=4.1 Hz, 1H;
b-H), 7.95 (t, J=4.6 Hz, 1H; b-H), 7.29 (d, J=4.6 Hz, 1H; b-H), 6.70 (d,
J=4.6 Hz, 1H; b-H), 6.21 (d, J=4.6 Hz, 1H; b-H), 6.17 (d, J=5.0 Hz,
1H; b-H), 5.89 (s, 1H; NH), 5.78 (d, J=4.6 Hz, 1H; b-H), 5.67 (d, J=
5.0 Hz, 1H; b-H), 5.05 (d, J=5.0 Hz, 1H; b-H), 4.85 (d, J=4.6 Hz, 1H;
b-H), 4.63 (s, 1H; b-H (H1 in Figure 5)), 4.40 (brs, 1H; b-H), 4.39 (t, J=
4.1 Hz, 1H; b-H), 3.46 ppm (brs, 1H; b-H); 19F NMR (565 MHz, CDCl3,
298 K): d=À121.4 (d, J=23.3 Hz, 1F; o-F), À123.7 (d, J=21.5 Hz, 1F;
o-F), À125.5 (m, 1F; o-F), À129.6 (d, J=20.7 Hz, 1F; o-F), À129.7 (s,
1F; o-F), À133.2(m, 1F; o-F), À133.6 (m, 1F; o-F), À136.9 (d, J=
20.7 Hz, 1F; o-F), À136.2(d, J=23.3 Hz, 1F; o-F), À136.6 (m, 1F; o-F),
À136.7 (m, 1F; o-F), À136.8 (m, 2F; o-F), À137.0 (d, J=23.3 Hz, 1F; o-
F), À137.1 (d, J=21.5 Hz, 1F; o-F), À138.2(d, J=22.4 Hz, 1F; o-F),
À138.9 (d, J=18.1 Hz, 1F; o-F), À140.0 (dd, J=53.4 Hz, J=26.7 Hz, 1F;
o-F), À147.2(s, 1F; p-F), À150.0 (m, 2F; p-F), À150.6 (m, 1F; p-F),
À150.9 (t, J=21.4 Hz, 1F; p-F), À151.4 (t, J=20.7 Hz, 1F; p-F), À151.9
(t, J=21.5 Hz, 1F; p-F), À152.1 (t, J=20.7 Hz, 1F; p-F), À152.4 (t, J=
20.7 Hz, 1F; p-F), À153.5 (m, 1F; m-F), À153.4 (m, 1F; m-F), À158.8
(m, J=23.3 Hz, 1F; p-F), À158.9 (t, J=21.5 Hz, 1F; p-F), À159.3 (t, J=
21.5 Hz, 1F; p-F), À159.4 (m, 3F; p-F), À159.6 (m, 3F; p-F), À160.0 (m,
2F; p-F), À160.1 (m, 2F; p-F), À160.7 (t, J=20.7 Hz, 1F; p-F), À160.9 (t,
J=20.7 Hz, 1F; p-F), À161.1 ppm (t, J=19.8 Hz, 1F; p-F); UV/Vis
(CH2Cl2): lmax (e)=377 (44000), 466 (66000), 649 (18000), 827 nm
(63000); HR-ESI-TOF-MS: m/z: calcd for C99H15F45N9ZnPd2: 2459.8129;
found: 2459.8140 [MÀH]À.
Bis-CuII complex of [40]nonaphyrin (8): UV/Vis (CH2Cl2): lmax (e)=348
(84000), 594 (90000), 780 nm (94000); HR-ESI-TOF-MS: m/z: calcd for
C99H17F45N9Cu2: 2311.9486; found: 2311.9511 [MÀH]À.
ZnII complex of [42]nonaphyrin (9): NaBH4 (3.8 mg, 0.1 mmol, 10 equiv)
was carefully added in small portions to a stirred solution of 6 (22.5 mg,
10 mmol) in a 1:1 mixture of CH2Cl2 and methanol and stirring was con-
tinued for a further 30 min. The reaction was then quenched with water
and the mixture was washed with brine and dried over Na2SO4. Removal
of the solvent left a quantitative yield of the mono-Zn complex of
[42]nonaphyrin 9. Alternatively, treatment of 5 with Zn(OAc)2·2H2O
R
1
gave the same product in 78% yield. H NMR (600 MHz, CDCl3, 298 K):
d=9.94 (s, 1H; NH), 8.86 (d, J=4.8 Hz, 1H; b-H), 8.59 (s, 1H; NH),
7.47 (d, J=4.4 Hz, 1H; b-H), 7.38 (d, J=4.9 Hz, 1H; b-H), 7.21 (d, J=
4.3 Hz, 1H; b-H), 7.09 (d, J=4.5 Hz, 1H; b-H), 7.06 (s, 1H; b-H), 6.92
(s, 1H; b-H), 6.67 (s, 1H; b-H), 6.61 (s, 1H; b-H), 6.43 (s, 1H; b-H), 6.27
(d, J=4.8 Hz, 1H; b-H), 6.00 (d, J=4.4 Hz, 1H; b-H), 5.62(d, J=4.2Hz,
1H; b-H), 4.76 (d, J=4.1 Hz, 1H; b-H), 4.40 (s, 1H; b-H), 4.03 (d, J=
4.1 Hz, 1H; b-H), 3.41 (s, 1H; NH), 3.15 (d, J=4.8 Hz, 1H; b-H), 3.10
(d, J=4.8 Hz, 1H; b-H), 2.69 ppm (s, 1H; NH); 19F NMR (565 MHz,
CDCl3, 298 K): d=À131.3 (dd, J=65.6 Hz, J=23.3 Hz, 1F; o-Ar),
À131.9 (d, J=20.7 Hz, 1F; o-Ar), À132.0 (d, J=22.5 Hz, 1F; o-Ar),
À134.0 (d, J=24.2 Hz, 1F; o-Ar), À135.2(m, 1F; o-Ar), À135.6 (d, J=
25.9 Hz, 1F; o-Ar), À136.0 (m, 1F; o-Ar), À136.3 (m, 1F; o-Ar), À136.9
(m, 1F; o-Ar), À137.1 (m, 3F; o-Ar), À137.7 (d, J=20.7 Hz, 1F; o-Ar),
À138.1 (d, J=24.2 Hz, 1F; o-Ar), À138.4 (d, J=19.0 Hz, 1F; o-Ar),
À139.2(dd, J=28.5 Hz, J=18.9 Hz, 1F; o-Ar), À143.3 (d, J=24.2 Hz,
1F; o-Ar), À143.6 (d, J=27.6 Hz, 1F; o-Ar), À149.6 (t, J=20.7 Hz, 1F;
p-Ar), À150.0 (t, J=20.7 Hz, 1F; p-Ar), À150.6 (t, J=21.6 Hz, 1F; p-
Ar), À151.5 (t, J=20.7 Hz, 1F; p-Ar), À152.8 (t, J=21.6 Hz, 1F; p-Ar),
À153.0 (t, J=21.6 Hz, 2F; p-Ar), À153.2(t, J=20.7 Hz, 1F; p-Ar),
CuII–PdII complex (12) and CuII–PdII–PdII complex (13) of [40]nonaphyr-
in: Pd(OAc)2 (22.4 mg, 0.1 mmol, 10 equiv) was added to a stirred solu-
A
tion of the mono-CuII complex 7 (22.5 mg, 0.01 mmol) in a 1:10 mixture
of CH2Cl2 and methanol under N2 at room temperature. After 2h, the re-
action mixture was washed with brine and dried over Na2SO4, and the
solvent was removed. The residual mixture was separated by using
column chromatography on silica gel (Wako gel C-400) to give the CuPd1
complex 12 (3.8 mg, 1.6 mmol, 16%) and the CuPd2 complex 13 (11.3 mg,
4.6 mmol, 46%). When the metalation was performed in the presence of
sodium acetate, complex 13 was formed almost quantitatively. Crystals of
13 suitable for X-ray crystallographic analysis were grown by means of
vapor diffusion of hexane into a solution of the compound in CHCl3.
Chem. Eur. J. 2007, 13, 1620 – 1628
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
1627

A. Osuka et al.
CuII–PdII complex of [40]nonaphyrin (12): HR-ESI-TOF-MS: m/z: calcd
for C99H17F45N9CuPd: 2354.9253; found: 2354.9250 [MÀH]À.
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(47000); HR-ESI-TOF-MS: m/z: calcd for C99H15F45N9CuPd2: 2458.8138;
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Acknowledgements
This work was partly supported by a Grant-in-Aid (B) (No. 17350017)
from the Ministry of Education, Culture, Sports, Science and Technology
of Japan and a CREST (Core Research for Evolutional Science and
Technology) award from the Japan Science and Technology Agency
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Received: September 11, 2006
Published online: November 23, 2006
1628
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Chem. Eur. J. 2007, 13, 1620 – 1628