N-fusion approach in construction of contracted carbaporphyrinoids: formation of N-fued telluraporphyrin

Article abstract of DOI:10.1002/chem.200900841

Insertion of PCl₃ into 5,10,15,20-tetraaryl-21-telluraporphyrin leads to a phosphorus complex of N-fused dihydrotelluraporphyrin with an inverted tellurophene ring. Its CNN coordination core places the macrocycle in the family of contracted car

Full text of DOI:10.1002/chem.200900841

DOI: 10.1002/chem.200900841
N-Fusion Approach in Construction of Contracted Carbaporphyrinoids:
Formation of N-Fused Telluraporphyrin
Ewa Pacholska-Dudziak, Filip Ulatowski, Zbigniew Ciunik, and
Lechosław Latos-Grazyn´ski*[a]
˙
Dedicated to Professor Marilyn M. Olmstead
Abstract: Insertion of PCl3 into 5,10,15,20-tetraaryl-21-telluraporphyrin leads to a
phosphorus complex of N-fused dihydrotelluraporphyrin with an inverted telluro-
phene ring. Its CNN coordination core places the macrocycle in the family of con-
Keywords: fullerenes · macrocycles ·
tracted carbaporphyrinoids. A cycle of direct transformations affords an elegant
porphyrinoids · template synthesis ·
triangle of three mutually convertible N-fused porphyrinoids, with distinct spectro-
supramolecular chemistry
scopic features: antiaromatic, nonaromatic and aromatic. The nonaromatic species
has a dome shaped skeleton which forms in the solid state a ball and socket struc-
ture with C60.
Introduction
Porphyrins reveal considerable structural flexibility that re-
sults in severely nonplanar core conformations. The forma-
tion of N-fused porphyrin (2)[1] occupies a very special place
in the search for the limits of porphyrin skeleton distortions.
N-Confused porphyrin 1 transforms into an 18-p-electron ar-
omatic porphyrinoid with a fused tripentacyclic ring in the
macrocyclic core: N-fused porphyrin 2.[2,3]
Significantly, inversion of the N-confused pyrrole ring in
the N-confused porphyrin skeleton is a prerequisite for an
intramolecular fusion step that clearly demonstrates the pe-
porphyrins initiated the N-confused pyrrole inversion fol-
À
lowed by C N bond formation (e.g., [2reduced]-PO).
Herein we explore a possibility to create a heteroana-
logue of N-fused porphyrin derived from 21-telluraporphyr-
in by applying a coordination template approach. 5,10,15,20-
Tetraaryl-21-telluraporphyrin 3 with a large core heteroatom
is nearly planar[9;10] and reveals characteristic spectroscopic
features of an aromatic 21-heteroporphyrin. Bearing in
mind the nonorthodox structure of 5,10,15,20-tetraaryl-
21,23-ditelluraporphyrin,[11] one can presume that the con-
formation of 3, which has an inverted tellurophene ring,
might be energetically accessible if stabilized by coordina-
tion or as a transient species of N-fusion process.
culiar plasticity of the [18]porphyrin
ACHTUNGERTN(NUNG 1.1.1.1)-like frame. The
intermediary inverted macrocyclic conformation was trap-
ped in the bisACHTUNGTRENNUNG[iridium(I)] complex of N-confused porphy-
rin[4] or obtained by cleavage of the bridging C N bond in
the C2–C2’ dimer of 2.[5] A template factor has been recog-
nized as the fusion driving force; that is, insertion of rheni-
À
ACHTUNGTRENNUNG ACHTUNGTRENNUNG
um(I),[6] boron(III),[7] or phosphorus(V)[8] into N-confused
[a] Dr. E. Pacholska-Dudziak, F. Ulatowski, Prof. Dr. Z. Ciunik,
´
Prof. Dr. L. Latos-Graz˙ynski
Wydział Chemii
Uniwersytetu Wrocławskiego
ul. F. Joliot-Curie 14
50-383 Wrocław, POLAND
Fax : (+48)71-32-823-48
E-mail: llg@wchuwr.pl
Results and Discussion
21-Telluraporphyrin 3 reacts with PCl3 in triethylamine to
give phosphorus(V) dihydro-N-fused 21-telluraporphyrin, 4-
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.200900841.
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Chem. Eur. J. 2009, 15, 10924 – 10929

FULL PAPER
PO (55%), after chromatographic workup. The rearranged
macrocycle acts as triaanionic tridentate ligand
(Scheme 1). Therefore, the insertion of phosphorus into 3
both contain identical macrocyclic frames. In the same line
of consideration, macrocycles 4 and 5 are (formally) mutual-
ly convertible by a hydrogenation/dehydrogenation step. In
terms of oxidation state, N-fused 21-telluraporphyrin 5 is
two-electron oxidized with respect to 21-telluraporphyrin 3.
Cyclic voltammetry (Figure S5 in the Supporting Informa-
tion) demonstrates that 4-PO undergoes two consecutive, re-
versible one-electron oxidations with half-wave potentials of
À0.127 and +0.239 V and two consecutive, reversible one-
electron reductions with half-wave potentials of À1.568 and
À1.708 V (vs. ferrocene/ferrocenium (Fc/Fc+), tetra-n-butyl-
a
prompted inversion of the tellurophene ring and formation
AHCTUNGTRENNUNG
.
Treatment of 4-PO with m-chloroperoxybenzoic acid
(MCPBA) produces nonaromatic N-fused telluraphlorin
6(O)-PO (i.e., heteroderivative of N-fused phlorin[8]). The
macrocyclic skeleton of 6(O)-PO (Scheme 3) contains an sp3
Scheme 1. Insertion of phosphorus into telluraporphyrin (Ar=p-meth-
ACHTUNGTRENNUNGoxyphenyl).
of antiaromatic 4-PO, in which the contracted CNN core of
the N-fused porphyrin provides a favorable match for the
small radius of phosphorus(V). Although the appropriate
mechanism remains unknown at present, the coordination
of phosphorus is obviously a precondition of a sequence of
transformations that lead to 4-PO. Despite several attempts,
we could not remove phosphorus(V) from 4-PO. Significant-
ly, the dihydro-N-confused telluraporphyrin ligand 4, albeit
built into the 4-PO structure, can be recognized as an antiar-
omatic constitutional isomer of aromatic 21-telluraporphyrin
3 (Scheme 2). Novel porphyrinoid 4 is also related to hypo-
thetical aromatic N-fused 21-telluraporphyrin 5 because
Scheme 3. Oxidation of 4-PO (oxidant=MCPBA, DDQ or AgBF4).
meso carbon atom as confirmed by 13C NMR spectroscopy.
The 13C chemical shift of C20 (d=73.8 ppm) is consistent
with tetrahedral hybridization of a carbon atom substituted
with one oxygen. Oxidation of 4-PO with DDQ (2,3-di-
chloro-5,6-dicyanobenzoquinone) or with AgBF4 followed
by addition of water gave 6(O)-PO as well. Formation of a
transient 5-PO2+ dication that is prone to nucleophilic
attack is readily included into the mechanism of 6(O)-PO
formation. The oxidation may be reversed by treating 6(O)-
PO with PCl3 in boiling pyridine.
Scheme 2. Telluraporphyrin 3 (aromatic), dihydro-N-fused 21-tellurapor-
phyrin 4 (antiaromatic), and N-fused 21-telluraporphyrin 5 (aromatic).
Titration of 6(O)-PO with acids (HX: trifluoroacetic acid
(TFA), HBF4, (1R)-(À)-10-camphorosulfonic acid), moni-
Abstract in Polish: W wyniku insercji trꢀjchlorku fosforu do
5,10,15,20-tetraarylo-21-telluraporfiryny otrzymano fosforo-
wy kompleks skondensowanej dihydrotelluraporfiryny z od-
1
tored by H NMR spectroscopy, initially results in a proto-
nation to give a nonaromatic 6(O)-POH+ ion (Figure 1,
traces a)–d); Scheme 4) that remains in fast exchange with
6(O)-PO, as indicated by smooth changes in the chemical
shifts observed in this titration range. Subsequent addition
of excess acid gave an aromatic [5-P(OH)2X]+ ion that
adopts a macrocyclic structure of 5 with an 18-p-electron de-
localization pathway (Scheme 4; Figure 1, trace f).
In fact, all phosphine oxide complexes of N-fused tellura-
porphyrin derivatives (4-PO, [5-P(OH)2X]+, and 6(O)-PO)
are chiral and their syntheses lead to racemic mixtures.
Thus, once a chiral acid ((1R)-10-camphorosulphonic acid)
is used in reaction with 6(O)-PO instead of achiral TFA or
´
wrꢀconym pierscieniem tellurofenowym. Trꢀjkoordynacyjny
´
rdzen CNN tak powstałego makrocykla klasyfikuje go do ro-
dziny zmniejszonych karbaporfirynoidꢀw. Zsyntezowano
trzy pokrewne kompleksy tego typu (antyaromatyczny, nie-
aromatyczny i aromatyczny), moga˛ce wzajemnie przekształ-
´
´
´
cac sie˛ w siebie. Rꢀz˙nia˛ sie˛ one zasadniczo własciwosciami
spektroskopowymi. Zwia˛zek niearomatyczny charakteryzuje
sie˛ bardzo pofałdowanym szkieletem i kokrystalizuje z fule-
renem C60 dopasowuja˛c sie˛ wkle˛sła˛ strona˛ do jego wypukłej
powierzchni.
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´
L. Latos-Graz˙ynski et al.
Figure 2. 1H NMR spectra (CDCl3, 298 K) of a) 4-PO, b) 6(O)-PO,
c) [5ÀP(OH)2X]+ (X=(1R)-(À)-10-camphorosulfonic acid anion). The
numbering is given for pyrrolic protons. The signal marked with * indi-
cates CH2Cl2 and ** indicates SO3H. The inset shows a doubled number
of AB-pattern signals for one pyrrole for X=(1R)-10-camphorosulfonate
(i) as compared with an achiral pyrrole X=TFAÀ (ii).
trum (b-H: d=6.6–7.7 ppm)[13–16] caused by the presence of
tetrahedral carbon atom (C20) that disrupts the delocaliza-
tion pathway. Finally, clear aromatic features have been de-
tected for [5-P(OH)2X]+ (d=7.5–9.0 ppm). The marked
changes in electronic structures detected for 4-PO, 6(O)-PO,
and [5-P(OH)2X]+ corroborate well with the distinct differ-
ences in 31P chemical shifts: d=10.09, À71.38, and 1.08 ppm
respectively. The d=À16.9 and À32.3 ppm chemical shifts
have been determined for related phosphorus(V) complexes
of N-fused porphyrin and N-fused phlorin, respectively,[8]
whereas the d=À160 to À230 ppm range is characteristic
for phosphorus complexes of regular porphyrins.[17] An enor-
Figure 1. Titration of 6(O)-PO with (1R)-(À)-10-camphorsulfonic acid
monitored by 1H NMR spectroscopy (CDCl3, 298 K, 600 MHz). Molar
ratio of 6(O)-PO to added (1R)-(À)-10-camphorsulfonic acid: a) 1:0,
b) 1:0.3, c) 1:1, d) 1:6.5, and e) 1:6.5 after 1 day, f) 1:6.5 after 3 weeks. The
signal marked with ** indicates SO3H.
mously large 1J
detected for P-C22 bond in 6(O)-PO whereas the corre-
sponding, 1J
(C,P) value for 4-PO is 161 Hz.
ACHTUNGTRENN(UNG C,P) coupling constant (214 Hz) has been
Scheme 4. Reactions of 6(O)-PO with acid (X=TFAÀ, (1R)-(À)-10-cam-
AHCTUNGTRENNUNG
phorosulfonate anion).
Compounds 4-PO and 6(O)-PO were structurally charac-
terized (Figures 3 and 4).[18] X-ray quality crystals were ob-
tained by slow diffusion of 4-PO in benzene into hexane to
give 4-PO·C6H6. For compound 6(O)-PO, addition of fuller-
ene C60 in benzene to the porphyrinoid solution was essen-
tial for monocrystal growth. Compound 6(O)-PO cocrystal-
lizes with fullerene to give 2(6(O)-PO)·C60·3C6H6 similar to
examples of fullerene–regular metalloporphyrin assem-
blies.[19–22]
HBF4, the b-pyrrolic signals are doubled in the 1H NMR
spectrum (Figure 2c, inset). This observation reflects the co-
ordination of the chiral anion and formation of two diaste-
ACHTUNGTRENNUNGreoisomers.
1
The H NMR spectra of 4-PO, [5-P(OH)2X]+, and 6(O)-
PO present essential features consistent with suggested mo-
lecular and electronic structures (Figure 2). The perimeter
hydrogen atoms of 4-PO reveal a relatively widely spread
set of upfield b-H resonances. The observed spectral range
(d=3.8–4.7 ppm) indicates the paratropic effect and proves
the essential influence of the macrocyclic 20-electron p-de-
localization pathway.[12] In contrast with the clearly antiaro-
matic character of 4-PO, 6(O)-PO presents nonaromatic
macrocyclic behavior as manifested on the 1H NMR spec-
The coordination environment of phosphorus(V) in 4-PO
resembles a distorted trigonal pyramid with one carbon and
two nitrogen atoms occupying equatorial positions with the
À
oxygen atom lying at the unique apex. The P N bond
lengths of 4-PO resemble those determined for phosphor-
us(V) N-fused porphyrin.[8] The porphyrin skeleton contains
two pyrrole rings and the fused, practically planar tripenta-
cyclic ring. The localization of double bonds within the N-
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Chem. Eur. J. 2009, 15, 10924 – 10929

Formation of N-Fused Telluraporphyrin
FULL PAPER
hedron of phosphorus resem-
bles a trigonal bipyramid. The
macrocylic ligand coordinates
in the facial mode because the
two pyrrolic nitrogen (N23,
N24) and one carbon (C22)
donors lie at the vertices of the
single trigonal face. The equa-
torial plane is formed by C22,
N24, and O1 atoms. The apical
position are occupied by O2
and N23 donors and the O2-P-
N23 angle is somewhat bent
À
(1678) and the P N23 bond
elongated as a consequence of
strain imposed by O2 bound to
the skeleton of restricted plas-
ticity. In fact, the aryl ring
bound to the sp3 C20 carbon,
the phosphorus, and two coor-
dinated oxygen atoms are lo-
cated on the same crowded
side of the CN2 macrocyclic
Figure 3. Molecular structures of 4-PO (left) and 6(O)-PO (right). Thermal ellipsoids are drawn at the 50%
À
À
À
probability level. Selected bond lengths [ꢁ] for 4-PO: P C22 1.754(6), P N23 1.689(5), P N24 1.681(5); and
À
À
À
À
À
for 6(O)-PO: P C22 1.816(5), P N23 1.989(4), P N24 1.743(4), C22 O2 1.430(6), P O2 1.709(3).
plane. The other side is bowl-shaped and forms a ball-and-
socket structure with C60, making contact with the shortest
Hporph···Cfuller distance being 2.73 ꢁ. The fullerene is ordered
and each C60 cage is surrounded by two identical enantio-
mers of 6(O)-PO that sit on opposite sides of the fullerene.
The racemic pairs of 6(O)-PO are aligned in close face-to-
face proximity.
Conclusions
In conclusion, an insertion of phosphorus into 21-tellurapor-
phyrin triggers a profound rearrangement of the macrocyclic
structure and gives a series of compounds that contain new
types of contracted carbaporphyrinoids imprinted into an N-
fused porphyrin frame. These molecules introduce unique
structural patterns as distinguished by the location of two ni-
trogen atoms and one carbon atom at corners of CNN coor-
dination triangle. Importantly, their formation extends the
N-fusion concept, which until recently was applicable to N-
confused[2;3] and expanded (hetero)porphyrins,[23–30] on 21-
heteroporphyrins. In addition, a new structural element has
been introduced that can be applied for supramolecular as-
semblies that place molecular surfaces around the curved
exteriors of fullerenes.
Figure 4. Packing in 2·(6(O)-PO)·C60·3C6H6. a) The view down the crys-
tallographic a axis shows a ribbon of (6(O)-PO) and C60 molecules in
2·(6(O)-PO)·C60·3C6H6. b) The view down the c axis (disordered solvent
(benzene) molecules that fill the clearly visible channels have been omit-
ted for clarity). A color version of this figure is available in the Support-
ing Information (Figure S6).
fused framework indicates the structure depicted at
Scheme 2 is the major resonance contributor.
Experimental Section
The 6(O)-PO molecule is strongly distorted from planari-
ty, however, the condensed tripentacyclic ring preserves the
approximately planar shape although the deviation is a bit
bigger than in the structure of 4-PO (mean deviation 0.08 ꢁ
compared with 0.065 ꢁ for 4-PO). The coordination poly-
NMR spectroscopy: NMR spectra were recorded by using high-field
spectrometers (1H frequency 500.13 or 600.15 MHz), equipped with a
broadband inverse gradient probehead. Spectra were referenced to the
residual solvent signals ([D]chloroform, d1H =7.26, d13C =77.16 ppm) or
H3PO4 as an external 31P reference. Two-dimensional NMR spectra were
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L. Latos-Graz˙ynski et al.
recorded with 2048 to 4096 data points in the t2 domain and up to 1024
points in the t1 domain, with a 1 s recovery delay.
(d, 2J
ACTHUNGETRN(NUG C,P)=5.7 Hz, C20), 55.7 (15-OCH3), 55.4 ppm (20-OCH3);
31P NMR (202.4 MHz, CDCl3, 298 K): d=À71.38 ppm; UV/Vis (CH2Cl2):
l (loge)=402 (4.68), 455 (4.20), 558 (4.08), 760 nm (3.92); HRMS (ESI):
m/z calcd for C46H31N3O4P130Te: 850.1109; found: 850.1064 [M+H]+.
Electrochemistry: Cyclic voltammograms were measured in nitrogen-de-
ACHTUNGTRENNUNGaerated dichloromethane solutions at RT (nBu4NClO4 as the supporting
electrolyte, Ag/AgCl as the reference electrode, and glassy carbon as the
working electrode, scan rate 50 mVsÀ1, ferrocene as the internal refer-
ence).
[5ÀP(OH)2X]+[X]À (X=(1R)-(À)-10-camphorsulfonate): An NMR
sample of 6(O)-PO (ꢀ5 mg) in CDCl3 was titrated with a saturated solu-
tion of (1R)-(À)-10-camphorsulfonic acid in CDCl3 and formation of
6(O)-POH+ was observed. Solid (1R)-(À)-10-camphorsulfonic acid was
then added to the sample to form a saturated solution and 6(O)-POH+
slowly transformed into [5ÀP(OH)2X]+ (two diastereoisomers). The
compound was not isolated (evaporation of solvents led to 6(O)-PO re-
generation). 1H NMR (600 MHz, CDCl3, 298 K): d=4.07 (s, 6H; OCH3),
7.30 (d, J=8.8 Hz, 2H; m-Ar-15), 7.39 (d, J=8.8 Hz, 2H; m- Ar-20), 7.47
(2 overlapping d, Jꢀ4.9 Hz, 1H; H-17), 7.59 (m, 1H; p-Ph-10), 7.73 (m,
2H; m-Ph-10), 7.87 (m, 4H; H-18, m,p-Ph-5), 8.02 (d, Jꢀ7.9 Hz, 2H; o-
Ar-15), 8.05 (2 overlapping d, Jꢀ4.8 Hz, 1H; H-3), 8.09 (2 overlapping d,
Jꢀ8.6 Hz, 2H; o-Ph-10), 8.23 (d, J=3.7 Hz, 1H; H-2), 8.31 (2 overlap-
ping d, Jꢀ8.1 Hz, 2H; o-Ar-20), 8.53 (brm, 2H; o-Ph-5), 8.84 (2ꢂd, J
ꢀ5.3 Hz, 1H; H-12), 8.98 ppm (2ꢂd, Jꢀ5.3 Hz, 1H; H-13); coordinated
(1R)-(À)-10-camphorsulfonate signals in exchange with the noncoordi-
nated anions: d=0.66 (s, H-8), 0.80 (s, H-9), 1.22 (m, H-5), 1.39 (m, H-6),
1.81 (m, H-3, H-5), 1.96 (m, H-4, H-6), 2.27 (d, H-3), 2.47 (d, H-10a),
2.86 ppm (d, H-10b); 13C NMR (150.9 MHz, CDCl3, 298 K): d=219.8 (C-
2cam), 164.2 (p-Ar-20), 161.6 (p-Ar-15), 158.7 (br), 150.3 (br), 148.7 (br.),
148.4 (a-pyrr) , 148.3, 148.2, 147.73 and 147.68 (ipso-Ar), 145.6 (d, 2J-
Synthesis of 4-PO: 5,20-Bis(4-methoxyphenyl)-10,15-diphenyl-21-tellura-
[10]
porphyrin
(3; 100 mg, 1.27ꢂ10À4 mol) was dissolved in freshly distilled
triethylamine (20 mL). Nitrogen was bubbled through the solution for
20 min and the solution was brought to a boil. Freshly distilled PCl3
(0.35 mL, 2.5ꢂ10À3 mol) was added dropwise and the mixture was heated
at reflux under nitrogen for 1 h (or more if TLC monitoring still showed
the presence of substrate). The solvent was evaporated and the solid resi-
due was dissolved in dichloromethane, filtered through basic Al2O3, and
separated by column chromatography on SiO2. The first fraction (eluent:
CH2Cl2) was substrate 3, the second orange fraction (eluent: 2% MeOH
in CH2Cl2) was recrystallized from CH2Cl2 and hexanes to give the de-
sired product 4-PO as a black solid (55% yield). 1H NMR (500 MHz,
C6D6, 305 K): d=3.14 (s, 3H; OMe(20)), 3.16 (s, 3H; OMe(15)), 3.82 (d,
3J
G
E
ACHTUNGTRENNUNG
1H; H-18), 4.29 (m, 2H; H-3, H-12), 4.43 (dd, 4J
E
ACHTUNGTRENNUNG
ꢀ6 Hz, 1H; H-13), 4.75 (dd, 4J
ACHTUNGTRENNUNG
6.44 (d, 3J(H,H)=8.8 Hz, 2H; m-Ar-20), 6.48 (d, 3J
ACHTUNGTRENNUNG ACHTUNGTRENNUNG
m-Ar-15), 6.59 (brs, 2H; o-Ar-15), 6.68 (d, 3J
6.76 (d, 3J
ACHTUNGTRENNUNG
ACHUTNGRENNUG AHCTUNGTRNE(NUGN C,P)=26 Hz) (a-pyrr, 2 diastereoisomers),
(C,P)=26 Hz) and 145.5 (d, 2J
ACHTUNGTRENNUNG
143.9, 143.8 (C-13), 140.5, 140.4, 140.1 (o-Ar-20), 138.0 (meso-Ar), 137.90
and 137.87 (a-pyrr), 136.79 and 136.75 (o-Ar-15), 136.54 and 136.47
(ipso-Ar), 135.00 and 134.93 (o-Ph-5), 133.0 (ipso Ph), 132.4 (C-18),
131.23 and 131.19 and 131.09 and 131.05 (2 doublets, C-2, 2 diastereoiso-
mers), 130.6 (o-Ph-10), 130.34 and 130.31 (m-Ph, 2 diastereoisomers),
129.93 (p-Ph-5), 129.89, 129.8 (C-17), 129.4 (Ar-5), 125.8 and 125.7 (C-3),
121.9 and 121.8 (C-12), 115.5 (m-Ar-20), 113.5 (m-Ar-15), 58.6 (C-1cam),
56.1 (OCH3), 55.9 (OCH3), 48.7 (C-7cam), 48.4 (C-10cam), 43.0 (C-3cam),
42.7 (C-4cam), 26.8 (C-5cam), 26.1 (C-6cam), 19.9 (C-9cam), 19.5 ppm (C-8cam);
31P NMR (202.4 MHz, CDCl3, 298 K): d=1.08; HRMS (ESI): m/z calcd
for C46H31N3O4P130Te: 850.1109; found: 850.1127 [MÀX]+ (M=[5-
AHCTUNGTRENNUNG
G
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
ACHTUNGTRENNUNG
N
ACHTUNGTRENNUNG
P(OH)2X]+); m/z calcd for [C46H33N3O5P130Te] +: 868.1214; found:
G
ACHTUNGTRENNUNG
+
ACHTUNGTRENNUNG
À
868.1235 [MÀ
C
55.28 (OCH3), 55.25 ppm (OCH3); 31P NMR (202.4 MHz, CDCl3, 298 K):
d=10.09 ppm; UV/Vis (CH2Cl2): l (loge)=346 (sh), 388 (4.54), 447 (sh),
463 nm (4.53); HRMS (ESI): m/z calcd for C46H30N3O3P130Te: 833.10815;
found: 833.1083 [M]+.
6(O)-PO: Complex 4-PO (30 mg, 3.6ꢂ10À5 mol) was dissolved in CH2Cl2
(20 mL) and AgBF4 (37 mg, 9.4ꢂ10À5 mol) was added. After stirring for
5 min, a few drops of water were added and the solvents were evaporated
on a rotary evaporator. The solid residue was dissolved in CH2Cl2 and
passed through a short Al2O3 column. The first fraction (eluent: CH2Cl2)
was the substrate, the second fraction (eluent: 5% MeOH in CH2Cl2)
was recrystallized from CH2Cl2 and hexanes to give the desired product
Acknowledgements
Financial support from the Ministry of Science and Higher Education
(grant no. PBZ-KBN-118/T09/2004) is gratefully acknowledged.
[1] M. O. Senge, Chem. Commun. 2006, 243–256.
[2] H. Furuta, T. Ishizuka, A. Osuka, T. Ogawa, J. Am. Chem. Soc.
1999, 121, 2945–2946.
[3] H. Furuta, T. Ishizuka, A. Osuka, T. Ogawa, J. Am. Chem. Soc.
2000, 122, 5748–5757.
1
6(O)-PO as a dark brown solid (85% yield). H NMR (600 MHz, CDCl3,
3
300 K): d=3.825 (s, 3H; OCH3(20)), 3.94 (s, 3H; OCH3(15)), 6.58 (d, J-
3
G
N
(d, 3J(H,H)=3.6 Hz, 1H; H-3), 7.13 (d, 3J
ACHTUNGTRENNUNG ACHTUNGTRENNUNG
[4] M. Toganoh, J. Konagawa, H. Furuta, Inorg. Chem. 2006, 45, 3852–
3854.
[5] T. Ishizuka, A. Osuka, H. Furuta, Angew. Chem. 2004, 116, 5187–
5191; Angew. Chem. Int. Ed. 2004, 43, 5077–5081.
[6] M. Toganoh, T. Ishizuka, H. Furuta, Chem. Commun. 2004, 2464–
2465.
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG
´
´
[7] A. Młodzianowska, L. Latos-Graz˙ynski, L. Szterenberg, M. Ste˛pien,
ACHTUNGTRENNUNG
Inorg. Chem. 2007, 46, 6950–6957.
[8] A. Młodzianowska, L. Latos-Graz˙ynski, L. Szterenberg, Inorg.
3
G
ACHTUNGERTN(NUNG C,P)=5.4 Hz), 133.8 (o-
´
ACHTUNGTRENNUNG
Chem. 2008, 47, 6364–6374.
A
ACHTUNGTRENNUNG
´
[9] L. Latos-Graz˙ynski, E. Pacholska, P. J. Chmielewski, M. M. Olm-
stead, A. L. Balch, Angew. Chem. 1995, 107, 2467–2469; Angew.
Chem. Int. Ed. Engl. 1995, 34, 2252–2254.
AHCTUNGTRENNUNG
A
[10] M. Abe, M. R. Detty, O. O. Gerlits, D. K. Sukumaran, Organometal-
lics 2004, 23, 4513–4518.
AHCTUNGTRENNUNG
10928
www.chemeurj.org
ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2009, 15, 10924 – 10929

Formation of N-Fused Telluraporphyrin
FULL PAPER
´
[11] E. Pacholska, L. Latos-Graz˙ynski, Z. Ciunik, Angew. Chem. 2001,
[22] A. L. Balch, M. M. Olmstead, Coord. Chem. Rev. 1999, 185–186,
601–617.
113, 4598–4601; Angew. Chem. Int. Ed. 2001, 40, 4466–4469.
[12] J. A. Pople, K. G. Untch, J. Am. Chem. Soc. 1966, 88, 4811–4815.
[23] J.-Y. Shin, H. Furuta, A. Osuka, Angew. Chem. 2001, 113, 639–641;
Angew. Chem. Int. Ed. 2001, 40, 619–621.
´
´
[13] M. Ste˛pien, L. Latos-Graz˙ynski, Chem. Eur. J. 2001, 7, 5113–5117.
´
´
[14] R. Mysliborski, L. Latos-Graz˙ynski, Eur. J. Org. Chem. 2005, 5039–
[24] C. H. Hung, J. P. Jong, M. Y. Ho, G. H. Lee, S. M. Peng, Chem. Eur.
J. 2002, 8, 4542–4548.
5048.
´
´
[15] R. Mysliborski, L. Latos-Graz˙ynski, L. Szterenberg, Eur. J. Org.
[25] S. Saito, A. Osuka, Chem. Eur. J. 2006, 12, 9095–9102.
[26] S. Shimizu, N. Aratani, A. Osuka, Chem. Eur. J. 2006, 12, 4909–
4918.
Chem. 2006, 3064–3068.
[16] M. Ste˛pien, L. Latos-Graz˙ynski, L. Szterenberg, J. Org. Chem. 2007,
´
´
72, 2259–2270.
[27] S. Mori, J. Y. Shin, S. Shimizu, F. Ishikawa, H. Furuta, A. Osuka,
Chem. Eur. J. 2005, 11, 2417–2425.
[28] Y. Inokuma, T. Matsunari, N. Ono, H. Uno, A. Osuka, Angew.
Chem. 2005, 117, 1890–1894; Angew. Chem. Int. Ed. 2005, 44, 1856–
1860.
[29] M. Suzuki, R. Taniguchi, A. Osuka, Chem. Commun. 2004, 2682–
2683.
[30] A. Srinivasan, T. Ishizuka, H. Furuta, Angew. Chem. 2004, 116, 894–
897; Angew. Chem. Int. Ed. 2004, 43, 876–879.
[17] T. Barbour, W. J. Belcher, P. J. Brothers, C. E. F. Rickaed, D. C.
Ware, Inorg. Chem. 1992, 31, 746–754.
[18] Crystal data for 4-PO and 6(O)-PO are given in the Supporting In-
formation. CCDC-719514 (4-PO) and -719515 (6(O)-PO) contain
the supplementary crystallographic data for this paper. These data
can be obtained free of charge from The Cambridge Crystallograph-
ic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
[19] S. Stevenson, C. J. Chancellor, H. M. Lee, M. M. Olmstead, A. L.
Balch, Inorg. Chem. 2008, 47, 1420–1427.
[20] P. D. W. Boyd, C. A. Reed, Acc. Chem. Res. 2005, 38, 235–242.
[21] A. Hosseini, M. C. Hodgson, F. S. Tham , C. A. Reed, P. D. W. Boyd,
Cryst. Growth Des. 2006, 6, 397–403.
Received: June 8, 2009
Published online: September 11, 2009
Chem. Eur. J. 2009, 15, 10924 – 10929
ꢀ 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
10929