Tetraphenylbenziporphyrin - A ligand for organometallic chemistry

Article abstract of DOI:10.1002/1521-3765(20011203)7:23<5113::AID-CHEM5113>3.0.CO;2-V

6,11,16,21-Tetraphenylbenziporphyrin (TPBPH)H, an analogue of tetraphenylporphyrin with one of the pyrrole groups replaced by a benzene ring, is formed in good yield in the condensation of the appropriate precursor with pyrrole and benzaldehyde. (TPBPH)H

Full text of DOI:10.1002/1521-3765(20011203)7:23<5113::AID-CHEM5113>3.0.CO;2-V

FULL PAPER
Tetraphenylbenziporphyrin–A Ligand for Organometallic Chemistry
Marcin St eŒ pie n¬ and Lechos¯aw Latos-Gra z« y n¬ ski*[a]
II
II
Abstract: 6,11,16,21-Tetraphenylbenzi-
porphyrin (TPBPH)H, an analogue of
tetraphenylporphyrin with one of the
pyrrole groups replaced by a benzene
ring, is formed in good yield in the
condensation of the appropriate precur-
sor with pyrrole and benzaldehyde.
um(ii), [(TPBP)Pd ] and [(TPBP)Pt ],
in which the metal ion is bound in the
macrocyclic cavity by three pyrrolic
nitrogen atoms and a carbon atom of
the benzene ring. In the reaction with
silver(i) acetate benziporphyrin does not
yield a stable complex but undergoes
selective acetoxylation at the internal
carbon atom. (TPBPH)H is reversibly
reduced to 6-benziphlorin and reacts
with a water or methanol molecule to
give 6-hydroxy- or 6-methoxy-6-benzi-
phlorin, respectively.
Keywords: porphyrinoids ¥ macro-
cyclic ligands ¥ NMR spectroscopy ¥
platinum ¥ palladium
(
TPBPH)H gives organometallic com-
plexes with palladium(ii) and platin-
Introduction
hydroxy substituent, suitably placed to form2-hydroxybenzi-
porphyrin, offers access to the aromatic oxybenziporphyrin
through an enol ± keto tautomerization.[
In light of these we have synthesized 6,11,16,21-tetraphe-
nylbenziporphyrin (1). Formally this macrocycle has been
±, 13]
Modifications of the porphyrin core involving the introduc-
tion of a CH unit in place of one of the nitrogen atoms have
led to the preparation of a series of monocarbaporphyrinoids
that may have interesting properties both in terms of their
aromatic character and their potential ability to bind metal
ions.[
1±±]
Such a replacement preserves three regular pyrrole
moieties, while the CNNN core becomes the denominator of
monocarbaporphyrinoid structure.[
5, 6]
These macrocycles
bear functional resemblance to certain polydentate ligands,
which, by virtue of a favorably oriented carbon donor,
afforded rare organometallic compounds of transition ele-
ments, often stabilizing untypical oxidation states or unusual
coordination geometries.[
7±1ꢀ]
The structure of carbaporphy-
rinoids suggests their prospective use as nontrivial ligands and
consequently their coordination properties have aroused
particular interest. Thus the inverted porphyrin (2-aza-21-
carba-5,1ꢀ,15,2ꢀ-tetraarylporphyrin) and its methylated de-
rivatives revealed a remarkable tendency to stabilize peculiar
organometallic compounds containing nickel(i), paramagnetic
constructed by replacement of one of the pyrrole rings of
5
,1ꢀ,15,2ꢀ-tetraphenylporphyrin (TPPH ) with a benzene
2
moiety. To indicate the chemical difference between the 22-
C and 2±-N protons we will use the symbol (TPBPH)H for 1.
6,11,16,21-Tetraphenylbenziporphyrin has a relationship to
nickel(ii) (including a high-spin species with two NiÀC bonds),
nickel(iii), copper(ii), palladium(ii), and silver(iii).[1, 11±16]
8
,9,13,1±,18,19-hexaalkylbenziporphyrin similar to that of
8
,19-Dimethyl-9,13,1±,18-tetraethylbenziporphyrin
was
[3, 13]
tetraarylporphyrins to octaalkylporphyrins since identical
substituents at b- and meso-positions are present in both pairs.
synthesized previously,
and it was demonstrated that a
[
a] Prof. L. Latos-Gra z« y n¬ ski, M. St eŒ pie n¬
Department of Chemistry, University of Wroc¯aw
± F. Joliot-Curie St., Wroc¯aw 5ꢀ 383 (Poland)
1
Results and Discussion
Fax : (‡71)32823±8
E-mail: llg@wchuwr.chem.uni.wroc.pl
Tetraphenylbenziporphyrin
Scheme 1) in a condensation of pyrrole, benzaldehyde, and
1,3-bis(phenylhydroxymethyl)benzene (2), which was ob-
1
has been synthesized
Supporting information (1D 13C NMR spectra for compounds 1, 1-NO
,
2
(
3
, 4, 7, and 8) for this article is available on the WWW under
http://www.wiley-vch.de/home/chemistry/ or from the author.
Chem. Eur. J. 2001, 7, No. 23
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5113

L. Latos-Gra z« y n¬ ski and M. St eŒ pie n¬
FULL PAPER
NH resonance (d ˆ 1ꢀ.3ꢀ) (Trace A, Figure 2). Scalar coupling
detected between 2±-NH and 13,1±-H pyrrole protons is
consistent with the prevalence of the symmetrical tautomer 1.
Treatment of (TPBPH)H with two equivalents of silver
acetate produced 21-acetoxy-6,11,16,21-tetraphenylbenzipor-
phyrin (3). This oxidative acetoxylation proceeds cleanly and
selectively under mild conditions according to reaction (1).
1
‡ 2Ag(OAc) À! 3 ‡ 2Ag ‡ AcOH
(1)
Scheme 1. Synthesis of 1.
tained in the reaction of phenylmagnesium bromide with
isophtalaldehyde. The procedure follows the methodology
previously utilized for the synthesis of heteroporphyrins.[5]
After chromatographic workup the compound was obtained
in 15% yield. The electronic spectrumof 1 and its dication
1-H2]2 is shown in Figure 1.
‡
[
The structure of 3 was determined in an X-ray diffraction
study (Figure 3).[ The six-membered ring is sharply tipped
1±]
out of the N(23)-N(2±)-N(25) plane, making room for the
6
,21-phenyl groups, which are almost coplanar with the
macrocycyle. The p bonds within the tripyrrane subunit are
largely localized in the manner indicated by valence structure
3
. On the other hand, the bond lengths in the six-membered
ring are almost equal and benzene-like. The C(21)ÀC(1) and
C(5)ÀC(6) distances (1.±76(2) ä and 1.±7±(2) ä) approach
2
2
the single-bond limit for C(sp )ÀC(sp ). These structural
features confirmthat the benzene ring incorporated in the
framework of 3 completely blocks macrocyclic delocalization
while retaining unperturbed [6]annulene aromaticity. In the
crystal acetoxybenziporphyrin acts as an acceptor of one
molecule of water, which is coordinated through two hydro-
gen bonds to N(23) and N(25). The water molecule is situated
above the macrocyclic plane on the opposite side to the
acetoxy substituent.
‡
Figure 1. The electronic spectra of 1 (––, green), [1-H
yellow), 7 ( ¥¥ - -, orange-brown), and 8 (- - - -, green) in CH
2
]2 ( ¥¥¥¥, brownish
2
2
Cl (298 K).
For topological reasons the molecule 1 cannot retain the
macrocyclic aromaticity typical of porphyrins. The H NMR
spectrumof 1 presents the resonances at positions consistent
with a nonaromatic structure. Thus the aromatic ring current
is absent, as clearly illustrated by the downfield shift of the 2±-
1
1
The H NMR spectrumof 3 (see Experimental Section)
closely resembles that of 1. Presumably the remarkable
differentiation of the 8,19-H and 9,18-H resonances seen for
1
and 3 is related to the location of 8,19-H in the deshielding
Abstract in Polish:
6,11,16,21-Tetrafenylobenziporfiryna
instead of shielding zone of the neighboring meso phenyl
groups.
Benziporphyrin 1 reacts with sodiumborohydride to
produce 6,11,16,21-tetraphenyl-6-benziphlorin (4, one of the
TPBP, analog tetrafenyloporfiryny, wkto¬rym jeden z pier s¬ cie-
ni pirolowych zast aŒ piony jest benzenowym, powstaje z dobr aŒ
wydajno s ci aΠwkondensacji odpo iwe dniego prekursora z
pirolem i benzaldehydem. TPBP tworzy metaloorganiczne
II
po¯ aÀ czenia
z
palladem(ii)
i
platyn aΠ(ii), (TPBP)Pd
i
II
(
TPBP)Pt , wkto ¬rych jon metalu zwi aŒ zany jest we wn eŒ ce
makrocyklicznej poprzez trzy pirolowe atomy azotu i atom
w eΠgla pier s cienia benzenowego. W reakcji z octanem srebra(i)
benziporfiryna nie tworzy trwa¯ego kompleksu, natomiast
ulega selektywnej acetoksylacji na wewn eΠtrznym atomie w eΠgla.
TPBP ulega odwracalnej redukcji do 6-benzifloryny a tak z« e
przy¯ aŒ ,cza cz aŒ steczk eŒ wody b aŒ d z¬ metanolu daj aŒ c odpowiednio
6-hydroksy- i 6-metoksy-6-benzifloryn eΠ.
5114
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Chem. Eur. J. 2001, 7, No. 23

Tetraphenylbenziporphyrin
5113±5117
three possible tautomers),
which structurally resembles
porphyrin-derived
phlorins
and is analogous to an alkyl-
substituted benziphlorin re-
ported previously.[ The reac-
tion is selective as the satura-
tion at the 6-position was solely
3]
1
observed. The H NMR spec-
trumreflects sy mme try lower-
ing of 4 in comparison to 1. The
three pyrrolic AB patterns, two
inner NH signals, and 6-H res-
onance can easily be identified.
The C(6) carbon atomof
produces a resonance at d ˆ
1.5, which is consistent with a
4
5
tetrahedral geometry. The reac-
tion with NaBH can be consid-
±
ered a special case of the typical
reactivity of 1 with respect to
nucleophiles. For example, the
reaction of 1 with water or
methanol yields 6-hydroxy-
6
,11,16,21-tetraphenyl-6-benzi-
phlorin (5) and 6-methoxy-
,11,16,21-tetraphenyl-6-benzi-
6
phlorin (6), respectively. This
reactivity resembles the nucle-
ophilic meso-addition of hy-
dride
[(TPP)Au Cl]
phenylporphyrin)
or
hydroxide
(TPP ˆ tetra-
to yield
to
III
Figure 2. 1H NMR spectra (5ꢀꢀ MHz, CDCl
) of A) 1, B) 7, C) 8. D) The 195Pt-edited spectrumof 8, which
3
exposes the patterns of Pt satellites. Resonance assignments (obtained from COSYand NOESY maps) follow the
numbering scheme given for 1 in Scheme 1.
phlorin or hydroxyphlorin com-
plexes.[ Addition of gaseous
15]
HCl to 5 or 6 resulted in water or alcohol elimination,
respectively, and quantitative recovery of 1. The easy acces-
sibility of phlorins 4 ± 6 is related to the loss of aromaticity
suffered by 1.
Insertion of palladium(ii) or platinum(ii) into 1 yields
II
II
[
(TPBP)Pd ] 7 (orange-brown) and [(TPBP)Pt ] 8 (green),
whose electronic spectra differ essentially fromthat of
1
(
Figure 1). The most notable feature of 7 and 8 is the
Figure 3. Crystal structure of 3 (thermal ellipsoids at 5ꢀ% probability
level). O atoms are shown in black, N atoms in gray, and selected H atoms
are represented by small circles.
coordination through the unprotonated C(22) carbon atomof
the benzene ring as inferred fromthe disappearance of the 22-
Chem. Eur. J. 2001, 7, No. 23
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L. Latos-Gra z« y n¬ ski and M. St eŒ pie n¬
FULL PAPER
1
H resonance in the H NMR spectra (Figure 2, Traces B and
residue was recrystallized fromCH
2
Cl
2
/n-hexane to afford several batches
1
2
of the product (white solid). Yield (first batch): d ˆ 1.21 g (56%). H NMR
C). A chemical shift of d ˆ 1±5.5 (d ˆ 139.3), typical for sp
(
298 K, mixture of stereoisomers): d ˆ 7.±7, 7.±5 (2t, J ꢀ 2 Hz; 2-H); 7.21 ±
.36 (m, 13H, remaining aryl protons); 5.81, 2.18 (AB: J ꢀ 3 Hz; CHOH,
CHOH).
: (TPBP)H (58 mg) and Ag(OAc) (3ꢀ mg, 2.16 equiv) were refluxed for
hybridization, has been detected for the coordinated C(22)
7
atomin the 13C NMR spectra of 7 (8). In addition the H- N
HMBC spectrumof 8 gave the assignments of three pyrrole
nitrogen atoms at d ˆ À226 (23,25-N) and d ˆ À216 (2±-N),
1
15
3
15 min in a mixture of CHCl and MeCN (15 ‡ 15 mL). The solution was
3
II
then evaporated to dryness and the residue chromatographed (grade II
that is upfield with respect to the signal for [(TPP)Pt ] (d ˆ
1
95
basic alumina, CH
2
1
Cl
2
) to yield 3 (±2 mg; 66% after a recrystallization from
À252 vs. MeNO ). The Pt resonance of 8 (d ˆ 56ꢀ) is shifted
2
2 2
CH Cl
/MeOH). H NMR (298 K): d ˆ 9.51 (s; 2±-NH); ꢁ7.55 (m, ±H;
II
[16]
upfield relative to that of [(TPP)Pt ] (d ˆ 1235 ) reflecting
the presence of a different donor in the coordination core.
Owing to the coordination of a metal ion the pyrrole and
benzene resonances of 7 and 8 are downfield shifted with
respect to their positions for the free base 1. In 7 or 8 the metal
ion is located in the CNNN plane, which forces a coplanar
position of the benzene ring. The effectively orthogonal
position of the meso-phenyl groups removes the source of
shift differentiation for 8,19-H and 9,18-H resonances seen for
6
,21-o-Ph); ꢁ7.±8 (m, ±H; 11,16-o-Ph); 7.39 ± 7.±5 (m, 12H; 6,21,11,16-m,p-
3
3
Ph); 7.16, 7.ꢀ7 (AB
2
: J ˆ 7.6 Hz; 3-H, 2,±-H); 7.29, 6.52 (AB: J ˆ ±.8 Hz;
13
8,19-H, 9,18-H); 6.83 (s; 13,1±-H), 1.31 (s; CH
3
); C NMR (partial data,
98 K): d ˆ 169.9 (OÀCˆO); 17ꢀ.2, 156.6 (1ꢀ,17;7,2ꢀ-C); 1±ꢀ.5 (1,6-C);
3±.8 (8,19-C); 133.8 (1,5-C); 131.2 (9,18-C); 131.2 (2,±-C); 13ꢀ.2 (13,1±-C);
26.5 (3-C); 118.1 (22-C); 2ꢀ.3 (CH ); UV/Vis (CH Cl
2
1
1
3
2
2
): lmax (log e) ˆ 31ꢀ
(
±.±8), ±ꢀ9 (±.8±), 7ꢀ2 nm(±.28); HRMS (ESI): m/z: 68±.2658 (68±.26±6 for
‡
C H N O
ꢀ
±
8
33
3
2
‡
H ); elemental analysis (%) calcd for C H N O ¥
±6 33
3
2
.±CH
2
Cl
2
: C 8ꢀ.9ꢀ, H ±.75, N 5.85; found: C 8ꢀ.8ꢀ, H ±.96, N 5.76.
4: (TPBP)H (2.5 mg) was dissolved in a small volume of CHCl3 and
reduced with a solution of NaBH in EtOH. The reaction was monitored
spectrophotometrically. The solvents were removed at room temperature
under reduced pressure. The residue was extracted with CH Cl , filtered,
1
1
1
and 3. The H NMR spectrumof 8 displays four-bond H ±
Pt scalar couplings to pyrrole b-protons and, consistent with
the formation of a Pt-C(22) bond, to 2,±-benzene protons
±
1
95
2
2
and evaporated to dryness. Alternatively, 4 was obtained directly in the
condensation reaction, if p-chloranil (52ꢀ mg, 2.1 equiv) was used in place
(
Figure 2, Trace D).
1
In conclusion, the nonaromatic tetraphenylbenziporphyrin
may serve as a valuable ligand for organometallic inves-
tigations of benzene reactivity by efficiently protecting the
metal ± carbon s bond through the encapsulation of the metal
center in the CNNN coordination core.
of DDQ. H NMR (333 K): d ˆ 9.79, 7.87 (2b, 2H; NH); 7.89, 7.22, 6.92, 6.22
3
3
±
±
(
3
5
(
ABCD:
JA,B ˆ 7.8 Hz,
J
B,C ˆ 7.9 Hz,
JA,D ˆ 1.1 Hz,
J
C,D ˆ 1.2 Hz; ±-H,
1
3
-H, 2-H, 22-H); 7.ꢀ ± 7.6 (m, 1ꢀH; 6,11,16,21-Ph), 6.92, 6.67 (AB: J ˆ
3
.6 Hz; 19H, 18-H); 6.78, 6.±ꢀ (AB: J ˆ ±.8 Hz; 13-H, 1±-H); 6.63, 6.±8
3
13
AB: J ˆ 3.9 Hz; 8-H, 9-H); 5.69 (s; 6-H); C NMR (partial data, 333 K):
d ˆ 126.5 (±-C), 128.3 (2-C), 129.± (19-C), 128.1 (3-C), 135.ꢀ (13-C), 128.8
(
18-C), 111.ꢀ (8-C), 12ꢀ.8 (9-C), 128.1 (1±-C), 51.5 (6-C); UV/Vis (CH Cl ):
2
2
l
max (log e) ˆ 3ꢀꢀ (±.±1), 399 (±.7±), 666 nm(±.5±); electronic spectra of the
remaining phlorins are virtually indistinguishable; HRMS (ESI): m/z:
Experimental Section
‡
6
28.2738 (628.27±7 for C±6
H
33
N
3
‡ H ).
5
: (TPBP)H (2.5 mg) was added to THF (1ꢀ mL) containing water (1%)
1
(
: 1,3-Bis(phenylhydroxymethyl)benzene (2; 29ꢀ mg, 1 mmol), pyrrole
2ꢀ8 mL, 3 mmol), and benzaldehyde (2ꢀ± mL, 2 mmol) were added to dry
CH Cl (9ꢀꢀ mL) under nitrogen. Et O ¥ BF (1ꢀꢀ mL) was then added and
and a trace of HCl. The mixture was stirred until the starting material had
dissolved. The resultant blue solution was neutralized and dried with
2
2
2
3
anhydrous K
2
CO
3
and evaporated to dryness under reduced pressure.
the reaction mixture was protected from light and stirred for 2 h. 2,3-
Dichloro-5,6-dicyano-1,±-benzoquinone (DDQ; 75ꢀ mg, 3 mmol) was sub-
sequently added and the mixture evaporated under reduced pressure. The
residue was subjected to chromatography (grade II basic alumina, CH
The desired product eluted as a green band following a trace of H
Recrystallization fromCH Cl /hexane yielded deep blue crystals. The
1
H NMR (298 K): d ˆ 9.±2, 7.79 (2b, 2H; NH); 8.26 (d, ±-H); 7.3 ± 7.6 (m,
2
ꢀH; 6,11,16,21-Ph); 7.23 (t; 3-H); 7.ꢀꢀ, 6.75; 6.87, 6.5ꢀ; 6.81, 6.±5 (3AB:
8
,9-H; 13,1±-H; 18,19-H); 6.9± (d; 2-H); 6.16 (b; 22-H), 2.53 (b; OH);
2
Cl
2
).
‡
HRMS (ESI): m/z: 6±±.2685 (6±±.2696 for C±6
H
33
N
3
O ‡ H ).
2
TPP.
2
2
6: (TPBP)H (1ꢀ mg) was dissolved in CHCl (5 mL) and transformed into
the dication with gaseous HCl. MeOH (3ꢀ mL) was then added and the
3
filtrates contained sizable amounts of hydroxybenziphlorin 5, which was
dehydrated to give a second batch of the product. Total yield 93 mg (15%).
mixture cooled in the freezer (À2ꢀ8C). The cold mixture was neutralized
1
H NMR (298 K): d ˆ 1ꢀ.29 (s; 2±-NH); 7.37 ± 7.±6 (m; 6,11,16,21-Ph); 7.33,
2 3
with anhydrous K CO (ca. 5ꢀ mg), filtered, and the filtrate evaporated to
±
3
7
(
.29, 6.99 (ABC
2
: JA,C ˆ 1.7 Hz, JB,C ˆ 7.8 Hz; 22-H, 3-H, 2,±-H); 7.19, 6.52
dryness under reduced pressure. The deep blue product was too unstable to
be chromatographed but the conversion was close to quantitative. H NMR
AB: 3J ˆ ±.8 Hz; 8,19-H, 9,18-H), 6.7± (s; 13,1±-H); C NMR (partial
13
1
data, 298 K): d ˆ 172.ꢀ, 156.6 (7,2ꢀ,1ꢀ,17-C); 1±7.7 (12,15-C); 1±±.5 (6,21-
(
CD
3
OD, 273 K, monocation): d ˆ 8.13 (d; ±-H); 7.±1 ± 7.91 (m, 2ꢀH;
C); 138.1 (1,5-C); 136.6 (8,19-C); 133.± (2,±-C); 13ꢀ.5 (9,18-C); 129.8
6
,11,16,21-Ph); 7.±ꢀ, 6.82, 7.26, 6.72, 6.99, 6.67 (3AB: 8,9,13,1±,18,19-H);
(
13,1±-C); 128.8 (3-C); 1ꢀ9.± (22-C); UV/Vis (CH
2
Cl
2
): lmax (log e) ˆ 319
7.3± (3-H), 7.ꢀꢀ (2-H); NH signals and the CH peak cannot be observed
due to deuteration. In other solvents the spectrumis dyna mi cally
broadened.
3
(
±.53), ±11 (±.89), 723 nm(±.ꢀ9); HRMS (ESI): m/z: 626.26±6 (626.2591 for
‡
C
±
±6
H
31
N
3
‡ H ); elemental analysis (%) calcd for C±6
31 3
H N : C 88.32, H
.96, N 6.72; found (sample dried at 15ꢀ8C for 2± h): C 88.ꢀ8, H ±.82, N 6.98.
,21-Diphenyl-11,16-bis(4-nitrophenyl)benziporphyrin (1-NO ): Com-
was obtained analogously to 1, by using ±-nitrobenzaldehyde
7
2
: (TPBP)H (15 mg) and PdCl (±.5 mg, 1.2 equiv) were added to dry
6
2
MeCN (2ꢀ mL) and the mixture was refluxed for 2 h. The solution was
allowed to cool down, the violet precipitate was filtered off, washed with
pound 1-NO
2
1
(
3ꢀ2 mg, 2 mmol) instead of benzaldehyde. Yield 126 mg (17%). H NMR
1
MeCN, and dried in air. Yield 8.5 mg (±9%). H NMR (298 K): d ˆ 7.75,
3
(
298 K): d ˆ 1ꢀ.3ꢀ (s; 2±-NH); 8.31, 7.6± (AA'BB': JA,B ˆ 9.7 Hz; 11,16-m-
3
7.17 (A
2
B:
J
A,B ˆ 7.7 Hz; 2,±-H, 3-H); 7.5± ± 7.59 (m; 6,11,16,21-o-Ph);
3
Ph, 11,16-o-Ph); 7.±ꢀ ± 7.5ꢀ (m; 6,21-Ph); 7.33, 7.31, 7.ꢀ1 (ABC
2
:
J
A,C
ˆ
3
7.±2 ± 7.5ꢀ (m; 6,11,16,21-m,p-Ph); 7.16 (s; 13,1±-H); 7.ꢀ6, 6.96 (AB: J ˆ
5
±
3
7
.7 Hz, JB,C ˆ 1.7 Hz; 3-H, 22-H, 2,±-H); 7.27, 6.±6 (AB: J ˆ ±.8 Hz; 8,19-
1
3
.2 Hz; 8,19-H, 9,18-H); C NMR (partial data, 298 K): d ˆ 157.6, 1±5.5
H, 9,18-H), 6.76 (s; 13,1±-H); HRMS (ESI): m/z: 716.23ꢀ2 (716.2292 for
(
1
8,19;9,18-C); 152.6 (12,15-C); 1±5.5 (22-C); 1±±.1 (6,21-C); 1±2.3 (2,±-C);
35.3 (8,19-C); 13±.2 (1,5-C); 133.6 (13,1±-C); 126.± (9,18-C); 12±.8 (3-C);
‡
C
±6
H
29
N
5
O
±
‡ H ).
2
: Isophthalaldehyde (1 g, 7.±6 mmol) was dissolved in dry degassed THF
UV/Vis (CH
2
Cl
2
): lmax (log e) ˆ 3±9 (±.3±), ±3± (±.7±), 5±6 (3.61), 787 (3.68),
(
25ꢀ mL). PhMgBr (3 mL of a 3m solution in Et O, 9 mmol) was added,
2
‡
8
75 nm(3.65); HRMS (ESI): m/z: 73ꢀ.1589 (73ꢀ.1±69 for C±6
H
29
N
3
Pd ).
which caused the reaction mixture to turn blue-violet. After the mixture
had been stirred for 1 h, the solution was heated and refluxed for an
additional ꢀ.5 h. The reaction mixture was hydrolyzed with aqueous
Palladium 6,21-diphenyl-11,16-bis(4-nitrophenyl)benziporphyrin (7-NO
2
):
Compound 7-NO
2
was obtained analogously to 7 by using 1-NO
2
as the
1
3
ammonium chloride and extracted with CH
2
Cl
2
. The extracts were washed
ligand. H NMR (298 K): d ˆ 8.38, 7.78 (AA'BB': JA,B ˆ 8.8 Hz; 11,16-m-
3
twice with water and the solvent was removed under reduced pressure. The
Ph, 11,16-o-Ph); 7.77, 7.19 (A
2
B: JA,B ˆ 7.8 Hz; 2,±-H, 3-H,); 7.±5 ± 7.55 (m,
5116
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Tetraphenylbenziporphyrin
5113±5117
3
1
H).
8
ꢀH; 6,21-Ph); 7.15, 6.88 (AB: J ˆ 5.2 Hz; 8,19-H, 9,18-H), 7.12 (s; 13,1±-
[7] a) G. van Koten, Pure Appl. Chem. 1989, 61, 1681; b) M. H. P.
Rietveld, D. M. Grove, G. Van Koten, New. J. Chem. 1997, 21, 751;
c) R. A. Gossage, L. A. van de Kuil, G. van Koten, Acc. Chem. Res.
1998, 31, ±23.
2
: (TPBP)H (5ꢀ mg) and PtCl (22 mg, 1 equiv) were refluxed in
benzonitrile (2ꢀ mL) for ± h under nitrogen. The solvent was removed in
a streamof nitrogen at about 1ꢀꢀ 8C. The solid residue was chromato-
[8] a) M. Gozin, A. Weisman, Y. Ben-David, D. Milstein, Nature 1993,
364, 699; b) N. Ashkenazi, A. Vigalok, S. Parthiban, Y. Ben-David,
L. J. W. Shimon, J. M. L. Martin, D. Milstein, J. Am. Chem. Soc. 2000,
122, 8797.
[9] G. R. Newkome, W. E. Puckett, V. K. Gupta, G. E. Kiefer, Chem. Rev.
1986, 86, ±51.
graphed (CH
as the first band. Yield after recrystallization (CH
2
Cl
2
, grade II basic alumina), the green product 8 was eluted
Cl /MeOH) 11.5 mg
2
2
1
3
(
2ꢀ%). H NMR (298 K): d ˆ 7.67, 7.16 (A
2
B: JA,B ˆ 7.6 Hz; 2,±-H, 3-H);
3
7
8
1
.±3 ± 7.6ꢀ (m; 6,11,16,21-Ph); 7.27 (s; 13,1±-H); 7.ꢀ5, 7.ꢀ2 (AB: J ˆ 5.3 Hz;
,19-H, 9,18-H); 13C NMR (partial data, 298 K): d ˆ 157.7, 1±2.9 (7,2ꢀ;
ꢀ,17-C); 151.5 (12,15-C ); 1±7.5 (6,21-C); 1±±.3 (2,±-C); 139.3 (22-C); 136.6
[1ꢀ] G. R. Giesbrecht, G. S. Hanan, J. E. Kickham, S. J. Loeb, Inorg. Chem.
(
(
(
8,19-C); 133.7 (13,1±-C); 131.5 (1,5-C); 127.3 (9,18-C); 123.ꢀ (3-C); UV/Vis
1992, 31, 3286.
CH
2
Cl
2
): lmax (log e) ˆ 3±9 (±.52), ±32 (±.71), 615 (3.88), 726 (3.±5), 782 nm
[11] a) P. J. Chmielewski, L. Latos-Gra z« y n¬ ski, J. Chem. Soc. Perkin Trans. 2
1995, 5ꢀ3; b) P. J. Chmielewski, L. Latos-Gra z« y n¬ ski, T. G¯owiak, J.
Am. Chem. Soc. 1996, 118, 569ꢀ; c) P. J. Chmielewski, L. Latos-
Gra z« y n¬ ski, Inorg. Chem. 1997, 36, 8±ꢀ; d) P. J. Chmielewski, L. Latos-
Gra z« y n¬ ski, Inorg. Chem. 2000, 39, 5639; e) P. J. Chmielewski, L. Latos-
Gra z« y n¬ ski, I. Schmidt, Inorg. Chem. 2000, 39, 5±75.
[12] a) H. Furuta, T. Ogawa, Y. Uwatoko, K. Araki, Inorg. Chem. 1999, 38,
2676; b) H. Furuta, N. Kubo, H. Maeda, T. Ishizuka, A. Osuka, H.
Nanami, T. Ogawa, Inorg. Chem. 2000, 39, 5±2±; c) T. Ogawa, H.
Furuta, M. Takahashi, A. Morino, H. Uno, J. Organomet. Chem. 2000,
‡
3.53); HRMS (ESI): m/z: 818.2ꢀ16 (818.2ꢀꢀ± for C±6
H
29
N
3
Pt ).
Instrumentation: NMR spectra were recorded on a 5ꢀꢀ MHz Bruker
Avance spectrometer equipped with a broadband inverse gradient probe-
head. Proton data are referenced to the residual CHCl
3
signal (d ˆ 7.2±).
1
Data for heteronuclei were obtained from H-detected correlation spectra.
1
3
13
15
C shifts are referenced to CDCl
3
(d ˆ 77.ꢀ), N to neat external MeNO
2
1
95
[16]
(
d ˆ ꢀ), and Pt to external [Pt(TPP)] in CDCl (d ˆ 1235, X-scale). The
3
1
195
H ± Pt 1D HMQC experiment used an evolution time of 5ꢀ ms and was
processed in the magnitude mode.
6
11, 36.
[
[
13] T. D. Lash, S. T. Chaney, D. T. Richter, J. Org. Chem. 1998, 63, 9ꢀ76.
1±] Crystal data for 3 (1ꢀꢀ K): Crystals obtained by slow evaporation of a
Acknowledgements
CHCl
3
solution,
C
±8
H
33
N
3
O
2
¥ CHCl
≈
3
¥ H
2
O, rhombic plate, ꢀ.25 Â
ꢀ
1
.25  ꢀ.1ꢀ mm, triclinic P1, a ˆ 9.977(1), b ˆ 13.268(1), c ˆ
Financial support fromthe State Committee for Scientific Research KBN
of Poland (Grant 3 Tꢀ9A 155 15) and the Foundation for Polish Science is
kindly acknowledged. We thank Prof. Tadeusz Lis for valuable discussions.
7.18±(1) ä, a ˆ 67.97(1), b ˆ 8ꢀ.89(1), g ˆ 76.53(1)8, Vˆ 2ꢀ±±.3(3)
3
ä , Z ˆ 2, l ˆ ꢀ.71ꢀ73 ä. Structure solved with SHELXS-97 and
2
refined against jF j using SHELXL-97 (G. M. Sheldrick, University
of Gˆttingen, Germany, 1997): R1 ˆ ꢀ.ꢀ6±3, wR2 ˆ ꢀ.127ꢀ, S ˆ 1.ꢀ8±
for 1ꢀ9±9 reflections with I > 2s(I) and 625 parameters; max./min
À3
[
1] P. J. Chmielewski, L. Latos-Gra z« y n¬ ski, K. Rachlewicz, T. G¯owiak,
residual electron density ‡ꢀ.±2/ À ꢀ.±7 eä . Crystallographic data
Angew. Chem. 1994, 106, 8ꢀ5; Angew. Chem. Int. Ed. Engl. 1994, 33,
(excluding structure factors) have been deposited with the Cambridge
Crystallographic Data Centre as supplementary publication no.
CCDC-156372. Copies of the data can be obtained free of charge on
application to CCDC, 12 Union Road, Cambridge CB21EZ, UK (fax:
(‡±±)1223-336-ꢀ33; e-mail: deposit@ccdc.cam.ac.uk).
7
79.
[
[
2] H. Furuta, T. Asano, T. Ogawa, J. Am. Chem. Soc. 1994, 116, 767.
3] K. Berlin, E. Breitmaier, Angew. Chem. 1994, 106, 1356; Angew.
Chem. Int. Ed. Engl. 1994, 33, 12±6.
[
[
±] T. Lash, Angew. Chem. 1995, 107, 27ꢀ3; Angew. Chem. Int. Ed. Engl.
[15] a) H. Sugimoto, J. Chem. Soc. Dalton Trans. 1982, 1169; b) H. Segawa,
R. Azumi, T. Shimidzu, J. Am. Chem. Soc. 1992, 114, 756±.
[16] L. R. Milgrom, R. J. Zuurbier, J. M. Gascoyne, D. Thompsett, B. C.
Moore, Polyhedron 1992, 11, 1779.
1
995, 34, 2533.
5] L. Latos-Gra z« y n¬ ski, ™Core Modified Heteroanalogues of Porphyrins
and Metalloporphyrins∫ in The Porphyrin Handbook, Vol. 2 (Eds:
K. M. Kadish, K. M. Smith, R. Guilard), Academic Press, New York,
2
000, p. 361.
[
6] T. Lash, ™Syntheses of Novel Porphyrinoid Chromophores∫ in The
Porphyrin Handbook, Vol. 2 (Eds.: K. M. Kadish, K. M. Smith, R.
Guilard), Academic Press, New York, 2000, p. 125.
Received: June 19, 2ꢀꢀ1 [F3352]
Chem. Eur. J. 2001, 7, No. 23
¹ WILEY-VCH Verlag GmbH, D-69±51 Weinheim, 2ꢀꢀ1
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5117