Extrusion of boron(III) subporphyrin from meso-heptakis(pentafluorophenyl) [32]heptaphyrin upon cooperative CuII and BIII metalation

Article abstract of DOI:10.1002/anie.200701682

(Chemical Equation Presented) An uneven split: Cooperative Cu^II and B^III metalation of meso-heptakis(pentafluorophenyl)[32] heptaphyrin (1) triggers an extrusion reaction to produce B^III meso-tris(pentafluorophenyl)[14]subporphyrin (2) along with a Cu^II porphyrin (3-Cu). Subporphyrin 2 exhibits unique optical properties that reflect the rotational restriction of its electron-withdrawing substituents.

Full text of DOI:10.1002/anie.200701682

Angewandte
Chemie
DOI: 10.1002/anie.200701682
Porphyrinoid Interconversion
Extrusion of Boron(III) Subporphyrin from meso-
Heptakis(pentafluorophenyl)[32]heptaphyrin upon Cooperative CuII
and BIII Metalation**
Shohei Saito, Kil Suk Kim, Zin Seok Yoon, Dongho Kim,* and Atsuhiro Osuka*
In recent years, there has been a surge in the discovery of
chemical transformations that interconnect different porphyr-
inic macrocycles.[1] Recent representative examples include a
These results strongly suggest that some porphyrinic
macrocycles are not robust but susceptible to drastic skeletal
rearrangements under suitable conditions. Here we report the
extrusion reaction of boron(III) meso-tris(pentafluorophen-
transannular skeletal rearrangement of
a diketo octa-
phyrin(1.1.1.0.1.1.1.0) to a spirodicorrole upon metalation
with NiII ion,[2] a porphyrin-to-corrole ring contraction upon
metalation with [Re2(CO)10],[3] a spontaneous corrole-to-
porphyrin ring expansion,[4] a corrole-to-hemiporphycene
ring expansion in the reaction with carbon tetraiodide,[5] and
double pyrrolic rearrangement of meso-aryl-substituted hex-
aphyrin to doubly N-confused hexaphyrin upon treatment
with CuI ion.[6] Additionally, we reported the thermal splitting
reaction of a bis-copper(II) octaphyrin into two copper(II)
porphyrins, a novel topological process that proceeds quanti-
tatively with perfect material balance in a metathesis fashion
(Scheme 1).[7]
yl)subporphyrin
from
meso-heptakis(pentafluorophen-
yl)[32]heptaphyrin(1.1.1.1.1.1.1) (1) upon cooperative metal-
ation of CuII and BIII ions as a novel metathesis-type
transformation.
Until our first synthesis of tribenzosubporphines in
2006,[8,9] subporphyrin was a long-sought but elusive ring-
contracted porphyrin analogue despite its simple structure
and important position in porphyrin chemistry. This is in sharp
contrast to subphthalocyanines, which have been extensively
studied since the first report by Meller and Ossko in 1972.[10]
The difference can be ascribed largely to a particular synthetic
difficulty of subporphyrins. While subphthalocyanines can be
prepared in more than 50% yield in favorable cases, syntheses
of subporphyrin require harsh reaction conditions and tedious
separation. The synthesis of tribenzosubporphines was
accomplished at most in 1.4% yield, and meso-aryl-substi-
tuted subporphyrins were synthesized also in low yields
(< 6%).[11] Boron(III) meso-tris(pentafluorophenyl)sub-
porphyrin (2) is an important ring-contracted porphyrin to
complete the series of meso-pentafluorophenyl-substituted
porphyrinoids including expanded porphyrins,[12] but it has
been elusive, as the previous protocols of subporphyrin
synthesis were not applicable to this particular macrocycle.
Heptaphyrin 1 adopts a distorted figure-of-eight structure
consisting of a semiporphyrin-like tetrapyrrolic segment and a
tripyrrolic segment.[13] In both sites, the pyrrolic nitrogen
atoms all point inwards, a favorable orientation for metal
coordination. It occurred to us that the simultaneous metal-
ation of 1 with a divalent metal ion at the semiporphyrin-like
pocket and BIII ion at the tripyrrolic pocket might trigger a
splitting reaction into a metalloporphyrin and a boron(III)
subporphyrin in a similar manner to the splitting reaction of
bis-copper(II) octaphyrin into two copper(II) porphyrins
(Scheme 2).
Scheme 1. Splitting reaction of bis-copper(II) octaphyrin.
[*] K. S. Kim, Z. S. Yoon, Prof. Dr. D. Kim
Department of Chemistry
Yonsei University
Seoul 120-749 (Korea)
Fax: (+82)2-2123-2434
E-mail: dongho@yonsei.ac.kr
S. Saito, Prof. Dr. A. Osuka
Department of Chemistry
Graduate School of Science
Kyoto University
Sakyo-ku, Kyoto 606-8502 (Japan)
Fax: (+81)75-753-3970
E-mail: osuka@kuchem.kyoto-u.ac.jp
Thus, we examined the metalation of 1 at the semi-
porphyrin-like pocket by treating 1 with a solution of
Zn(OAc)2·2H2O in methanol at room temperature which
provided 1-Zn in quantitative yield. Complex 1-Zn shows the
parent ion peak at m/z 1767.0182 (calcd for C77H16F35N7Zn
[M]+: m/z 1767.0194) in its high-resolution electrospray
ionization (HR-ESI) mass spectrum, and it exhibits a simple
1H NMR spectrum that reveals its C2-symmetric structure in
solution (Supporting Information).
[**] This work was partlysupported bya Grants-in-Aid (A) for Scientific
Research from the Ministryof Education, Culture, Sports, Science,
and Technology, Japan (no. 19205006; A.O.), and the Star Faculty
Program of the Ministryof Education and Human Resources, Korea
(D.K.). S.S. acknowledges the Research Fellowships of the JSPS for
Young Scientists. D.K. acknowledges a fellowship from the BK 21
Program from the Ministryof Education and Human Resources
Development.
Supporting information for this article is available on the WWW
under http://www.angewandte.org or from the author.
Angew. Chem. Int. Ed. 2007, 46, 5591 –5593
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5591

Communications
be similar to that of 1-Zn, where the CuII ion is bound
to the tetrapyrrolic segment with overall molecular
symmetry close to C2 (Figure 2).[14b] The complex 1-Cu
was treated with a source of boron(III) such as BBr3 or
BCl3, and the presence of a product with blue-green
fluorescence in the reaction mixture was noted. This
product was separated in yields of 1–10% through a
silica gel column by monitoring its fluorescence. To our
delight, this product turned out to be subporphryin 2.
The preparation of 2 was reproducible, and after many
experiments an improved yield of 36% was obtained
Scheme 2. Extrusion reaction of 1-Zn and 1-Cu: a) BBr3 (100 equiv), EtN(iPr)2
(150 equiv), CH2Cl2, room temperature, 24 h, and then aqueous NaHCO3;
b) MeOH, reflux, 3 h.
under
optimized
reaction
conditions
(BBr3
The structure of 1-Zn was confirmed by single-crystal X-
ray diffraction analysis (Figure 1), which shows that the ZnII
ion is coordinated at the tetrapyrrolic segment in a distorted
Figure 2. X-raycrystal structure of 1-Cu: top view (upper) and side
view (lower, with pentafluorophenyl substituents omitted for clarity.
(100 equiv), EtN(iPr)2 (150equiv), CH 2Cl2; stirring at room
temperature for 24 h), along with CuII-porphyrin 3-Cu in 13%
yield. In the reaction, the CuII-BIII bis-metalated complex was
not detected. This extrusion reaction is initiated by the simple
treatment of 1-Cu with BBr3 in the presence of an appropriate
base without particular thermal activation.
Figure 1. X-raycrystal structure of 1-Zn: top view (upper) and side
view (lower, with pentafluorophenyl substituents omitted for clarity).
Subporphyrin 2 shows the parent ion peak at m/z 794.0480
(calcd for C34H9F15N3BONa [M + Na]+: m/z 794.0497) in its
HR-ESI mass spectrum. Single-crystal X-ray diffraction
analysis of 2 revealed a bowl-like triangular structure with a
bowl depth of 1.37 Š (Figure 3).[14c,15] The meso-pentafluoro-
phenyl substituents of 2 are tilted by 61–798 relative to the
square-planar fashion.[14a] Note that ZnII metalation of 1 led to
complete suppression of N-fusion reactions,[13] which are
rather facile in the free-base heptaphyrin 1. Next, we
attempted metalation of 1-Zn with BIII using BBr3 or BCl3
under various conditions, which, however, gave a complicated
mixture containing 1, a ZnII-BIII bis-metalated complex
(< 6%), and subporphyrin 2 (< 1%). Formation of ZnII-por-
phyrin 3-Zn was not detected. The ZnII-BIII bis-metalated
complex easily decomposed without forming 2 or 3-Zn upon
heating it at reflux in CH2Cl2.
Then, we changed the substrate to the copper(II) complex
1-Cu, which was prepared in quantitative yield by metalation
of 1 with Cu(OAc)2. Complex 1-Cu shows the parent ion peak
at m/z 1766.0218 (calcd for C77H16F35N7Cu [M]+: m/
z 1766.0199) in its HR-ESI mass spectrum. The valence
state of the Cu(II) ion was confirmed by magnetic suscept-
ibility analysis of 1-Cu (Supporting Information). The struc-
ture of 1-Cu was determined by X-ray diffraction analysis to
Figure 3. X-raycrystal structure of 2: top view (left) and side view
(right). Thermal ellipsoids are shown at the 50% probabilitylevel.
5592
www.angewandte.org
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2007, 46, 5591 –5593

Angewandte
Chemie
subporphyrin framework (compared with 38–568 for ortho-
free meso-aryl-substituted subporphyrins). Importantly,
19F NMR spectroscopy revealed an inhibited rotation of the
meso-pentafluorophenyl substituents of 2 even at 413 K in
solution (Supporting Information).
As the first example of a subporphyrin bearing rotation-
ally frozen electron-withdrawing meso substituents, 2 displays
optical properties that are different to those of other meso-
aryl-substituted subporphyrins. The absorption spectrum of 2
features an intense Soret-like band at 359 nm that is the most
blue-shifted among the meso-aryl subporphyrins reported to
date, and three Q-like bands at 422 (shoulder), 449, and
470nm. Its fluorescence spectrum exhibits distinct bands at
487 and 517 nm (Figure 4) with a quantum yield of 12%.[16]
Keywords: boron · copper · expanded porphyrins ·
porphyrinoids
.
´
[1] a) L. Latos-Graz˙ynski, Angew. Chem. 2004, 116, 5234; Angew.
Chem. Int. Ed. 2004, 43, 5124; b) M. O. Senge, N. N. Sergeeva,
Angew. Chem. 2006, 118, 7654; Angew. Chem. Int. Ed. 2006, 45,
7492.
[2] E. Vogel, M. Michels, L. Zanders, J. Lex, N. S. Tuzun, K. N.
Houk, Angew. Chem. 2003, 115, 2964; Angew. Chem. Int. Ed.
2003, 42, 2857.
[3] M. K. Tse, Z. Zhang, T. C. W. Mak, K. S. Chan, Chem. Commun.
1998, 1199.
[4] C. P. Gros, J.-M. Barbe, E. Esponosa, R. Guilard, Angew. Chem.
2006, 118, 5770; Angew. Chem. Int. Ed. 2006, 45, 5642.
[5] R. Paolesse, S. Nardis, M. Stefanlli, F. R. Fronczek, M. G. H.
Vicente, Angew. Chem. 2005, 117, 3107; Angew. Chem. Int. Ed.
2005, 44, 3047.
[6] M. Suzuki, M.-C. Yoon, D. Y. Kim, J. H. Kwon, H. Furuta, D.
Kim, A. Osuka, Chem. Eur. J. 2006, 12, 1754.
[7] Y. Tanaka, W. Hoshino, S. Shimizu, K. Youfu, N. Aratani, N.
Maruyama, S. Fujita, A. Osuka, J. Am. Chem. Soc. 2004, 126,
3046. Similar metathesis-type isomerization was reported for the
bis-PdII complex of octaphyrin(1.1.1.0.1.1.1.0) in Ref. [2].
[8] Y. Inokuma, J. H. Kwon, T. K. Ahn, M.-C. Yoo, D. Kim, A,
Osuka, Angew. Chem. 2006, 118, 975; Angew. Chem. Int. Ed.
2006, 45, 961.
´
´
[9] R. Mysliborski, L. Latos-Graz˙ynski, L. Szterenberg, T. lis,
Angew. Chem. 2006, 118, 3752; Angew. Chem. Int. Ed. 2006,
45, 3670.
Figure 4. UV/Vis absorption (c) and fluorescence (lexc =359 nm,
g) spectra of 2 in CH2Cl2.
[10] a) A. Meller, A. Ossko, Monatsh. Chem. 1972, 103, 159; b) C. G.
Claessens, D. Gonzµlez-Rodríguez, T. Torres, Chem. Rev. 2002,
102, 835.
[11] a) N. Kobayashi, Y. Takeuchi, A. Matsuda, Angew. Chem. 2007,
119, 772; Angew. Chem. Int. Ed. 2007, 46, 758; b) Y. Inokuma,
Z. S. Yoon, D. Kim, A. Osuka, J. Am. Chem. Soc. 2007, 129, 4747.
[12] J.-Y. Shin, H. Furuta, K. Yoza, S. Igarashi, A. Osuka, J. Am.
Chem. Soc. 2001, 123, 7190.
Thus, the Stokes shift of 2 is about 700 cmÀ1, which is the
smallest among the reported meso-aryl subporphyrins (1200–
2900 cmÀ1).[11] The fluorescence of 2 involves single-exponen-
tial decay with a lifetime of 2.34 ns.
Besides its synthetic merit, the extrusion of 2 from 1-Cu is
mechanistically interesting, as it can be regarded as a formal
metathesis that involves two double-bond cleavages and two
double-bond formations.[1,7] A marked difference in the
reactivity of 1-Zn and 1-Cu is also notable, suggesting a
crucial role of CuII ion in the extrusion reaction. The detailed
reaction mechanism is not clear at the present stage, however,
a subtle structural difference between 1-Cu and 1-Zn may be
important as the tilting angle of the pyrrole rings E and G is
slightly but distinctly smaller in 1-Cu (118) than in 1-Zn (208)
(Figures 1 and 2). The smaller tilting angle between the
pyrrole rings that cyclize to form a subporphyrin macrocycle
might be favorable for the extrusion reaction. Alternatively,
the CuII ion may serve as an important electronic factor in
helping the extrusion reaction.
In summary, we have described the extrusion of subpor-
phyrin from [32]heptaphyrin 1 upon cooperative metalation
with CuII and BIII ions which demonstrates a wider applic-
ability of transannular formal metathesis-type transformation
of expanded porphyrins to produce even a ring-contracted
porphyrin. Further study on the extrusion reaction is under-
way to explore its scope and limitation as well as its
mechanistic details.
[13] S. Saito, A. Osuka, Chem. Eur. J. 2006, 12, 9095.
[14] a) Crystallographic data for 1-Zn: C89H47F35N7O3Zn, Mw =
¯
1992.71, triclinic, space group P1 (No.2), a = 15,716(6), b =
15.898(4), c = 18.477(5) Š, a = 105.143(11), b = 100.739(13),
g = 107.991(12)8, V= 4055(2) Š3, 1calcd = 1.632 gcmÀ3
,
Z = 2,
R1 = 0.0563 [I > 2.0s(I)], Rw = 0.1317 (all data), GOF = 0.802
[I > 2.0s(I)]. b) Crystallographic data for 1-Cu:
176H32F70N14O5Cu2, Mw = 3879.24, monoclinic, space group C2/
C
c (No.15), a = 42.784(5), b = 11.319(5), c = 33.927(5) Š, b =
99.353(5)8, V= 16211(8) Š3, 1calcd = 1.589 gcmÀ3, Z = 4, R1 =
0.0749 [I > 2.0s(I)], Rw = 0.2343 (all data), GOF = 1.049 [I >
2.0s(I)]. c) Crystallographic data for 2: C34H9BF15N3O2.62, Mw =
797.25, orthorhombic, space group Pbcn (No.60), a = 25.096(3),
b = 18.170(2), c = 14.3348(18) Š, V= 6536.6(14) Š3, 1calcd
=
1.620gcm À3, Z = 8, R1 = 0.0989 [I > 2.0s(I)], Rw = 0.2615 (all
data), GOF = 1.105 [I > 2.0s(I)]. CCDC-643985 (1-Zn), 648936
(1-Cu), and 648937 (2) contain the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
[15] The bowl depth is defined as the distance from the mean plane of
six b-peripheral carbon atoms to the boron atom.
[16] The quantum yield was determined by using meso-phenyl
subporphyrin as the standard (Ref. [11b]).
Received: April 17, 2007
Published online: June 20, 2007
Angew. Chem. Int. Ed. 2007, 46, 5591 –5593
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
5593