1926 J. Org. C h e m .

1996,60, 1926-1931

Articles
Facile Synthesis of meso-Tetraaryl Cofacial Diporphyrins
James P. Collman,* David A. Tyvoll, Leng Leng Chng, and H. T. Fish
Department of Chemistry, Stanford University, Stanford, California 94305

Received October 17, 1994@

Metalated derivatives of cofacial diporphyrin ligands have been employed in the binding and
catalytic multielectron redox transformations of small molecules. To date, the syntheses of these
interesting molecules have been extremely cumbersome and low yielding. In addition, their
synthetic methodologies have presented no convenient way to modify the electronic and structural
properties of the constituent porphyrins. Here, we report a new method for the synthesis of a
family of cofacial diporphyrin ligands in which the two porphyrins are attached via one rigid aromatic
linker. The synthesis is considerably shorter-three steps from a suitable dialdehyde bridge-utilizes
inexpensive, commercially available reagents, results in markedly increased yields, and allows for
convenient variation of the constituent porphyrins. The method involves the monoprotection of a
dialdehyde using 1,3-propanedithiol. The monoprotected aldehyde is then cocondensed under
modified Lindsey conditions with pyrrole and the aromatic aldehyde of choice. The aldehyde of
the resulting species is subsequently deprotected using DDQ and BFB*O(Et)2-a new method for
cleavage of dithiane protecting groups. A second Lindsey condensation results in formation of the
cofacial diporphyrin ligand. Employing thii method, we have synthesized a wide variety of cofacial
hetero- and homodiporphyrin ligands, the metalated derivatives of which are currently under
investigation in our laboratories.

Introduction diastereomers is produced which are difficult to separate;

and (3) the synthesis is quite long.2
Cofacial metallodiporphyrins have been used as mo- Subsequently, two other cofacial diporphyrins were
lecular catalysts for the multielectron redox transforma- developed: the H4DPA ( l b ) and H4DPB (IC),first syn-
tions of small molecules (e.g., 0 2 , Nz, and Hz).l The thesized by Chang et al. in 1983.3 Here the two porphy-
catalysts were designed to accommodate small substrates rin rings are bridged by a single, rigid, aromatic linker
inside the cavity, thereby bridging the two metal centers. (anthracene for H4DPA and biphenylene for H4DPB).
The first cofacial metallodiporphyrin to accomplish the
catalytic four-electronreduction of dioxygen was COZFTF~
( l a ) developed in 1979 by Collman et aL2

The two etio-type porphyrin structures are held to-

gether by amide linkages at the ,&pyrrolic positions.
Though the synthesis of these amide-linked porphyrins
is versatile in that the interporphyrin distances can be
varied by incorporating bridges of different lengths, it
suffers from at least three disadvantages: (1)the amide
linkages can be hydrolyzed or reduced; (2) a mixture of
In both cases the proximity of the two porphyrins
@ Abstract published in Advance ACS Abstracts, March 1 , 1995. allows for activation of small molecules between the
(1)Collman, J. P.;Wagenknecht, P. S.; Hutchison, J. E. Angew. metal centers. In particular, the cobalt derivatives of
Chem., Int. Ed. Engl. 1994,33,1537-1554 and references contained
therein.
(2)(a) Collman, J.P.; Denisevich, P.; Konai, Y.; Marrocco, M.; Koval, (3)(a) Chang, C. K.; Abdalmuhdi, I. J. Org. Chem. 1983,48,5388-
C.; Anson, F. C. J.Am. Chem. SOC.1980,102,6027-6036.(b) Durand, 5390.(b) Chang, C. K.; Abdalmuhdi, I. Angew. Chem., Int. Ed. Engl.
R.R., Jr.; Bencosme, C. S.; Collman, J. P.; Anson, F. C. J.Am. Chem. 1984,23,164-165. (c) Eaton, S.S.; Eaton, G . R.; Chang, C. K. J.Am.
SOC.1983,105,2710-2718. Chem. SOC.1985,107,3177-3184.

0022-326319511960-1926$09.00/00 1995 American Chemical Society

Synthesis of meso-Tetraaryl Cofacial Diporphyrins J. Org. Chem., Vol. 60, No. 7, 1995 1927

these molecules are potent four-electron dioxygen reduc- bridge.15J6 Some of these studies have utilized Lindsey
tion c a t a l y ~ t s .These
~ cofacial diporphyrins are chemi- preparations to synthesize their porphyrins. These
cally robust, and their final purification is straightfor- molecules have been used mainly as models for the study
ward.5 Despite considerable effort to improve the original of electron transfer in photosynthetic systems. No ex-
synthetic scheme, however, their syntheses remain for- amples of multielectron catalysis have yet been reported.
midable tasks: the most efficient synthesis to date In a similar fashion, we have applied the Lindsey
requires 21 steps for H4DPA (24 for H4DPBh6 method toward our own research needs. Thus, using
In spite of their difficult syntheses, extensive studies modified Lindsey conditions12in the presence of biphen-
ylene or anthracene dialdehydes has allowed the syn-
of these remarkable molecules have been rewarding.
thesis of a family of cofacial, meso-tetraarylporphyrin
Significant examples include: dioxygen binding and
dimers. By judicious choice of the benzaldehyde deriva-
efficient 4e- reduction to water by the bis-cobalt deriva- tive, we have a means of addressing all the issues
t i v e ~ ,the ~ ~microscopic
,~~ reverse of dinitrogen fixation mentioned above pertaining to the existing cofacial
achieved with the bis-ruthenated species of l ~and, the ~ diporphyrins. Namely, we have developed a general,
isolation and characterization of a bridging dihydrogen expedient method for cofacial diporphyrin synthesis
adduct of the bis-ruthenated derivative of which allows for systematic variation of the structural
The accomplishments of these past studies have and electronic properties of these molecules.
spawned new questions regarding small molecule reac- In addition, during the course of this work we discov-
tivity, particularly in the context of activation by two ered a convenient and high yield method for the depro-
metals. Unfortunately, the cofacial diporphyrins devel- tection of dithiane derivatives. Details will be provided
oped to date are of limited use in further endeavors; the in the Results and Discussion.
rigidity imposed by their arduous syntheses precludes
any systematic variation of their electronic and structural Experimental Section
properties. Four features of these molecules are worthy
General. Reagent grade CHzCl2 and CHC13 (ethanol
of mention at this time: (1)the electronic properties of stabilized) were purchased from Fisher and used as received.
the porphyrin significantly influence the redox properties Flash silica was purchased from EM Science with particle size
of the metal; (2) the planar nature of the porphyrins finer than 230 mesh ASTM. Activated neutral alumina,
allows intra- and intermolecular metal-metal bond Brockman I standard grade (-150 mesh), was purchased from
f ~ r m a t i o n(3)
; ~ the two porphyrins are identical to each Aldrich. Doubly distilled boron trifluoride etherate (BF3)was
other; and (4) further chemical modification (e.g., for the purchased from Aldrich and used as received. It was stored
in an inert atmosphere Nz box ( 0 2 < 1ppm) during the interim.
purposes of covalent attachment to surfaceslO 1 is im- Pyrrole (Aldrich) was distilled under nitrogen and likewise
practical. stored under inert atmosphere. Benzaldehyde derivatives
In 1986 a modification of the Rothemund porphyrin were either purchased from Aldrich or TCI and used as
synthesisll was introduced by Lindsey.12 The method received or synthesized by published procedures. 2,3-Dichloro-
5,6-dicyano-l,4-benzoquinone (DDQ) was purchased from Jan-
involves condensation of pyrrole and benzaldehyde de- ssen Chimica and used as received. 1,8-Diformylbiphenylene6"
rivatives in the presence of an acid catalyst at room and 1,8-diformylanthra~ene~~ were synthesized according t o
temperature. This results in formation of a porphyrino- literature procedures. All glassware and syringes were oven
gen, which is subsequently oxidized in situ to yield the dried immediately prior to use. 'H NMR spectra (CDC13 and
porphyrin. This pioneering method has made possible C6D6) were obtained with a Nicolet NMC-300 MHz or a Varian
the synthesis of numerous new porphyrins.13 Recently, XI,-400 MHz spectrometer. UV-vis spectra were obtained
with a Hewlett-Packard 8450A diode array spectrometer.
a number of papers have appeared that describe the Mass spectra were done by the Mass Spectrometry Facility at
synthesis of meso-di- or -tetraarylporphyrin dimers linked the University of California at San Francisco. Elemental
by either an extended phenanthr~linel~ or a phenyl analyses were performed by Midwest Microlab. Full charac-
terization data will be presented for two representative cofacial
dimers. Their syntheses are essentially identical,varying only
(4) (a) Chang, C. K.; Liu, H. Y.; Abdalmuhdi, I. J. Am. Chem. SOC. in stoichiometry or choice of solvent. Thus, one general
1984,106, 2725-2726. (b) Liu, H. Y.; Abdalmuhdi, I.; Chang, C. K.;
Anson, F. C. J . Phys. Chem. 1985,89, 655-670. method will be described, with particular differences noted
(5)All syntheses mentioned thus far rely on the stepwise synthesis later. We emphasize that, thus far, we detect no reactivity
of pyrrole and dipyrrylmethane subunits. differences between the two bridges and that methodology
(6) (a) Collman, J . P.; Hutchison, J. E.; Lopez, M. A,; Tabard, A.; described for one particular bridge may be fully applicable to
Guilard, R.; Seok, W. K.; Ibers, J. A.; L'Her, M. J . Am. Chem. SOC. the other.
1992, 114, 9869-9877. (b) Guilard, R.; Lopez, M. A,; Tabard, A,;
Richard, P.; Lecomte, C.; Brandes, S.; Hutchison, J. E.; Collman, J . P. Synthesis. 1-(1,3-Dithiacyclohex-2-yl)S-formylanthra-
J . Am. Chem. SOC.1992,114, 9877-9889. cene(3a). The protection of the dialdehyde was accomplished
(7) Collman, J. P.; Hutchison, J. E.; Lopez, M. A,; Guilard, R. J . by modification of a procedure which used 1,2-ethanedithiol
Am. Chem. SOC. 1992,114, 8066-8073. as the protecting g r ~ ~ pAt. room~ ~ temperature,
~ J ~ ~ 2.00 g of
(8) Collman, J . P.; Hutchison, J . E.; Wagenknecht, P. S.; Lewis, N. l&difo~-mylanthracene~~ (8.54 mmol) and 924 mg of 1,3-
S.; Lopez, M. A,; Guilard, R. J . Am. Chem. SOC.1990,112,8206-8208.
(9) Collman, J . P.; Kim, K.; Garner, J . M. J . Chem. SOC.,Chem. propanedithiol(8.54mmol)were dissolved in 85 mL of dry CH2-
Commun. 1986, 1711-1713. Cl2. To the yellow solution was added 200yL of BF3 (1.6mmol)
(10) Illustrative examples can be found in: Molecular Design of via syringe. A fine yellow-white precipitate was observed
Electrode Surfaces; Murray, R., Ed.; Techniques of Chemistry; John within 10 min. After being stirred at least 1 h, the reaction
Wiley & Sons, Inc.: New York, 1992; Vol. 22. mixture was transferred to a separatory funnel and washed
(11)(a) Rothemund, P. J . Am. Chem. SOC. 1936, 58, 625-627. (b)
Rothemund, P. J . Am. Chem. SOC.1939,61, 2912-2915. '
(12) (a)Lindsey, J. S.; Schreiman, I. C.; Hsu, H. C.; Kearney, P. C.; (15) Osuka, A,; Nakajima, S.; Nagata, T.; Maruyama, K.; Toriumi,
Marguerettaz, A. M. J. 0rg.Chem. 1987,52, 827-836. (b) Lindsey, J. K. Angew. Chem., Int. Ed. Engl. 1991,30, 582-584.
S.; Wagner, R. W. J . Org. Chem. 1989,54, 828-836. (16)Meier, H.; Kobuke, Y.; Kugimiya, S. J . Chem. Soc., Chem.
(13) Lindsey, J . S. In Metalloporphyrins Catalyzed Oxidations; Commun. 1989,923-924.
Montanari, F., Casella, L., Eds.; Kluwer Academic Publishers: Dor- (17) (a) Marshall, J. A.; Belletire, J. L. Tetrahedron Lett. 1971,871-
drecht, 1994; pp 49-86. 874. (b) Greene, T. W.; Wats, P. G. M. Protective Groups in Organic
(14) Noblat, S.; Dietrich-Buchecker, C. 0.;Sauvage, J. P. Tetrahe- Synthesis, 3rd ed.; John Wiley & Sons, Inc.: New York, 1991; Chapter
dron Lett. 1987, 47, 5829-5832. 4, pp 198-207.
1928 J. Org. Chem., Vol.60, No. 7, 1995 Collman et al.

with 5% aqueous NaOH (1 x 100 mL) and water (2 x 100mL). Scheme 1

The organic layer was collected and stripped of solvent, and
the yellow residue was then chromatographed over flash silica
(5 x 30 cm). The column was eluted with CHzCldhexanes (9/
1). The product was isolated as the second of three yellow
bands (1.33 g, 48% yield): 'H NMR (CDC13) 6 10.43 (s, lH), 'SJ
10.42 (9, lH), 8.49 (s, lH), 8.24 (d, lH, J = 8.5 Hz), 8.00 (d, 2e, b b
lH,J=6.8Hz),7.96(d,lH,J=8.5Hz),7.87(d,lH,J=7.0
Hz), 7.61 (dd, lH, J1 = 8.5 Hz, Jz = 6.8 Hz), 7.52 (dd, lH, Ji
= 8.5 Hz, J Z = 7.0 Hz), 6.20 (9, lH), 3.40 (m, 2H), 3.05 (m,
2H), 2.30 (m, lH), 2.05 (m, 1H).
1-(1,3-Dithiacyclohex-2-yl)-8-formylbiphenylene (3b).
The monoprotected biphenylene dialdehyde was synthesized
from the dialdehydesa under identical conditions as described L
above. Yields ranged from 45-48%: 'H NMR (CDCl3) 6 10.28
(s, 1 H), 7.14 (d, lH, J = 8.3 Hz), 6.96 (d, l H , J = 8.4 Hz),
6.86 (m, 2 H), 6.73 (d, l H , J = 6.8 Hz), 6.61 (d, lH, J = 6.7
Hz) 5.67 (s, lH), 3.13 (m, 2H), 2.89 (m, 2H), 2.16 (m, lH), 1.92
(m, 1H).
l-(B-Tris(10,15,20-(pentafluorophenyl)porphyrinyl))-8-
formylbfphenylene(11). Three hundred mg (1mmol) of the
monoprotected biphenylene-dialdehyde was dissolved in 1.6
L of CH2Clz in a 3-L three-neck flask fitted with rubber septa
and a condenser. The solution was purged continuously with
a stream of nitrogen. To this was added 1.852 mL of pen-
tafluorobenzaldeyde (15 mmol) and 1.11 mL of pyrrole (16
mmol), thus maintaining a 1:15:16 stoichiometry of aryl bridge: 5a, b 6a, b
benza1dehyde:pyrrole. BF3 (0.65 mL, 5.28 mmol) was then
added via syringe. Its concentration is 3.3 x M, thus mmol), 588 mg of pentafluorobenzaldehyde (3.0 mmol), 0.221
maintaining recommended Lindsey conditions.12 The reaction mL of pyrrole (3.19 mmol), 0.130 mL of BF3 (1.06 mmol), 320
was stirred in the dark for 80 min. At this time DDQ (2.72 mL of CHzC12, and 1 g of DDQ. After normal workup and
grams, 12 mmol) was added and the mixture was stirred for
at least 1 h. The acid catalyst was neutralized with the
addition of 0.81 mL (1.1equiv) of triethylamine. The volume
-
elution from the alumina column the product was purified by
silica chromatography (5 x 25 cm, 8:l hexanes:CH&lz 2:l
hexanes:CHzClz): yield 114 mg (32% based on the bridge
of the reaction was then reduced to approximately 300 mL porphyrin); mass spectrum m / e 1763 (M+);'H NMR (CDC13)
(-20% of the original volume) by rotoevaporation and then 6 8.66 (d, 2H, J = 4.7 Hz), 8.45 (d, 2H, J = 4.7 Hz), 8.07 (d,
loaded onto an alumina column (6 x 25 cm) packed in 1:l 2H, J = 4.6 Hz), 7.83 (m, 2H), 7.58 (m, 6H), 7.36 (t, 2H, J =
hexanes:CHzClz and eluted with CHzClz until no more por- 6.8 Hz), 7.14 (m, 4H), 6.48 (br d, 2H, J = 3.2 Hz), -5.40 (s,
phyrinic product was detected (approximately 1.5 L). This 4H); UV/vis (CHzClZ)A, (nm) 402 (Soret), 514,546,590,644.
mixture was then concentrated to approximately 300 mL. To Anal. Calcd for C B ~ N ~ H U FC, ~ O59.88;
: H, 1.48; N, 6.35.
this was added 1mL of BF3 (8.13 mmol) and 1 g (4.4 mmol) of Found: C, 59.81; H, 1.60; N, 6.12.
DDQ and the mixture stirred overnight in air. In 100 mL 1,8-Bis(5-tris(10,15,20-mesitylporphyrinyl))anthra-
aliquots, the reaction mixture was washed 3x with 150 mL of cene (12). The second condensation proceeds identically to
10% NazC03 to remove catechol. With deprotection of the the first mesitaldehyde condensation: 570 mg of porphyrin
monoporphyrin monoaldehyde accomplished, purification was with formyl bridge, 7 (0.66 mmol), 1.461 g of mesitaldehyde
-
achieved by silica chromatography (6 x 30 cm, 8:l hexanes:
CHzCl2 1:l hexanes:CHzClz): yield 220 mg (22% based on
the bridge); mass spectrum m / e 985 (M+);'H NMR (CDC13) 6
(10.5 mmol), 0.705 mg of pyrrole (9.86 mmol), 0.427 mL of BF3
(3.47 mmol), 1.05 L of CHC13,1.79 g of DDQ (7.92 mmol). Final
9.33 (d, 2H, J = 4.9 Hz), 8.93 (s, 4H), 8.90 (d, 2H, J = 4.8 Hz),
7.73 (d, lH, J = 8.2 Hz), 7.34 (t, lH, J = 7.6 Hz), 7.19 (d, l H ,
-
purification was accomplished by silica chromatography (4 x
20 cm, 4:l hexanes:CHzClz 2:l hexanes:CHzClz): yield 130
mg (14% based on the bridged porphyrin); mass spectrum m le
J = 6.9 Hz), 6.99 (m, lH), 6.85 (m, 2H), 6.66 (9, 1H), -2.82 ( 8 ,
2H); UV/vis (CH2Clz)A,, (nm) 414 (Soret), 510,540,584,640.
+
1504 (M+ 1);'H NMR (CsD6) 6 9.26 (s, lH), 8.82 (s, lH),
8.55(d,4H,J=4.7Hz),8.42(d,4H,J=4.7Hz),8.27(d,2H,
Anal. Calcd for C51H17F15N40: C, 62.08; H, 1.74; N, 5.68. J = 7.5 Hz), 8.19 (d, 4H, J = 4.7 Hz), 7.95 (d, 4H, J = 4.7 Hz),
Found: C, 61.99; H, 1.94; N, 5.42. 7.35-7.4 (m, 4H), 7.08 (s, 2H), 6.98 (5, 4H), 6.92 (9, 4H), 6.64
1- (5-Tris( 10,15,20-mesitylporphyrinyl))-8-formylan- (s, 4H), 2.36 (s, 6H), 2.35 (9, 12H), 1.90 (s, 6H), 1.62 (s, 12H),
thracene (7). The above procedures were used with the 1.59 (s, 6H), 0.21 (s, 12H), -2.72 (br s, 4H); UV/vis (CHZClz)
following exceptions. CHC13 was used as the solvent (3.5 L). Amax (nm) 414 (Soret), 516, 550, 592, 646. Anal. Calcd for
The bridge:mesitaldehyde:pyrrole stoichiometry was 1:12:13. C108N8H94.HZO: C, 85.23; H, 6.36; N, 7.36. Found: C, 85.21;
Following the alumina column, the mixture was chromato-
graphed on silica (6 x 20 cm, 4:l hexanes:CHzCl~ 2:l
hexanes:CHzClz): yield 570 mg (24% based on the bridge);
- H, 6.48; N, 7.05.

mass spectrum m / e 868 (M+);'H NMR (CDC13)6 9.56 (9, lH), Results and Discussion
9.28 (s, lH), 8.81 (s, lH), 8.64 (d, 2H, J = 4.6 Hz), 8.62 (d, 2H, The general synthetic route is illustrated in Scheme
J = 4.6 Hz), 8.53 (d, 2H, J = 4.5 Hz), 8.49 (d, 2H, J = 4.5 Hz), 1. The dialdehyde bridge 2 (1,8-diformylbiphenyleneor
8.45 (d, l H , J = 8.6 Hz), 8.32 (d, lH, J = 8.6 Hz), 8.23 (d, lH,
J = 6.3 Hz), 7.90 (dd, l H , J1 = 8.6 Hz, J 2 = 6.2 Hz), 7.73 (d, 1,8-diformylanthracene) is first monoprotected with 1
l H , J = 6.3 Hz), 7.51 (dd, lH, J1 = 8.6 Hz, J 2 = 6.3 H~),7.29 equiv of 1,3-propanedithiol. A mixture of three products
(9, lH), 7.26 (s, lH), 7.23 (s, 2H), 7.21 (s, 2H), 2.62 (s, 3H), (the diprotected, the monoprotected, and the unprotected
2.57 (s, 6H), 1.97 (s, 3H), 1.86 (s, 6H), 1.84 (s, 6H), 1.82 (s, dialdehyde) is produced, and these are separated on a
3H), -2.34 (br s, 2H); UV/vis (CHZClz),A (nm) 422 (Soret), silica column. The unreacted dialdehyde a n d the dipro-
516, 550, 590, 646. Anal. Calcd for C62H5zN40*1/2HzO: C, tected dialdehyde are isolated and recycled.
84.79; H, 6.09; N, 6.39. Found: C, 84.53; H, 6.25; N, 6.28.
Lindsey porphyrin preparations are crucially depend-
1,8-Bis(5-tris( 10,15,20-(pentafluoropheny1)porphyri-
ny1))biphenylene (20). The second Lindsey condensation ent on solvent choice. We note that our mixed condensa-
proceeds identically to the first pentafluorobenzaldehyde con- tions sometimes involve benzaldehyde derivatives of
densation: 197 mg of porphyrin with formyl bridge 11 (0.20 differing reactivity. Thus, we expect the chosen solvent
Synthesis of meso-Tetraaryl Cofacial Diporphyrins J. Org. Chem., Vol. 60, No. 7, 1995 1929
Table 1. Free-Base meeo-Tetraaryl Cofacial Diporphyrin

c Ar ( Yield, O/O ) a
- CHJ
Ar' ( Yield, O h )

7
CH;

10

11

-
a Isolated yield of monoporphyrin monoaldehyde, 5. Isolated yield of free-base cofacial diporphyrin, 6. Isolated yield of monometalated
cofacial diporphyrin when the second condensation is done after the first porphyrin is metalated with zinc or nickel.

to reduce the overall yield in these cases. Tolerance of Depending on the quantity of impurities present after
specific functional groups, steric limitations, and choice the alumina column, more DDQ may be needed to
of acid catalyst (BF3 o r trifluoroacetic acid) are issues complete the deprotection. (We sometimes deprotect
well-addressed by Lindsey.12J3 We have found that fresh prior to the alumina column, but this invariably requires
boron trifluoride etherate is essential to achieving good excess DDQ and BF3.1 The alumina column typically
yields in these reactions. allows isolation of essentially the desired product and the
The monoprotected monoaldehyde bridge 3 is then monomeric porphyrin (byproduct),and it is often possible
cyclized with pyrrole and the desired aryl aldehyde using to remove a large amount of the monomeric porphyrin
the Lindsey procedure,12with modified stoichiometry, to at this stage. The deprotection is usually accomplished
give the protected monoporphyrin 4 in moderate yield. before final purification, because typically the free alde-
This is then deprotected in situ with BF3 and DDQ to hyde is easier to separate from the monomeric porphyrin.
yield the monoporphyrin monoaldehyde 6 in >90% yield. The final cofacial diporphyrin 6 is then obtained by
1930 J.Org. Chem., Vol. 60,No. 7, 1995 Collman et al.

allowing 6 to react with pyrrole and the benzaldehyde of

choice in another Lindsey condensation. Successful
syntheses have been realized with stoichiometries vary-
ing from 1:12:13 to 1:31:32 (bridged-porphyrin:phenyl *SH
a1dehyde:pyrrole). The desired product is cyclized in
higher yields when higher reagent ratios are employed;
however, at high ratios the yield of the monomeric
porphyrin byproduct (usually the major component of the
product mixture) is increased disproportionately. Thus,
the choice of reagent ratio is a balance between higher
cyclization yields and difficulty of purification. We note
that the initial isolation and identification of the cofacial
porphyrin is greatly aided by two distinct spectroscopic
markers: the blue-shifted Soret in the UV/vis spectrum
and the high field signals of the N-pyrrolic resonances V
in the 'H NMR.
Through this general synthetic method, we are able Figure 1.
to synthesize cofacial homoporphyrin dimers (the two
porphyrin rings are identical), heteroporphyrin dimers porphyrin has low mobility on the silica (due to its
(the two porphyrin rings are different), as well as constituent benzaldehyde derivative); in general, the
heterometallic diporphyrins (two different metals in the isolated yield will be lower because of the preponderance
cofacial diporphyrin; the two porphyrin rings can be of impurities with low Rts.
identical or different). Although these cofacial diporphyrins are easily made
Heterometallic species are synthesized conveniently by in four steps (starting from the bridge), they are not
metallationla after the first porphyrin condensation. conveniently synthesized on a large scale (> 1g) because
Depending on the reactivity of the first metal to be they are prepared under high dilution conditions and rely
inserted (e.g., Ti), the monoporphyrin 4 may be isolated on silica chromatography as a means of purification. The
and purified prior to deprotection. For other metals (e.g., cofacial homoporphyrin 12 or 15 can be synthesized in
Ni, Zn) the aldehyde presence will not interfere with the one step by allowing 2a to react with pyrrole and the
metalation procedure and deprotection can be accom- correspondingbenzaldehyde. The yield of 12 or 15 in this
plished prior to metal insertion. f i r the final porphyrin case is comparable to the overall yield of the four step
condensation (performed under identical conditions as synthesis as shown in Scheme 1. The chromatographic
those described for unmetalated derivatives) the second separations are expectedly more difficult. We believe this
metal can be inserted. For the mesitaldehyde condensa- result can be extended to other benzaldehydes.
tions (e.g., 12), the subsequent yield of the second We initially attempted deprotection of 4 using the
porphyrin condensation is considerably increased (by various methods available for the deprotection of thio-
roughly a factor of 2) when nickel or zinc has been acetals and ketal~,''~e.g., oxidation reactionslg and
inserted into the first porphyrin. Presumably, this is the alkylations.20 These methods produced unsatisfactory
result of improved cyclization; the monometalated de- yields and undesirable side products. Sankarama et al.
rivative is not easier to isolate from the homoporphyrin recently reported that DDQ could effect photochemical
than is the bis-free base. Table 1shows some of the free- deprotection of a variety of thioacetals.21 Irradiation with
base cofacial diporphyrins that have been synthesized a mercury lamp or reflux in acetonitrile was required.
thus far. Lower yields were achieved when the reaction was
carried out at room temperature.22 In the course of our
The Lindsey conditions accommodate many different
work, we have found that DDQ in the presence of an acid
types of benzaldehydes12with varying results in yields.
catalyst (BF3 or CC13C02H)leads to clean deprotection
Lower yields are obviously a result of the inherent
of 4 in high yields (>go%). These reactions proceed at
reactivity of the parent benzaldehyde derivative, but
room temperature in CHzClz or CHCl3 in the presence of
other factors play a role as well. Since these are mixed
air (water is present as a byproduct of porphyrin con-
condensations, multiple porphyrin products are obtained
densations). The reaction is quite facile; indeed, care
and isolation of the desired product is correspondingly
must be taken in order to isolate 4 under the reaction
more difficult. Larger scale reactions tend to give lower
yields-again, we believe this to result from the difficulty conditions. The reaction requires catalytic amounts of
acid and stoichiometric amounts of DDQ. At higher
in purification. Poor solubility of the undesired mono-
meric porphyrin makes for difficult isolation of the concentrations (including that of BF3) the deprotection
desired porphyrin-invariably the symmetric monomeric is essentially instantaneous. Substituting p-chloranil for
DDQ does not afford deprotection of the aldehyde (the
porphyrin has a higher Rf(and lower solubility)than the
bridged porphyrin; this monomer partially precipitates le- reduction potential of the former is 0.5 V less than
that of DDQ).23 The reactions are run in normal labora-
on top of the column and then leaches through continu-
ously during the elution. This is a problem in particular tory light; no cleavage was detected under identical
conditions without the addition of an acid catalyst. This
with the phenyl and mesityl porphyrins. If the desired
(19) Hojo, M.; Masuda, R. Synthesis 1976, 678-679.
(18)Metallation of free base porphyrins are performed according (20) Fetizon, M.; Jurion, M. J. Chem. Soc., Chem. Commun. 1972,
to published procedures. (a) Fuhrhop, J. H.; Smith, IC M. In Porphyrins 382-383.
and Metalloporphyrins; Smith, K. M., Ed.; Elsevier Scientific Publish- (21) Mathew, L.; Sankararaman, S. J. Org. Chem. 1993,58,7576-
ing Co.: Amsterdam, 1975; Chapter 19, pp 795-804. (b) Buchler, J. 7577.
W. In The Porphyrins, Vol. 1, Structure and Synthesis, Part A; Dolphin, (22) Tanemura, K.; Dohya, H.; Imamura, M.; Suzuki, T.; Horaguchi,
D., Ed.; Academic Press, Inc.: New York, 1978; Chapter 10, pp 389- T.Chem. Lett. 1994,965-968.
483. (23) Peover, M. E. J . Chem. SOC.1962,4540-4549.
Synthesis of meso-Tetraaryl Cofacial Diporphyrins J. Org. Chem., Vol. 60, No. 7, 1995 1931
method allowed us to recycle the diprotected bridges in exchange of H O 2 , and we are employing it and its
high yield.24 ruthenium-nickel mixed metal analog in our investiga-
tions concerning the mechanism of this fundamental
Conclusion reaction.29 The activation of C-H bonds in methane and
small aromatic hydrocarbons by the bis-rhodium deriva-
We have developed an expedient, efficient, and general
tives of 12 are currently under examination in our
method for cofacial diporphyrin synthesis which allows
for the systematic variation of the structural and elec- laboratories. We believe the steric bulk of the constituent
tronic characteristics of these molecules. We are employ- porphyrins combined with the relatively long anthracene
ing cofacial metallodiporphyrins synthesized via this bridge precludes the formation of both intramolecular
method in our current investigations of the binding and and intermolecular metal-metal bonds involving 4d and
activation of small molecules. 5d metal^.^,^^,^^ Thus, the ability to support two electron-
The bis-cobalt derivatives of 18 and 21 (see Table 1) poor metals in close proximity may account for the
prove to be potent catalysts for the four electron reduction intriguing behavior of this molecule.
of dioxygen when adsorbed on edge plane pyrolytic
graphite electrode^.^^ The bis-cobalt trimercaptan de- Acknowledgment. The support of the National
rivative of 18 has been investigated for its catalytic Science Foundation is gratefully acknowledged. We
activity for dioxygen reduction when adsorbed on gold thank the Mass Spectrometry Facility at the University
electrodes (Figure 1).26 of California a t San Francicso, supported by NIH
Electronic and steric requirements for dioxygen reduc- Division of Research Resources grant RR01614 and by
tion are also being investigated at this time. Iridium NSF grant DIR8700766.
derivatives of 12 and 14 have been used in mechanistic
studies on dioxygen reduction catalysi~.~' SupplementaryMaterial Available: Characterization of
In addition to dioxygen activation, these cofacial por- 4a,b, 7(Ni, Zn), 8-10, 12(Ni, Zn), 13-19, and 21 (4 pages).
phyrins are also being used to study the binding and This material is contained in libraries on microfiche, im-
activation of other small molecules. Preliminary data mediately follows this article in the microfilm version of the
indicate that dinitrogen bridges the bis-ruthenium de- journal, and can be ordered from the ACS; see any current
rivative of 14.28 Bis-ruthenated 12 catalyses the painvise masthead page for ordering information.
509414579
(24) We were able to detect the presence of trimethylene disulfide
in the reaction mixture.
(25) Collman, J. P.; Tyvoll, D. A,; Chng, L. L. Unpublished results. (28) Collman, J. P.; Chng, L. L. Unpublished results.
(26) Collman, J. P.; Tyvoll, D. A; Chng, L. L. and Murray, R. W.; (29) Collman, J. P.; Fish, H. T. Unpublished results.
Hutchison, J. E.; Postlethwxite, T. A. Manuscript in preparation. (30)Sheny, A. E., Wayland, B. B. J.Am. Chem. SOC.1990, 112,
(27)(a) Collman, J. P.; Chng, L. L.; Tyvoll, D. A. Submitted for 1259-1261.
publication. (b) Collman, J. P.; Kim, K. J . Am. Chem. SOC.1986, 108, (31) Camenzind, M. J.; James, B. R.; Dolphin, D. J . Chem. SOC.,
7847-7849. Chem. Commun. 1986,1137-1139.