Jordan et al.

/ Electroreduction of Porphyrins and Metalloporphyrins 3857

result from increased covalency in the (MesCp^Mn (3) Evans, S.; Green, M. L. H.; Jewitt, B.; King, G. H.; Orchard, A. F. J. Chem.
Soc., Faraday Trans. 2 1974, 70, 356-376.
system. (4) Smart, J. C.; Robbins, J. L. J. Am. Chem. Soc. 1978, 100, 3936-3937.
(5) Almenningen, A.; Haaland, A.; Motzfeldt, T. “Selected Topics in Structure
Conclusions Chemistry", Universitetsforlaget: Oslo, 1967; p. 105.
(6) Almenningen, A.; Haaland, A.; Samdal, S., J. Organomet. Chem. 1978,
Our magnetic studies of decamethylmanganocene indicate 149, 219-229.
that permethylation of the Cp ring results in exclusively low- (7) Haaland, A.; Lusztyk, J.; Novak, D. P.; Brunvoll, J.; Sarovieysky, K. B. J.
Chem. Soc., Chem. Commun. 1974, 54-55.
spin behavior, in contrast to other manganocenes where (8) Freyberg, D. P.; Robbins, J. L.; Raymond, K. N.; Smart, J. C. J. Am. Chem.
high-spin states are thermally populated. From this result we Soc., 1979, 101, 892-897.
(9) Reynolds, L. T.; Wilkinson, G. W. J. Inorg. Nucí. Chem. 1954, 9, 86-92.
conclude that the ligand field strength of the Cp ring is sig- (10) Switzer, . E.; Rettig, M. F. J. Chem. Soc., Chem. Commun. 1972,
nificantly enhanced by the complete replacement of the hy- 687-688.
(11) Threlkel, R. S.; Bercaw, J. E. J. Organomet. Chem. 1977, 136, 1-5.
drogens with electron-donating methyl groups. The low-spin (12) King, R. B.; Bisnette, . B. J. Organomet. Chem. 1967, 8, 287-297.
configuration of (MesCp^Mn renders it inert toward ring (13) Duggan, D. M.; Hendrickson, D. N. Inorg. Chem. 1975, 14, 955-970.
displacement and hydrolysis but the complex does undergo (14) Orgel, L. E. “An Introduction to Transition Metal Chemistry”, 2nd ed.; Wiley:
New York, 1960; pp 78-79.
reversible oxidation and reduction to give low-spin 16- and
(15) Basolo, F.; Pearson, R. G. “Mechanisms of Inorganic Reactions", 2nd ed.;
18-electron species for which no analogues exist in the other Wiley: New York, 1967; pp 145-148.
(16) Taube, H. Chem. Rev. 1952, 50, 69-110.
manganocenes. Further studies on other first-row transition-
(17) Cooke, A. H.; Duffus, H. J. Proc. Phys. Soc., London, Sect. A 1955, 68,
metal decamethylmetallocenes are now in progress. 32-38.
(18) Goldenberg, N. Trans. Faraday Soc. 1940, 36, 847-856.
Acknowledgment. This work was partially supported by the (19) In ref 4, the value of the second potential was erroneously reported as
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

-2.50 V.
Division of Nuclear Sciences, Office of Basic Energy Sciences, (20) Nicholson, R. S.; Shain, I. Anal. Chem. 1964, 36, 706-723.
U.S. Department of Energy, under Contract W-7405-Eng- (21) Similar reactions with Cp2Mn or (MeCp)2Mn did not yield tractable prod-
ucts.
48.
(22) (a) Geiger, W. E., Jr. J. Am. Chem. Soc. 1974, 96, 2632-2634. (b) Holloway,
Downloaded via UNIV OF LIVERPOOL on June 28, 2025 at 15:33:26 (UTC).

J. D. L; Bowden. W. L; Geiger, W. E„ Jr. ibid. 1977, 99, 7089-7090.

References and Notes (23) Warren, K. D. Struct. Bonding (Berlin) 1976, 27, 45-159.
(24) Bünder, W. Dissertation, Universitát Hamburg, 1974.
(1) (a) Lawrence Berkeley Laboratory, (b) University of California. (25) Ammeter, J. H, J. Magn. Reson. 1978, 30, 299-325.
(2) (a) Wilkinson, G.; Cotton, F. A.; Birmingham, J. M. J. Inorg. Nucí. Chem. (26) Evans, D. F. J. Chem. Soc. 1959, 2003-2005.
1956, 2, 95-113. (b) Switzer, . E.; Wang, R.; Rettig, M. F.; Makl, A. H. J. (27) Warren, K. D. Inorg. Chem. 1974, 13, 1317-1324.
Am. Chem. Soc. 1974, 96, 7669-7674. (c) Ammeter, J. H.; Bucher, R.; (28) Gordon, K. R.; Warren, K. D. Inorg. Chem. 1978, 17, 987-994.
Oswald, N. ibid. 1974, 96, 7833-7835. (29) Makl, A. H.; Berry, T. E. J. Am. Chem. Soc. 1965, 87, 4437-4441.

Substituent Effects in the Electroreduction

of Porphyrins and Metalloporphyrins1
A. Giraudeau,2 H. J. Callot,3 Joseph Jordan,*4 I. Ezhar,2
and Maurice Gross2
Contribution from the Université Louis Pasteur, Strasbourg, France,23
and the Department of Chemistry, Pennsylvania State University,4
152 Davey Laboratory, University Park, Pennsylvania 16802. Received August 25, 1977

Abstract: Electron affinities and electron transfer reactivities of selected mesotetraphenylporphyrin (TPP) moieties have been
investigated by controlled potential coulometry, polarography, and cyclic voltammetry. The effect of /3-pyrrole substituents
(OEt, Cl, Br, SCN, CN, NO2) on the electroreduction of TPP was remarkably large, accounting for polarographic half-wave
potential (£1/2) shifts as great as 0.35 V per substituent, which correlated linearly with Hammett's ~. Polysubstitution of
cyano groups had an additive effect on £1/2 shifts, but polysubstitution of bromine did not. Insertion of electroreducible cat-
ions, such as Mn(Ill), Fe(III), and Co(Il), did not affect the magnitude of the substituent shifts observed on TPP per se. Sub-
stituent effects on the £1/2 of the inserted metal were invariably smaller. Thus, the effect of ß substitution on metalloporphy-
rins provides a simple diagnostic criterion for distinguishing between electron transfer implicating the central cation vs. elec-
trons inserted into the porphyrin ligand.

A renaissance of interest in the electrochemistry of por- natural porphyrins. Recently, several papers16"18 have been
phyrins and metalloporphyrins was engendered in the mid- devoted to the electrochemistry of synthetic phenyl-substituted
1960s by several papers published in this journal.5"8 An ap- tetraphenylporphins. Qualitatively, the same trends were ob-
preciable number of subsequent studies have been devoted to served as with the natural porphyrins, yielding Hammett-Taft
the electrooxidation-reduction of pyrrole-substituted por- linear free energy relationships. In metalloporphyrins, sub-
phyrins and of phenyl-substituted tetraphenylporphyrins and stituents on the porphyrin ligand have been reported to have
corresponding metalloporphyrins.9 20 Classical literature on little or no effect on the reduction potential of the inserted
naturally occurring porphyrins contains indications that sub- cation.176·22 To clarify the effect of substituents on the elec-
stituents affect redox behavior,21 as indeed expected on theo- troreduction of porphyrins, we decided to investigate pyrrole
retical considerations. Typically, electron-releasing substitu- substitution with strong electron-withdrawing groups.15 The
ents induce cathodic shifts of the reduction potentials whereas relevant macrocycles are identified in Figure 1. Results are
electron-withdrawing substituents exert the opposite effect. presented and discussed in this paper, including potential shifts
However, these potential shifts tend to be small in the case of as large as V, which are unprecedented. Based on these
1

0002-7863/79/1501-3857S01.00/0 © 1979 American Chemical Society

3858 Journal of the American Chemical Society / 101:14 / July 4, 1979

trophotometer, supplied by Varían, Palo Alto, Calif.), mass spec-

trometry (Model 9000 mass spectrometer, supplied by LKB-Pro-
dukter AB, Bromma, Sweden), and elemental analysis (performed
by the Service Central de Microanalyse du CNRS, Division de
Strasbourg, France).
2-Chlorotetraphenylporphine, H2TPP(CI). H2TPP (200 mg) plus
400 mg of TV-chlorosuccinimide were refluxed for 2 h in 60 mL of
1,2-dichloroethane. Solvent was evaporated and the residue washed
with MeOFl, dissolved in 1:1 cyclohexane-toluene, and chromato-
graphed on 300 g of silica gel using the same eluent, yielding a first
fraction (21 mg) of dichlorinated products which were discarded. The
Name^* 1
R1 R2 R3 R4 M second fraction (98 mg), which was the desired product, was recrys-
tallized from CFI2Cl2-MeOFL Visible spectrum peaks in CH2C12:
h2tpp H H H H h2
417 nm (e 356 000), 517 (22 300), 552 (7200), 595 (6500), 651
H2TPP(X) X H H H h2
Br Br H H
(5300). Mass spectrum: m/e 648 (M+, reference), 613 (— Cl, 32%,
H2TPP(Br)2ab h2 m* 578.5). Anal. Caled for C44H29N4C1: C, 81.40; H, 4.50; N, 8.62.
H2TPP(Br)2ac Br H Br H h2 Found: C, 81.51; , 4.11; N, 8.89.
H2TPP(Br)3 Br Br Br H h2 Copper 2-Thiocyanatotetraphenylporphine, CuTPP(SCN). (SCN)2
Cu TPP H H H H c/ was prepared by adding 1.6 g of bromine to 1.52 g of NH4SCN in 15
CuTPP(X) X H H H CiF mL of AcOH; 650 mg of CuTPP in 60 mL of CH2C12 was subse-
Mn [TPPtCNl^CI CN CN CN CN Mn™CI
quently added. The mixture was stirred at room temperature for 40
Fe CTPP(CN)4]CI CN CN CN CN Fe”Cl min, washed with water, and dried over Na2S04. The organic layer
Co TPP(CN)3 CN CN CN H Co1 was evaporated and the residue dissolved in toluene and chromato-
Co TPP(CN)4 CN CN CN CN Co1 graphed on 100 g of silica gel (eluent toluene). The first fraction was
unreacted starting material; the second fraction was the desired
*The groups shown in brackets are /3-pyrrole -substituents,
those without are bonded directly to the metal. product (304 mg). CuTPP(SCN) was recrystallized from
CH2Cl2-MeOH. Visible spectrum in CH2C12: 415 nm (e 340 000),
Figure I. Notation used for identifying structural features of porphyrin 542 (20 000), 575 (4650). Mass spectrum: mje Til (M+, reference),
moieties, 707 (86%), 705 (90%), 674 (- SCN, 52%, m* 622). Anal. Caled for
C45H27N5SCu: C, 73.70; , 3.71; N, 9.55; S, 4.37. Found: C, 73.09;
H, 3.72; N, 9.57; S, 4.51.
findings, a new, simple, and dependable criterion is described
for localizing electron-transfer sites in metalloporphyrins, in 2-Thiocyanatotetraphenylporphine, H2TPP(SCN). CuTPP(SCN)
(50 mg) was dissolved in 5 mL of concentrated sulfuric acid, stirred
order to differentiate between electroreduction of the inserted for 3 min at room temperature, poured into concentrated aqueous
metal and electroreduction of the porphyrin ring. ammonia, and extracted in CH2C12. The organic solvent layer was
evaporated to dryness and the residue recrystallized from
Experimental Section CH2Cl2-MeOH, yielding 34 mg of H2TPP(SCN). Visible spectrum
Electroanalytical Measurements. Polarography at the classical in CH2C12: 420 nm (e 302 000), 519 (20 800), 554 (4600), 595
dropping mercury electrode (DME) was performed with the aid of (6000), 652 (5700). Mass spectrum: m/e 671 (M+, reference), 646
a potentiostat (Model PRT 20-2X, supplied by S.O.L.E.A.-Tacussel, (47%), 644 (49%), 613 (- SCN, 59%, m* 561). Anal. Caled for
69100 Villeurbanne, France), a voltage programmer (Model Servovit C45H29N5S: C, 80.51; H, 4.35; N, 10.43; S, 4.77. Found: C, 79.47;
2, supplied by S.O.L.E.A. Co.), an electronic millivoltmeter , 4.30; N, 10.59; S, 4.39.
(S.O.L.E.A. Model S6B, input impedance 12 ), and a recording Copper 2-Nitrotetraphenylporphine, CuTPP(N02). Cu(N03)2·
microammeter (Model BGSO, supplied by Sefram Co., 75739 Paris 6H20 (500 mg) in 50 mL of Ac20 was added to 550 mg of CuTPP
Cedex 15). A Model PRG 4 instrument package (S.O.L.E.A.-Ta- dissolved in a mixture of 500 mL of chloroform plus 10 mL of acetic
cussel) was used for cyclic voltammetry at the dropping mercury acid. The reaction mixture was stirred at 30-35 °C for h, at which
1

electrode (DME). This was accomplished by appropriate current time no more starting material was detectable by TLC. The solution
sampling on successive drops, while the potential was programmed was subsequently washed with water and aqueous K2C03, dried over
by a triangular sweep. The procedure is equivalent to conventional Na2S04, and concentrated in vacuo. Methanol was added yielding
cyclic voltammetry at Kemula’s hanging drop mercury electrode. 400 mg of CuTPP(NO)2. Spectrum in CH2C12: 420 nm (e 186 000),
Coulometry at controlled potential was performed at a mercury pool 547 (13 000), 582 (8400). Mass spectrum: m/e 720 (M+, reference),
working cathode. A fritted glass barrier was interposed between the 690 (97%), 675 (85%). Anal. Caled for C44H27N502Cu: C, 73.27; H,
working electrode and a platinum foil counterelectrode. 3.77; N, 9.71. Found: C, 73.83; H, 3.77; N, 10.06.
A so-called “three-electrode” system was used in all electrochemical 2-Nitrotetraphenylporphlne, H2TPP(N02). CuTPP(NG2) (200 mg)
measurements, consisting of the appropriate indicator (or working) in 6 mL of concentrated sulfuric acid was poured into concentrated
electrode (viz., the DME or a mercury pool), an auxiliary (or aqueous ammonia and extracted with chloroform. The extract was
“counter"-) electrode, and a reference electrode. The latter was a dried over sodium sulfate and evaporated to dryness. The residue was
conventional aqueous saturated calomel electrode (SCE), equipped dissolved in toluene and eluted with the same solvent through a column
with a salt bridge which consisted of DMF (containing 0.1 M TEAP) of 200 g of alumina. The major eluted fraction was again evaporated
and water (saturated with KC1) separated by a porous glass frit sep- to dryness and the residue recrystallized from a CH2Cl2-MeOH
tum. The electroreactive species (various porphyrins and metallo- solvent mixture yielding 140 mg of H2TPP(NG2). Spectrum in
porphyrins) were dissolved in AVV-dimethylformamide (DMF), CH2C12: 426 nm (e 216 000), 527 (15 000), 565 (4000). Mass
containing 0.1 M tetraethylammonium perchlorate (TEAP) as sup- spectrum: m/e 659 (M+, reference), 629 (23%), 613 (— N02, 54%,
porting electrolyte. m* 561.5). Anal. Caled for C44H29N502: C, 80.10; H, 4.44; N, 10.61;
All electrochemical measurements were carried out at 25 °C. Po- O, 4.85. Found: C, 75.23; H, 4.66; N, 10.44; O, 4.52. Note: The low
tentials are referred to the SCE, using the sign convention of the In- carbon value is accounted for by analytical difficulties encountered
ternational Union of Pure and Applied Chemistry (1UPAC),23 i.e., by other authors in porphyrin analysis.40
the more reducing a potential, the more negative its assignment. Copper 2-Bromotetraphenylporphine, CuTPP(Br). This metallo-
Materials. DMF and TEAP were purified as described in a previous porphyrin was prepared from H2TPP(Br) and copper acetate in
communication.15 The porphyrins H2TPP(Br), H2TPP(Br)2, chloroform-MeOH. Spectrum in CH2C12: 416 nm (e 405 000), 541
H2TPP(Br)3, H2TPP(OEt), H2TPP(-2-py+)-C104-, and (19 500), 575 (3300). Mass spectrum: m/e 753, 755 (M+, 65% and
H2TPP(CN) were prepared by known procedures.24·25 Other por- 100%), 674 (60%). Anal. Caled for C44H27BrN4Cu: C, 69.98; , 3.60;
phyrins and metalloporphyrins were synthesized as outlined below, N, 7.42. Found: C, 68.92; H, 3.52; N, 7.46.
separated (and purified) on columns of silica gel (Merck silica gel 60, Copper 2-Cyanotetraphenylporphine, CuTPP(CN). This metallo-
70-230 mesh) or alumina (activity grade I—11, Merck standardized), porphyrin was prepared from H2TPP(CN) by the same procedure
and authenticated by spectroscopy (using a Cary Model 18 spec- 1 as CuTPP(Br). Spectrum in CH2CI2: 420 nm (e 465 000), 510
Jordan et al. / Electroreduction of Porphyrins and Metalloporphyrins 3859

(5600), 545 (21 000), 583 (12 500). Mass spectrum: m/e 700 (M+,
reference), 622 (13%). Anal. Caled for C45H27N5CU: C, 77.07; H,
3.88; N, 9.99. Found: C, 76.98; H, 3.96; N, 10.20.
Chloromanganese(III) Tetracyanotetraphenylporphine,
Mn[TPP(CN)4]Cl. (CN)4TPP24 ( 200 mg) and 500 mg of manganese
acetate were dissolved in DMF and refluxed for 0.5 h. The solvent was
evaporated in vacuo. The residue was dissolved in chloroform and
chromatographed on 120 g of silica gel. Elution with CHCl3-MeOH
(95:5) yielded successive fractions of the starting material (72 mg)
and of Mn[TPP(CN)4]Cl. The eluate was shaken for 48 h with 2 M
HC1 in excess. Evaporation of the organic layer and recrystallization
from CFHCH-petroleum ether (bp 40-60 °C) yielded 61 mg of
product. Spectrum in CH2CI2: X 400 nm (c 65 000), 510 (130 000), Potential of Dropping Mercury Electrode, volt versus SCE
610 (11800), 675 (14 000), 713 (21200). Anal. Caled for
C48H24ClN8Mn: C, 71.78; , 3.0; N, 13.96. Found: C, 71.06; , 3.06; Figure 2. Polarogram of 0.0023 M H2TPP(Br) in DMF. Supporting
N, 14.15. electrolyte: 0.1 TEAP. Waves identified by Roman numerals in order
Chloroiron(HI) Tetracyanotetraphenylporphine, Fe[TPP(CN)4]CI. of increasing cathodic character.
This metalloporphyrin was prepared by a procedure entirely analogous
to the one used in synthesizing Mn[TPP(CN)4]Cl. Spectrum in
CPI2CI2: X 433 nm (e 89 000), 675 (19 400). Mass spectrum: m/e 768 (drawn-out) analytical geometry. The shape of wave IV tended
(- Cl, 100%), 743 (78%). Anal. Caled for C48H24ClN8Fe: C, 71.70; to beill defined. In view of this situation, the emphasis in this
, 3.01; N, 13.95. Found: C, 71.09; H, 3.33; N, 13.98. paper is placed on the quantitative characterization of waves
Cobalt(II) Tetra- and Tricyanotetraphenylporphine, CoTPP(CN)4 I and II.
and CoTPP(CN)3. Cobaltous acetate (600 mg) dissolved in 40 mL of
MeOH was added to 530 mg of TPP(Br)4 in 400 mL of CHCI3. Cyclic voltammetry yielded four reduction peaks, but only
Successive evaporation, addition of MeOH, and filtration yielded two converse reoxidation peaks which corresponded to waves
CoTPP(Br)4; 530 mg of that product and g of CuCN were refluxed
1
I and II of Figure 2. The peak separation =
(££p,a £p-c)
—

in 35 mL of pyridine for 18 h under an atmosphere of nitrogen. The was approximately 2.2RT/F = 57 mV at relatively slow po-
solvent was evaporated to dryness and the residue extracted with tential scan rates (v < 0.1 V/s) and increased when 0.1 < v <
chloroform and chromatographed on 400 g of silica gel. Gradient 100 V/s. Electrochemical rate constants were estimated by
elution was employed, using chloroform containing ethyl acetate in Nicholson’s method26 for the first two electroreduction pro-
amounts increasing from 2 to 3%. Successive fractions yielded cesses (i.e., those which occurred most readily, at least negative
CoTPP(CN)3 and CoTPP(CN)4. Both compounds were recrystallized
from MeOH and authenticated as follows. potentials) of the moieties H2TPP(X).
CoTPP(CN)3. Spectrum in CH2C12: X 433 nm (e 108 000), 612 Findings were qualitatively similar in the presence of the
(14 800), 635 (13 600). Mass spectrum: m/e 746 (M+, reference,
substituents X = H, Br, Cl, CN, N02, and OEt, and relevant
100%), 721 (6%). Anal. Caled for C47H25N7Co-2H20: C, 72.12; H,
data are summarized in Tables I and II. On the other hand, the
3.73; N, 12.53. Found: C, 70.88; H, 3.67; N, 12.60. electrochemical behavior of the moieties H2TPP(py+),
CoTPP(CN)4. Mass spectrum: m/e 771 (M+, reference, 100%), 746 CuTPP(py+), H2TPP(SCN), and Cu"TPP(SCN) was
(47%), 721 (35%). Anal. Caled for C48H24N8Co-3H20: C, 69.81; H, anomalous, and the appropriate data are presented in Table
3.67; N, 13.57. Found: C, 69.03; H, 3.73; N, 13.66. III. The salient qualitative features of pyridinium and thio-
Results cyanate substitution are outlined below.
1. A fifth electroreduction “step” appeared in solutions of
Comparison of Substituent Effects in Compounds of the Type H2TPP(py+) and CuTPP(py+). This occurred “before” (i.e.,
H2TPP(X) and CuTPP(X). A typical polarogram of at potentials less negative) the waves whose characteristics are
H2TPP(Br) is illustrated in Figure 2. It is qualitatively similar summarized in Tables I and II (and exemplified in Figure 2)
to the previously reported6·710 current-voltage curves of and corresponded to a Nernst reversible electroreduction of
H2TPP and CuTPP exhibiting four successive reduction waves, pyridinium ion, viz.
implicating the porphyrin ring. In all instances, the first two
waves were diffusion controlled and approximated a Nernst- H2TPP(py+) + e =
H2TPP(py) £l/2 =
-0.82 V (1)
reversible one-electron transfer each, under the experimental -0.91 V (2)
conditions normally prevailing in steady-state dc polarography
CuTPP(py+) + e =
CuTPP(py) £,/2 =

at the DME (i.e when the potential was scanned at a rate of

, of H2TPP(SCN) and CuTPP(SCN), a total
2. In the case
1-2 mV/s). These conclusions were substantiated as fol- of six reduction The first (least negative)
waves were observed.
lows. among these had the analytic geometry of a Nernst-reversible
1. Coulometry at controlled potential yielded current-time one-electron transfer. Its half-wave potential was close to the
integrals corresponding to Faraday/mol of porphyrin; the
1 first wave of H2TPP and can therefore be reasonably assigned
relevant current-time curves decayed exponentially which to an analogous electroreduction of the porphyrin ring.
indicated the absence of complications due to chemical reac- Substituent Effects in the Series H2TPP(Br)„ and
tion kinetics. Cu"TPP(Br)n. To complement the picture of electrochemical
2. Plots of log /a vs. log h (where i¿ denotes the relevant— behavior trends emerging from Tables I—III, several poly-
appropriately corrected—limiting current and h the mercury substituted bromotetraphenylporphyrins were investigated.
pressure effective on the DME) yielded slopes of 0.5, as ex- Qualitatively, current-voltage curves were similar to Figure
pected when diffusion control prevails. 2. Quantitative data are summarized in Table IV.
3. Classical polarographic wave analysis plots of the quantity Substituent Effects in the Compounds Mnni[TPP(CN)4]CI,
log (/a
—

i)/i vs. the potential (£) of the DME yielded recip- Fe"I[TPP(CN)4]CI, Co"TPP(CN)3 and CollTPP(CN)4. Cor-
rocal slopes approximating the “Nernst slope” of (RT/F) In responding structures are identified in Figure 1. The electro-
10 = 0.06 V at 25 °C. chemical behavior of the relevant compounds is in striking
The heights (diffusion currents) of the first two waves contradistinction to CuuTPP and its substituted analogues,
(identified by Roman numerals I and II in Figure 2) were equal where the copper is known6·7 to remain in the divalent state,
and yielded consistent polarographic diffusion coefficients. In while the porphyrin ring undergoes stepwise electroreduction.
contradistinction, the heights of waves III and IV were greater In Mnm[TPP(CN)4]Cl, Co"TPP(CN)3, Co"TPP(CN)4, and
by a factor of 1.7 each and exhibited an evidently “irreversible” Fem[TPP(CN)4]Cl we have identified three well-defined
3860 Journal of the American Chemical Society / 101:14 / July 4, 1979
Table I. Polarographic Half-Wave Potentials0 (V) of Monosubstituted Porphyrin Moieties

electroreducible
free base electroreducible
porphyrin £>1/2 £"l/2 £*1/2
-

£'*1/2 metalloporphyrin £*1/2 £"1/2 £,l/2-£",/2

h2tpp* -1.08 -1.46 0.38 CuTPP -1.20 -1.68 0.48
H2TPP(Br)i -0.97 -1.30 0.33 CuTPP(Br) -1.12 -1.59 0.47
H2TPP(C1)-7 -0.95 -1.28 0.33
H2TPP(CN)c -0.84 -1.20 0.36 CuTPP(CN) -0.94 -1.44 0.50
H2TPP(N02K -0.73 -1.04 0.31 CuTPP(NQ2) -0.87 -1.31 0.44
H2TPP(OEt)« -1.12 -1.46 0.34

Waves identified by Roman numerals in order of increasing cathodic character, as shown in Figure 2. 6
0

d
\/ =
—2.34, £',vi/2 =
—2.49.
£m,/2 = -2.10, £ivi/2 = -2.33. £ ,/2 = 2.08, £IV,/2 = -2.28. £ 1/2 = -2.06, £lv1/2 = -2.26./£iii1/2 -2.44.
0 f =
-1.85, £1v,/2 =

*£mi/2 = 2.35.

Table II. Electrochemical Rate Constants0 (£s) and Polarographic

Diffusion Coefficients (£>) of Monosubstituted Free Base
Porphyrins
electroreactive D X 106, ks X 102, cm/s
moiety cm2/s wave I wave II
h2tpp 1.0 1.0 0.8
H2TPP(Br) 1.5 3.7 4.6
H2TPP(C1) 1.2 3.1 3.5
H2TPP(CN) 1.9 1.2 0.7
H2TPP(N02) 1.8 5.8 4.1
H2TPP(OEt) 1.3 1.4 2.3
0
Effective at the relevant conditional standard (“formal”) po-
tential.

Figure 4. Plot of half-wave potentials of wave 11 vs. Hammett’s .

In general agreement with previously published findings

emanating from several laboratories, it is apparent that in
monosubstituted TPP moieties electron-withdrawing groups
facilitate reactions 3 and 4 by shifting each of the relevant
half-wave potentials (i.e., £'1/2 on the one hand and £’iii/2 on
the other hand) to more positive (more anodic) values. The
sequence27 which transpires from Tables I and III is
OEt < < Br < Cl < SCN < CN < N02 (5)
This series is accounted for by classical intramolecular inter-
actions. Indeed, the maximum potential shift (0.35 V) was
engendered by the substituent with the greatest electron af-
Figure 3. Plot of half-wave potentials of wave I vs. Hammett’s finity, viz., N02. This is due to a corresponding change in the
energy level of the lowest unoccupied molecular orbital
(LUMO), because the substituent’s electron-withdrawing
voltammetric reduction waves, one of which implicates a effect produces a concomitant decrease in the electron density
change in the oxidation state of the metal. Results are sum- of the conjugated tetrapyrrole ring system. The potential shifts
marized in Table V. in series 5 evidently parallel the electron-withdrawing char-
acter of the substituents. The only electron-releasing group
Discussion
in that series, OEt, produced—as expected—the opposite ef-
Interpretative comments are offered below, in the context fect, viz., a cathodic potential shift. Remarkably, the insertion
of the results presented in Tables I-V. The discussion will be of divalent copper (which was electroinactive under the ex-
focused on the two monoelectronic reduction steps corre- perimental conditions) in the tetrapyrrole ring did not affect
sponding to waves I and II in Figure 2, which (1) occur at the the substituent shifts in series 5 (even though copper did have
least negative potentials; (2) yield well-defined Nernst-re- an appreciable effect on the absolute values of the half-wave
versible classical dc polarograms; (3) are known10™20 to im- potentials, vide infra); this is reasonable, because the LUMO
plicate the porphyrin ring in the reactions energy level change is thermodynamically equivalent to an
enhancement of electron affinity of the porphyrin ring, re-
TPP-moiety + e =
anion radical (3)
gardless of copper insertion. At this point, it is worthwhile to
anion radical + e =
dianion (4) observe that, for a given electron-withdrawing substituent, the
Jordan et al. / Electroreduction of Porphyrins and Metalloporphyrins 3861

Table III. Data Illustrating the Anomalous Electrochemical Behavior of Pyridinium and Thiocyanato Substituted Porphyrins and
Metalloporphyrins"
electroreactive half-wave potentials rate parameters
moiety £py+—py £' 1/2 E" 1/2 £'./2-£ui/2 D X 106 fc'sX 102 kns X 102

H2TPP(py+) -0.82 -1.06 -1.62 0.56 1.5 1.3 2.7

H2TPP(py+) -0.91 -1.17 -1.62 0.45
H2TPP(SCN)* -0.89 -1.15 0.26 1.3 5.6
CuTPP(SCN)" -1.05 -1.33 0.28
"
Roman numeral superscripts identify (in order of increasing cathodic character) successive electroreduction steps implicating the tetrapyrrole
porphyrin ring. Em i/2 = -1.26,£IV l/2 = -1.62, £v1/2 -2.35, £vii/2=- 2.45. c£iii,/2 = —1.47,£ivi/2 = —1.90, £v 1/2 = —2.35, £v,i/2
b =

= -2.50.

Table IV. Electroreduction Parameters of Polysubstituted Bromotetraphenylporphyrins“

electroreactive half-wave potentials rate parameters
moiety £'l/2 £1!i/2 Eh/2-E" ,/2 D X 106 fclsX 102 fc"sX 102

h2tpp* -1.08 -1.46 0.38 1.0 1.0 0.8

H2TPP(Br)*c -0.97 -1.30 0.33 1.5 3.7 4.6
H2TPP(Br)2,abc -0.87 -1.16 0.29
H2TPP(Br)2,ac -0.86 -1.14 0.28 1.6 1.0 0.8
H2TPP(Br)3¿ -0.80 -1.05 0.25
"
See footnote a, Table III. b
Data repeated from Tables I and II, in order to facilitate comparison. c
£m i/2 =
-24 1,£,v,/2= -2.30. dE"\n
=
-2.18, £1v,/2 = -
-2.36.

Table V. Monoelectronic Reduction Waves of Metalloporphyrin Moieties Depicted in Figure 2

3rd wave
1st wave 2nd wave £ i/2
reduction £ 1/2 per reduction £ i / per
2 reduction per
compound site" £i/2 cyano site" £l/2 cyano site" £i/2 cyano
MnmTPPCl -0.220 porphyrin -1.320 porphyrin -1.760
Mn,n —
11 -0.010
0 052
-0.360
0.24
-0.730
°·26
MnmTPP(CN)4Cl ring ring
FemTPPCl
Fem Feii -0.170 0.013
F»I1
re — Fe1
re -1.040 0.20 porphyrin
—
1.700
q 24
u'4
FemTPP(CN)4Cl -0.120 -0.260 ring -0.730
Co"TPP -0.820 porphyrin -1.920
0 13 0.27
Co"TPP(CN)3 Co" —
Co1 -0.420 ring -1.100
046 0.25
Co"TPP(CN)4 b -0.265 -0.850
*
Assigned in references 7, 13, and 39. A
“
Co(III)-Co(II) wave might have been observed at more positive potentials in solutions containing
ComTPP moieties.

observed anodic shift of the reduction potential (facilitating prevalence of resonance interations are particularly convincing
reduction) is at least five times larger when pyrroles, instead in this context. On the other hand, we now recognize that re-
of phenyls, are substituted in tetraphenylporphyrins. For in- liance on p and in two of our earlier papers15·19 was in error,
stance, in the First reduction step, four cyano groups induce the even though other authors have correctly used p and for
shift \/
=
+0.96 V (referred to the half-wave potential of phenyl-substituted moieties (where there are no resonant in-
H2TPP), when the pyrroles are substituted, and only AEi/2 teractions between the x-electron system of the porphyrin ring
=
+0.17 V when the phenyls are substituted.15,17a Plots28 of and the substituents on the phenyls).
the observed half-wave potential vs. Hammett’s ~ are shown The positive assignments for pT in eq 7 and 8 are consistent
in Figures 3 and 4.29 They substantiate the prevalence of linear with the a priori plausible (and experimentally substantiated)
free energy relationships, viz., enhancement of electron affinity in the presence of electron-
withdrawing substituents, which engender a decrease of elec-
]/2 =
~ (6) tron density in the porphyrin macrocycle. The pT assignments
yielding obtained in the present study illustrate the drastic effect of
pyrrole sub~*itution in porphyrins. Analogous large ef-
from wave I, =
+0.28 ± 0.002 for H2TPP(X) fects—and excellent linearity with ~—have been substan-
tiated by Pillsbury and Busch36 for substituents directly bound
and +0.29 ± 0.002 for CuTPP(X) (7) to conjugated systems of other macrocycles. On the other hand,
from wave II, px =
+0.32 ± 0.002 for H2TPP(X) entirely different p values have been reported16·17 for elec-
and +0.29 ± 0.002 for CuTPP(X) tron-withdrawing substituents on the peripheral phenyl groups
(8) of TPP, whose “efficiency” in lowering the electron density of
The rationale for using in eq 6 the parameters pr and ~ the porphyrin ring core appears to be much smaller.
(rather than p and ) is predicated on relevant fundamental As far as sequential polysubstitution is concerned, the
considerations30 and evidence available in the literature9·31™34 half-wave potential shifts in the bromo-TPP series (Table IV,
that reductive electron transfer to porphyrins implicates di- columns 1-3) warrant a further comment. The relevant data
rectly the x-bonded ring system to which the ß substituents are plotted in Figure 5. It is apparent that £,i/2 and £'I1i/2
are resonatively conjugated. Raman data32 substantiating the shifted anodically, as a function of the number of bromine
3862 Journal of the American Chemical Society / 101:14 / July 4, 1979

for identifying electron-acceptor sites in metalloporphyrins.

Invariant half-wave potential shifts of +0.25 V per cyano
substituents indicate electroreduction of the organic ligand,
regardless of the electroreducibility of the inserted cation. On
the other hand, potential shifts engendered by cyano substi-
tution are smaller and scattered when an inserted metal is
electroreduced. For optimum differentiation, reliance on the
first (least cathodic) poloarographic half-wave potential is
recommended.
In contradistinction to the drastic potential shifts, our
/3-pyrrole substituents did not change significantly the diffusion
coefficients of the parent porphyrin moieties, nor their elec-
troreduction rate constants. The relevant values, listed in Ta-
bles II—IV, are entirely comparable to those reported in the
literature16,37 for other porphyrins.

References and Notes

Figure 5. Plot of half-wave potentials as function of bromine substitution. (1) Supported by Centre National de la Recherche Scientifique (CNRS), France,
The isomers ab and ac are identified in Figure 1. and by Research Grant 794 from the Scientific Affairs Division of the North
Atlantic Treaty Organization (NATO).
(2) Laboratoire d’Electrochimie et de Chimie Physique du Corps Solide, E.R.A.
au CNRS, No, 468, Universíté Louis Pasteur, Strasbourg, France.
substituents.38 However, the shift was nonlinear, and decreased (3) Laboratoire de Chimie Organique Biologique, Universíté Louis Pasteur,
in magnitude as the number of bromines increased. This be- Strasbourg, France.
(4) Department of Chemistry, Pennsylvania State University, 152 Davey
havior is partly similar and partly at variance to that previously Laboratory, University Park, Pa. 16802.
reported15 in the polysubstituted cyano-TPP series. The sim- (5) J. Jordan and T. M. Bednarski, J. Am. Chem. Soc., 86, 5690 (1964).
(6) D. W. Clack and N. S. Hush, J. Am. Chem. Soc., 87, 4238 (1965).
ilarity is qualitative in the sense that stepwise bromo and cyano (7) R. H. Felton and H. Linschitz, J. Am. Chem. Soc., 88, 1113 (1966).
substitution both produced anodic half-wave potential shifts. (8) T. M. Bednarski and J. Jordan, J. Am. Chem. Soc., 89, 1552 (1967).
The difference is in the quantitative aspects of the half-wave (9) A. Stanienda, Z. Naturforsch. B, 23, 147 (1968).
(10) G. Peichal Heiling and G. Wilson, Anal. Chem., 43, 545, 550 (1971).
potential shifts: each cyano substitution shifted El\ji and (11) G. H. Fuhrhop, K. M. Kadish, and D. G. Davis, J. Am. Chem. Soc., 95, 5140
Eu 1/2 approximately by a constant 0.25 V; in contradistinction, (1973) .

the effect of bromo substitution was not only nonlinear, but also (12) D. Lexa and M. Relx, J. Chim. Phys. Phys.-Chim. Biol., 71,511 (1974).
(13) D. Lexa, M. Momenteau, J. Mlspelter, and J. M. Hoste, Bioelectrochem.
appreciably smaller, viz., 0.3-0.4 V for the cumulative effect Bioenerg., 1, 108 (1975).
of three bromine substituents vs. 0.75 for the cumulative shift (14) K. M. Kadish, G. Larson, D. Lexa, and M. Momenteau, J. Am. Chem. Soc.,
97, 282 (1975).
by three cyano substituents. The nonadditivity of bromine (15) H. J. Callot, A. Giraudeau, and M. Gross, J. Chem. Soc. Perkin Trans. 2,
substitution cannot be explained by polar or mesomeric in- 1321 (1975).
(16) K. M. Kadish, . M. Morrison, L. A. Constant, L. Dickens, and D. G. Davis,
teractions. However, it can reasonably be ascribed to steric J. Am. Chem. Soc., 98, 8387 (1976)
interactions between the bromines and the phenyls in “peri” (17) K. M. Kadish and . M. Morrison, J. Am. Chem. Soc., 98, 3326 (1976); Inorg.
Chem., 15, 980 (1976); Bioinorg. Chem., 7, 107 (1977).
positions. These may minimize the effect of the phenyls which (18) F. A. Walker, D. Beroiz, and K. M. Kadish, J. Am. Chem, Soc., 98, 3484
become more orthogonal and/or induce a deformation of the (1976).
molecule (e.g., between pyrroles and meso bridges) which (19) I. Ezhar, A. Giraudeau, M. Gross, H. J. Callot, and J. Jordan, Bioelectrochem.
would tend to eliminate an eclipsed bromine-phenyl confor- Bioenerg., 3, 519 (1976).
(20) For review see J. H. Fuhrhop in "Porphyrins and Metalloporphyrins”, K.
mation. The steric hindrance (which tends to reduce potential M. Smith, Ed., Elsevier, Amsterdam, 1975, Chapter 14, pp 593-623.

shifts) can be expected to become gradually more effective (21) J. E. Falk, "Porphyrins and Metalloporphyrins", Elsevier, Amsterdam,
1964.
when several bromine substituents are successively involved, (22) M. Tezuka, Y. Ohkatsu, and T. Osa, Bull. Chem. Soc. Jpn., 49, 1435
and thus account for the observed nonlinearity in Figure 5. As (1976) .

(23) M. L. McGlashan, Pure Appl. Chem., 21, 3 (1970).

in the cyanoporphyrin series15 the anodic shift is larger for (24) H. J. Callot, Tetrahedron Lett., 4987 (1973); Bull. Soc. Chim. Fr„ 1492
H2TPP(Br)2ac than for H2TPP(Br)2a¡J, and again parallels an (1974) .

increased bathochromic shift in the visible part of the electronic (25) A. G. Padilla, S. M. Wu, and H. S. Shine, J. Chem. Soc., Chem. Commun.,
237 (1976).
spectra. (26) R. S. Nicholson, Anal. Chem., 37, 1351 (1965).
Insertion of copper, which is not electroreducible, in the (27) We wish to emphasize that series 5 applies to shifts of either Éy2 or
but has no relevance to the differences (E'va —

E'va) listed In the last

monosubstituted porphyrins (Figures 3 and 4) did not modify column of Table I.
the E i/2 shifts engendered by the electron-withdrawing sub- (28) P. Zuman, Collect. Czech. Chem. Commun., 25, 3225 (1960).
stituents on the periphery of the porphyrin ring: the effect was (29) H2TPP(SCN) was advisedly omitted from Figures 3 and 4, for two reasons,
viz., anomalous polarographic behavior (six reduction waves, see Table
simply a constant (parallel) displacement of the Hammett III, footnote b) and unavailability of an appropriate assignment of ~ for
plots. The insertion of electroreducible cations [e.g., Fe(III), the substituent SCN.
O. Exner in “Advances in Linear Free
(30) See, e.g., Energy Relationships",
Mn(III)] into our pyrrole-substituted cyanoporphyrins (Table N. B. Chapman and J, Shorter, Eds., Plenum Press, New York, 1972,
V) yielded substituent effects on potential shifts, which de- Chapter 11, pp 1-69; C. D. Johnson, "The Hammett Equation", University
Press, Cambridge, 1973.
pended on the electron acceptor site, viz., (a) when the por- (31) M. Zerner and M. Gouterman, Theor. Chim. Acta, 4, 44 (1966).
phyrinic macrocycle was electroreduced, the potential shift was (32) W. H. Fuchsman, Q. R. Smith, and . M. Stein, J. Am. Chem. Soc., 99, 4190
not affected by the presence of the metal and remained a re- (1977) .

(33) C. Weiss, H. Kobayashl, arid M. Gouterman, J. Mol. Spectrosc., 16, 415

markably invariant (0.250 ± 0.002) V per cyano substituent; (1965).
(b) when the inserted cation was electroreduced the potential (34) . H. Inhoffen and P. Jager, Tetrahedron Lett., 1317 (1964).
shifts engendered by cyano substitution were unsystematically (35) The appropriateness of our choice of the (in preference to or 0)
is borne out by the excellent linearity of the plots in Figures 3 and 4.
scattered and generally smaller [e.g., 0.013 V per cyano sub- (36) D. G. Pillsbury and D. H. Busch, J. Am. Chem. Soc., 98, 7836 (1976).
stituent in FemTPP(CN)4Cl], (37) C. M. Newton and D. G. Davis, J. Magn. Reson., 20, 446 (1975).
The above “difference in sensitivity to /3-pyrrole substitu- (38) The tetrabromo derivative24 was Insoluble in DMF.
(39) L. J. Boucher and . K. Garber, Inorg. Chem., 9, 2644 (1970).
tion” provides an interesting prima facie diagnostic criterion (40) A. W. Johnson and M. Winter, Chem. Ind. (London), 351 (1975).