porphyrin products obtained were eluted from the column
in the following order: 2 (47 mg, 7.1%), 3 (121 mg, 8.0%) and 1
(17 mg, 1.6%). Compound 3: δH (500 MHz; CDCl3) 8.95 (4 H, s,
β-H), 8.86 (2 H, d, J 4.5 Hz, β-H), 8.73 (2 H, d, J 4.5 Hz, β-H),
7.38–6.65 (39 H, m, ArH), 5.06 (6 H, m, PhCHC3H7), 1.00–
0.16 (24 H, m, CH2CH2), 0.12 (6 H, t, J 7.4, CH3), Ϫ0.06 (6 H,
t, J 7.4, CH3), Ϫ0.20 (6 H, t, J 7.4, CH3), Ϫ2.42 (2 H, s, NH);
δC (68 MHz; CDCl3) 159.25, 159.11, 142.69, 142.61, 142.29,
129.44, 129.32, 128.23, 128.11, 127.93, 127.02, 126.92, 125.83,
125.71, 120.96, 113.16, 106.61, 106.29, 106.15, 79.84, 79.70,
79.52, 40.18, 40.08, 39.87, 18.32, 18.12, 18.02, 12.88, 12.82;
δF (254 MHz; CDCl3–CFCl3) Ϫ137.37 (2 F, dd, J 24.25 and 8.43
Hz, ortho-F), Ϫ154.59 (1 F, t, J 21.28 Hz, para-F), Ϫ163.39
(2 F, dt, J 23.02, 21.53 and 8.43 Hz, meta-F); λmax (CH2Cl2)/nm
β-H), 7.31–6.55 (26 H, m, ArH), 5.09 (2 H, t, J 6.53 Hz,
PhCHC3H7), 5.02 (2 H, dd, J 8.98 and 4.62 Hz, PhCHC3H7),
0.79–0.22 (16 H, m, PhCHCH2CH2CH3), 0.04 (6 H, t, J 7.05
Hz, PhCHCH2CH2CH3), Ϫ0.02 (6 H, t, J 7.26, PhCHCH2-
CH2CH3), Ϫ2.55 (2 H, s, NH); δC (68 MHz; CDCl3) 159.11,
158.79, 142.57, 142.23, 129.80, 128.25, 128.11, 127.10, 125.81,
125.59, 120.05, 115.68, 106.07, 106.03, 79.72, 79.40, 40.26,
39.83, 18.22, 18.04, 12.94, 12.82; δF (254 MHz; CDCl3, CFCl3)
Ϫ137.22 (dd, J 24.21 and 8.46 Hz, ortho-F), Ϫ137.42 (dd,
J 24.21 and 8.46 Hz, ortho-F), Ϫ153.52 (t, J 20.55 Hz, para-F),
Ϫ162.81 (m, meta-F); λmax (CH2Cl2)/nm 417 (ε/m2 molϪ1
3.42 × 104), 512 (2.04 × 103), 543 (329), 585 (730), 640 (74);
ϩ
ϩ
ESI-MS m/z 1387 (Mϩ , 100%); HRMS-FAB : found M ,
ؒ
1386.5084, C84H68F10N4O4 requires m/z 1386.5081.
418 (ε/m2 molϪ1 3.72 × 104), 512 (2.04 × 103), 544 (402), 587
(664), 641 (155); ESMS m/z 1593.4 (Mϩ , 100%); HRMS-FAB
ϩ
ؒ
Chloroiron 5,10,15,20-tetrakis[(R,R)-2,6-bis(1-phenylbutoxy)-
phenyl]porphyrin (Fe1)
m/z Mϩ, 1592.7325, C104H95F5N4O6 requires m/z 1592.7328.
Iodine (33 mg, 0.130 mmol) and Fe(CO)5 (0.1 cm3, 0.760 mmol)
were added to a solution of porphyrin 1 (56 mg, 0.031 mmol)
in toluene (150 cm3) under nitrogen. The mixture was stirred
under reflux until no more free-base could be detected by UV–
Vis analysis (2.5 h) and the solution was cooled to room
temperature and left stirring overnight under aerobic con-
ditions. Removal of the solvent with a rotary evaporator gave
a brownish residue which was dissolved in dichloromethane,
washed with water and dried (MgSO4). Column chroma-
tography of the crude product mixture on silica gel using
dichloromethane as eluant gave two main bands, the first was
bright red and was identified by UV–Vis spectroscopy to be a
hydroxo-iron porphyrin by comparison with literature spectra
for the hydroxoiron() meso-tetrakis(pentafluorophenyl)-
porphyrin.31 The second is believed to have iodide as the axial
ligand on the iron porphyrin arising from the iodine used in
the metallation process. The two fractions were converted with
10% hydrochloric acid solution to the same metalloporphyrin
with an axial chloride. The solution was dried over NaCl and
solvent removal gave the iron() porphyrin Fe1 (50 mg, 85%);
λmax (CH2Cl2/nm) 376 (ε/m2 molϪ1, 5.20 × 103), 421 (1.02 × 104),
510 (1.49 × 103), 584 (461); ESI-MS m/z 1853.7 [(M ϩ 1) Ϫ Cl,
100%].
5,15-Bis(pentafluorophenyl)-10,20-bis[(R,R)-2,6-bis(1-phenyl-
butoxy)phenyl]porphyrin (2)
A solution of compound 6 (785 mg, 1.51 mmol) and penta-
fluorobenzaldehyde (296 mg, 1.51 mmol) in chloroform
(150 cm3) was reacted with BF3ؒOEt2 and the products were
worked up as described for porphyrin 1 to give porphyrin 2
(184 mg, 18%); δH (270 MHz; CDCl3) 8.94 (4 H, d, J 4.5 Hz,
β-H), 8.78 (4 H, d, J 4.5 Hz, β-H), 7.38 (2 H, t, J 8.5 Hz, ArH),
7.97 (12 H, m, ArH), 6.76 (12 H, m, ArH), 5.09 (4 H, dd, J 4.8
and 6.0 Hz, PhCHC3H7), 0.97–0.82 (8 H, m, PhCHCH2C2H5),
0.56 (8 H, m, PhC2H3CH2CH3), 0.26 (12 H, t, J 7.2 Hz, CH3),
Ϫ2.55 (2 H, s, NH); δC (68 MHz; CDCl3) 159.03, 142.31,
129.96, 128.05, 126.96, 125.51, 120.15, 114.55, 106.43, 80.02,
40.20, 18.38, 12.98; δF (254 MHz; CDCl3–CFCl3) Ϫ137.42 (4 F,
dd, J 24.26 and 8.91 Hz, ortho-F), Ϫ153.71 (2 F, t, J 20.80 Hz,
para-F), Ϫ162.97 (4 F, dt, J 8.93 Hz, meta-F); λmax (CH2Cl2)/
nm 417 (ε/m2 molϪ1 2.75 × 104), 511 (1.67 × 103), 543 (381),
588 (538), 642 (262); ESI-MS m/z 1387.4 (Mϩ , 100%); HRMS-
ؒ
FABϩ m/z Mϩ, 1386.5083, C84H68F10N4O4 requires m/z
1386.5081.
5,10,15-Tris(pentafluorophenyl)-20-[(R,R)-2,6-bis(1-phenyl-
butoxy)phenyl]porphyrin (4) and 5,10-bis(pentafluorophenyl)-
15,20-bis[(R,R)-2,6-bis(1-phenylbutoxy)phenyl]porphyrin (5)
Chloroiron 5,15-bis(pentafluorophenyl)-10,20-bis[(R,R)-2,6-
bis(1-phenylbutoxy)phenyl]porphyrin (Fe2)
Compounds 7 (660 mg, 1.28 mmol) and 8 (400 mg, 1.27 mmol)
were reacted in chloroform (256 cm3) with pentafluorobenz-
aldehyde (308 mg, 3.16 mmol) as described above for porphyrin
1. The products were eluted from a silica gel column using
dichloromethane–hexane (60 : 40, v/v) in the following order:
porphyrin 4 (75 mg, 8.1%), 2 (96 mg, 8.8%) and 5 (24 mg, 2.2%).
Porphyrin 2 (44 mg, 0.032 mmol), Fe(CO)5 (0.1 cm3, 0.760
mmol) and iodine (33 mg, 0.130 mmol) were reacted in toluene
(15 cm3) using the same procedure as for Fe1 to give Fe2
(38 mg, 8%); λmax (CH2Cl2/nm) 373 (ε/m2 molϪ1 4.33 × 103), 417
(8.36 × 103), 508 (973), 605 (445); ESI-MS m/z 1440.2 (M Ϫ Cl,
100%); HRMS-FABϩ m/z Mϩ, 1440.4281, C84H68F10FeN4O4
requires m/z 1440.4274.
Porphyrin 4. δH (500 MHz; CDCl3) 8.96 (2 H, d, J 4.3 Hz, β-H),
8.90 (2 H, d, β-H), 8.88 (2 H, d, β-H), 8.76 (2 H, d, J 4.3 Hz,
β-H), 7.39 (1 H, t, J 8.6 Hz, ArH), 7.07 (2 H, t, J 7.1 Hz, ArH),
7.03 (4 H, t, J 7.4 Hz, ArH), 6.77 (4 H, d, J 7.1 Hz, ArH), 6.74
(2 H, d, J 8.6 Hz, ArH), 5.08 (2 H, dd, J 8.6 and 4.8 Hz,
PhCHC3H7), 0.95–0.88 (2 H, m, PhCHCH2CH2CH3), 0.79–
0.72 (2 H, m, PhCHCH2CH2CH3), 0.49–0.39 (4 H, m, PhCH-
CH2CH2CH3), 0.14 (6 H, t, J 7.3 Hz, CH3); δC (68 MHz;
CDCl3) 158.83, 142.15, 128.17, 127.14, 125.53, 106.29, 79.96,
40.12, 18.22, 12.90; δF (254 MHz; CDCl3–CFCl3) Ϫ137.10 (dd,
J 7.87 and 23.6 Hz, ortho-F), Ϫ137.46 (dd, J 7.87 and 23.58 Hz,
ortho-F), Ϫ152.47 (t, J 22.00 Hz, para-F), Ϫ152.68 (t, J 22.00
Hz, para-F), Ϫ162.37 (m, meta-F); λmax (CH2Cl2)/nm 415
Chloroiron 5-pentafluorophenyl-10,15,20-tris[(R,R)-2,6-bis(1-
phenylbutoxy)phenyl]porphyrin (Fe3)
Porphyrin 3 (50 mg, 0.031 mmol) and Fe(CO)5 (0.1 cm3,
0.760 mmol) were dissolved in toluene (15 cm3) and reacted
with iodine (27 mg, 0.106 mmol) using the same procedure as
for Fe1 to give Fe3 (45 mg, 85%); λmax (CH2Cl2/nm) 373 (ε/m2
molϪ1 4.79 × 103), 420 (8.79 × 103), 508 (1.25 × 103), 577 (475),
647 (377); ESI-MS m/z 1647.8 (M Ϫ Cl, 100%); HRMS-FABϩ
m/z Mϩ, 1646.6528, C104H95F5FeN4O6 requires m/z 1646.6521.
(ε/m2 molϪ1 2.50 × 104), 510 (1.62 × 103), 539 (252), 585 (561),
Chloroiron 5,10,15-tris(pentafluorophenyl)-20-[(R,R)-2,6-bis-
(1-phenylbutoxy)phenyl]porphyrin (Fe4)
Porphyrin 4 (20 mg, 0.017 mmol) and Fe(CO)5 (0.1 cm3, 0.760
mmol) were reacted with iodine (12 mg, 0.048 mmol) in toluene
(10 cm3) using the method for Fe1 to give Fe4 (16 mg, 74%); λmax
(CH2Cl2/nm) 354 (ε/m2 molϪ1, 5.83 × 103), 413 (1.12 × 104), 505
639 (100); FABϩ-MS m/z 1181 (Mϩ , 90%); HRMS-FAB
ϩ
ؒ
m/z Mϩ, 1180.2841, C64H39F15N4O2 requires m/z 1180.2834.
Porphyrin 5. δH (270 MHz; CDCl3) 8.98 (2 H, s, β-H), 8.89
(2 H, d, J 5.83 Hz, β-H), 8.88 (2 H, s, β-H), 8.76 (2 H, d, J 4.86 Hz,
1152
J. Chem. Soc., Perkin Trans. 2, 2001, 1145–1153