1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

Experimental Section 6
6.2.5.12 αα - 5 4 , 10 4 , 15 4 , 20 4 - Tetra - t - Butyl - 5 6 , 15 6 - Dimethyl - 5 , 10 , 15 , 20 -
HO 2 C
Tetraphenylporphyrinato-5 2 ,15 2 -Diethanoic Acid-Nickel(II), Ni(II)-77
Porphyrin diethanoic acid 77 (200 mg, 203 μmol) is
suspended in toluene and acidified with some drops of
glacial HOAc until a clear solution is obtained. Then,
261 mg (1.02 mmol, 5 eq.) of Ni(acac)2 are added and
the mixture is stirred under reflux conditions for 3 h
before the solvents are evaporated completely and the
residue is subjected to FC (silica, toluene : THF = 9 : 1) to
furnish 182 mg (175 μmol) of pure Ni(II)-77 as red
powder equiv. to 86.2 % based on 77.
1 H NMR (400 MHz, rt, THF-d8): δ [ppm] = -1.55 (2s, 18+18 H, t-BuH), 1.76 (s, 3 H, CH3), 3.19
(s, 2 H, CH2), 7.50 (d, 4 J = 1.4 Hz, 2 H, Ar’H), 7.62 (d, 4 J = 1.7 Hz, 2 H, Ar’H), 7.74 (d, 3 J = 8.5 Hz,
4 H, ArH), 7.96 (d, 3 J = 8.2 Hz, 4 H, ArH), 8.56 (d, 3 J = 4.9 Hz, 4 H, β-H), 8.69 (d, 3 J = 4.9 Hz, 2 H,
β-H), 10.2 (s br, 2 H, COOH).
13 C NMR (100.5 MHz, rt, THF-d8): δ [ppm] = 21.8, 31.9, 35.4, 35.5, 40.2, 117.1, 119.7, 124.7,
125.5, 125.8, 132.8, 133.1, 134.5, 137.0, 138.4, 139.2, 139.8, 143.6, 144.0, 151.4, 151.9,
172.5.
N
N
Ni
N
N
Ni(II)-77
C 66 H 68 N 4 NiO 4
M = 1039.96 g·mol -1
CO 2 H
MS (FAB+, NBA): m/z (%) = 1038 (100) [M] +· , 993 (10) [M-CO2H] +· .
IR (ATR): 𝜈� [cm -1 ] = 3030, 2964, 2905, 2869, 1726, 1694, 1605, 1554, 1509, 1461, 1422, 1394,
1352, 1267, 1205, 1074, 1004, 817, 799, 738, 715.
UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 415 (247500), 528 (20100).
EA: C66H68N4NiO4·THF. Calc.: C 75.60, H 6.89, N 5.04; found: C 75.53, H 7.04, N 5.01.
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