1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

6 Experimental Section
6.2.4.5 5 4 ,10 4 ,15 4 ,20 4 -Tetra-t-Butyl-[3 , 5 2 ]-Ethano-5 6 -Methyl-3 1 -Oxo-5,10,15,20-
O
150
Tetraphenylporphyrinato-Nickel(II), Ni(II)-53
In a 100 mL round bottom flask with reflux condenser,
porphyrin ethanoic acid 51 (100 mg, 110 μmol) and 282 mg
(1.1 mmol, 10 eq.) of Ni(acac)2 are dissolved in 40 mL of
toluene and heated under reflux (∼135 °C) for 3 h. After
evaporation of the solvent, the crude product is filtered over
a silica plug to remove residing metal salts (eluent: CH2Cl2,
polarity can be adjusted by addition of ethyl acetate) and
further subjected to step b. of GP III: CH2Cl2 (50 mL), C2O2Cl2
(2 mL); CH2Cl2 (30 mL), SnCl4 (1.0 mL, 8.54 mmol). Leaving out
the acidic demetallation step, the crude product obtained after work-up is purified by FC
(silica, hexanes and CH2Cl2 in a 1 : 1 ratio) to give 54 mg (56.8 μmol) of pure Ni(II)-53 as dark
green powder, equiv. to 51.7 % yield based on 51.
1 H NMR (300 MHz, rt, CDCl3): δ [ppm] = 0.93 (s, 3 H, CH3), 1.43 (s, 9 H, t-BuH), 1.53 (2s,
9+9 H, t-BuH), 1.54 (s, 9 H, t-BuH), 4.16 (d, 2 J = 11.9 Hz, 1 H, CH2), 5.60 (d, 2 J = 11.9 Hz, 1 H,
CH2), 7.17 (d, 4 J = 1.5 Hz, 1 H, Ar’H), 7.61 (d, 4 J = 1.5 Hz, 1 H, Ar’H), 7.67 (d, 3 J = 7.2 Hz, 6 H,
ArH), 7.88 (br s, 4 H, ArH), 8.55 (d, 3 J = 4.9 Hz, 1 H, β-H), 8.62 (m, 5 H, β-H), 8.75 (d,
3 J = 4.9 Hz, 1 H, β-H), 9.15 (s, 1 H, β-H).
13 C NMR (75.5 MHz, rt, CDCl3): δ [ppm] = 22.3, 31.4, 31.6, 34.7, 34.9, 53.6, 112.0, 118.2,
120.4, 124.0 (two signals), 124.1, 124.6, 127.2, 127.8, 132.3, 132.7, 132.9, 133.0, 133.3,
133.4, 134.6, 135.8, 136.2, 136.6, 137.0, 137.1, 138.2, 140.0, 140.3, 141.1, 143.0, 143.2,
143.4, 143.8, 144.0, 144.5, 150.7, 150.8, 151.0, 152.1, 192.3.
MS (MALDI-TOF, no matrix): m/z (%) = 951 (100) [MH] + .
IR (ATR): 𝜈� [cm -1 ] = 3030, 2962, 2904, 2870, 1683, 1543, 1505, 1479, 1461, 1396, 1350, 1268,
1199, 1162, 1111, 1069, 1050, 1011, 842, 818, 795, 717.
UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 443 (184000), 560 (9800), 605 (10600).
EA: C63H62N4NiO·0.5 H2O·0.5 C6H14. Calc.: C 79.11, H 7.04, N 5.59; found: C 79.03, H 6.94,
N 5.70.
N
N
Ni
N
N
Ni(II)-53
C 63 H 62 N 4 NiO
M = 949.89 g·mol -1