1.1 Porphyrins - Friedrich-Alexander-Universität Erlangen-Nürnberg

6 Experimental Section
6.2.5.13 αα-5 4 ,10 4 ,15 4 ,20 4 -Tetra-t-Butyl-[3,5 2 ],[15 2 ,17]-Diethano-5 6 ,15 6 -Dimethyl-3 1 ,17 1 -
O
174
N
Dioxo-5,10,15,20-Tetraphenylporphyrinato-Nickel(II), Ni(II)-67
N
Ni
N
Utilizing step b. of GP III, the following substances and
amounts are reacted with nickel(II) porphyrin diethanoic acid
Ni(II)-77 (150 mg, 144 μmol): C2O2Cl2 (2.5 mL), CH2Cl2 (30 mL);
SnCl4 (1.5 mL), CH2Cl2 (30 mL). Leaving out the demetallation
step, FC over silica with CH2Cl2 and hexanes as eluent (ratio:
3 : 1) furnishes pure Ni(II)-67 eluting as second major fraction.
The product appears as green crystalline solid in 77 mg
(76 μmol) yield, equiv. to 53 % based on Ni(II)-77.
1 H NMR (400 MHz, 40 °C, THF-d8): δ [ppm] = 1.03 (s, 6 H, CH3), 1.44 (s, 18 H, t-BuH), 1.52 (s,
9 H, t-BuH), 1.56 (s, 9 H, t-BuH), 4.09 (d, 2 J = 12.0 Hz, 2 H, CH2), 5.45 (d, 2 J = 11.6 Hz, 2 H,
CH2), 7.27 (d, 4 J = 1.6 Hz, 2 H, Ar’H), 7.35 (br s, 1 H, ArH), 7.63 (d, 4 J = 2.0 Hz, 2 H, Ar’H), 7.73
(d, 3 J = 8.4 Hz, 2 H, ArH), 7.80-7.96 (br m, 2+1 H, ArH), 8.32 (br s, 1 H, ArH), 8.53 (d,
3 J = 4.8 Hz, 2 H, β-H), 8.62 (d, 3 J = 4.9 Hz, 2 H, β-H), 8.83 (s, 2 H, β-H).
13 C NMR (100.5 MHz, 40 °C, THF-d8): δ [ppm] = 22.5, 31.9, 32.1, 35.6, 35.8, 54.0, 115.3,
125.6, 125.9, 128.9, 129.7, 134.4, 134.9, 136.0, 136.3, 136.8, 137.5, 137.8, 139.7, 141.8,
142.0, 143.8, 145.4, 145.5, 152.3, 153.8, 191.4.
MS (MALDI-TOF, no matrix): m/z (%) = 1003 (100) [M] +· .
IR (ATR): 𝜈� [cm -1 ] = 3029, 2965, 2908, 2868, 1681, 1540, 1508, 1458, 1421, 1357, 1264, 1110,
1073, 1052, 1017, 873, 797, 738.
N
C66H64N4Ni2 M = 1003.96 g·mol-1 O
Ni(II)-67
UV/Vis (CH2Cl2): λ [nm] (ε [M -1 ·cm -1 ]) = 456 (144400), 581 (10800), 633 (15900).