Transition Metal Complexes of Dimeric N-Confused Porphyrin
2
4
in a minimum amount of chloroform and precipitated by the
addition of hexane. The dark-green product, 8a, was collected by
filtration and dried in Vacuo. Yield: 20 mg (80%). A 10 mg sample
of the acetate complex, 8a, was converted into a bis(chloride)
complex by dissolving it in 10 mL of chloroform and vigorous
stirring with an aqueous solution of NaCl (1 M, 2 mL). The water
layer was then removed, and the organic phase was washed with
three portions of water (5 mL each). After separation of the organic
phase, the solution was filtered, and the solvent was removed. The
solid residue was dissolved in chloroform, and the product, 8b,
was crystallized slowly after the addition of hexane. Yield: 8 mg
(82%).
4JHH ) 1.4 Hz, JCdH ) 12.1 Hz, 1Hx); -0.40 (d, JHH ) 1.2 Hz,
4
2
dd, JHH ) 1.2 Hz, JCdH ) 11.5 Hz, 1Hy).
Synthesis of 2-(2′-(5,10,15,20-Tetrakis(p-tolyl)-2-aza-21-car-
baporphyrinatonickel(II))-o-xylene)-(5,10,15,20-tetrakis(p-tolyl)-
2-aza-21-carbaporphyrin, 10, and 2-(21′-(5,10,15,20-Tetrakis(p-
tolyl)-2-aza-21-carbaporphyrinatonickel(II))-o-xylene)-5,10,15,20-
tetrakis(p-tolyl)-2-aza-21-carbaporphyrin, 11. To a solution
containing 2 (25 mg, 0.07 mmol) and 9 (32 mg, 0.07 mmol) in
THF (20 mL) was added 10 mg of K2CO3 and 2 mg of [18]-crown-
6, and the mixture was stirred and refluxed under nitrogen for 3 h.
After that, the solution was filtered, the solvent was evaporated,
and the solid residue was dissolved in CH2Cl2. The solution was
passed down a silica-gel column with dichloromethane or a 1%
solution of ethanol in chloroform as the mobile phase. The fastest-
migrating band contained a small amount of unreacted 2; the second
band contained product 10, and the third contained product 11.
Solvents from the fractions containing the desired products were
evaporated, dissolved in chloroform, and precipitated with hexane.
The green product, 10, and brown product, 11, were separated from
the solution by filtration and dried in the air. Yields: 10, 25 mg
(47%); 11, 11 mg (20%).
Selected data for 8a. UV-vis (CH2Cl2) λ/nm (ꢀ·10-3): 258
(44.1); 321 (64.1); 403 (sh); 456 (sh); 478 (235.1); 560 (67.0); 608
(8.3); 669 (9.7); 739 (sh); 811 (57.8). 1H NMR (500 MHz, CDCl3,
298 K): δ 8.19 (d, 3JHH ) 4.6 Hz, dd, 3JHH ) 4.6 Hz, 4JCdH ) 4.2
3
3
4
Hz, 1Hy); 8.13 (d, JHH ) 4.8 Hz, dd, JHH ) 4.8 Hz, JCdH ) 4.4
3
3
Hz, 1Hx); 7.96 (d, JHH ) 7.9 Hz, 2Hy); 7.90 (d, JHH ) 4.8 Hz,
3
3
1Hx); 7.90 (d, JHH ) 7.6 Hz, 1Hx); 7.85 (d, JHH ) 5.0 Hz, 1Hy);
7.84 (d, JHH ) 4.6 Hz, 1Hy); 7.83 (d, JHH ) 4.8 Hz, 1Hy); 7.82
3
3
3
3
(d, JHH ) 4.2 Hz, 1Hx); 7.81 (d, JHH ) 4.2 Hz, 1Hx); 7.72 (d,
3JHH ) 4.6 Hz, dd, JHH ) 4.6 Hz, JCdH ) 4.3 Hz, 1Hy); 7.69 (b,
3
4
Selected data for 10. UV-vis (CH2Cl2) λ/nm (ꢀ·10-3): 253 (sh);
309 (sh); 364 (60.5); 433 (sh); 449 (100.0); 567 (14.6); 661 (10.1);
721 (11.2); 796 (5.4). 1H NMR (500 MHz, CDCl3, 298 K): δ 8.28
(s, 1H); 8.08 (d, 3JHH ) 5.0 Hz, 1H); 7.95 (d, 3JHH ) 4.8 Hz, 1H);
7.89 (d, 3JHH ) 7.8 Hz, 2H); 7.86 (s, 2H); 7.83 (d, 3JHH ) 7.8 Hz,
3
3
4
1Hy); 7.66 (d, JHH ) 5.0 Hz, dd, JHH ) 5.0 Hz, JCdH ) 3.6 Hz,
3
3
4
1Hy); 7.65 (d, JHH ) 4.8 Hz, dd, JHH ) 4.8 Hz, JCdH ) 4.4 Hz,
2Hx); 7.61 (b, 1Hy); 7.57 (d, 3JHH ) 7.1 Hz, 1Hx); 7.55 (d, 3JHH
)
3
3
7.3 Hz, 1Hx); 7.44 (d, JHH ) 7.6 Hz, 2Hx); 7.41 (d, JHH ) 7.9
Hz, 1Hy); 7.36 (m, 2Hx + 2Hy); 7.11 (m, 1Hx); 7.02 (b, 2Hy); 6.96
3
3
2H); 7.80 (d, JHH ) 5.0 Hz, 1H); 7.71 (d, JHH ) 4.4 Hz, 1H);
3
7.70 (d, 3JHH ) 5.0 Hz, 1H); 7.69 (d, 3JHH ) 5.0 Hz, 1H); 7.67 (d,
(d, JHH ) 7.3 Hz, 1Hx); 6.79 (m, 1Hy); 6.49 (m, 1Hy); 6.41 (d,
4JHH ) 1.5 Hz, 1Hy); 6.02 (b, 1Hx); 4.83 (d, 2JHH ) 16.2 Hz, 1Hx);
4.68; 4.53 (d, 2JHH ) 16.2 Hz, 1Hx); 4.32 (d, 2JHH ) 16.5 Hz, 1Hy);
2.56 (s, 3Hx + 6Hy); 2.55 (s, 6Hx + 6Hy); 2.51 (s, 3Hy); 2.09 (s,
3JHH ) 7.8 Hz, 2H); 7.64 (d, 3JHH ) 8.0 Hz, 2H); 7.62 (d, 3JHH
)
7.8 Hz, 2H); 7.60 (d, 3JHH ) 5.0 Hz, 1H); 7.53 (d, 3JHH ) 4.6 Hz,
3
3
1H); 7.49 (d, JHH ) 7.8 Hz, 2H); 7.47 (d, JHH ) 7.8 Hz, 2H);
4
7.40 (d, 3JHH ) 4.6 Hz, 1H); 7.39 (d, 3JHH ) 5.0 Hz, 1H); 7.38 (d,
3Hx); 1.12 (s, 3Hx + 3Hy, acetate); -0.47 (d, JHH ) 1.4 Hz, dd,
4JHH ) 1.4 Hz, JCdH ) 12.0 Hz, 1Hx); -0.54 (d, JHH ) 1.5 Hz,
2
4
3JHH ) 7.8 Hz, 2H); 7.36 (d, 3JHH ) 7.8 Hz, 2H); 7.35 (d, 4JHH
)
4
2
dd, JHH ) 1.5 Hz, JCdH ) 12.2 Hz, 1Hy). 13C NMR (126 MHz,
CDCl3, 298 K): δ 176.6; 163.3; 162.9; 160.2; 158.3; 154.3; 151.3;
139.2; 139.1; 138.7; 138.4; 137.8; 136.9; 136.7; 136.7; 136.4; 135.8;
134.9; 134.1; 134.1; 133.4; 133.0; 132.8; 132.2; 131.9; 131.4; 131.3;
130.9; 130.7; 129.0; 128.8; 128.9; 128.7; 128.6; 128.5; 128.4; 127.7;
127.6; 126.4; 126.2; 125.9; 122.7; 122.2 (C3y); 119.7 (C3x); 117.5;
75.3 (C21y); 73.0 (C21x); 51.0; 50.8; 29.7; 21.4; 21.4; 20.8; 21.0;
20.5. MS (ESI+): 1726.1 (observed); 1725.7 (calculated for
[(C104H80N8Cd2)(CH3CO2)]+); 833.0 (observed); 833.3 (calculated
for [C104H80N8Cd2]2+). Anal. calcd for C108H86N8Cd2O4 · CHCl3:
%C, 68.76; % H, 4.61; %N, 5.88. Observed: %C, 68.81; %H, 4.97;
%N, 5.50.
1.4 Hz, 1H); 7.34 (d, 3JHH ) 7.1 Hz, 2H); 7.32 (d, 3JHH ) 7.4 Hz,
3
3
2H); 7.31 (d, JHH ) 8.0 Hz, 2H); 7.00 (d, JHH ) 7.4 Hz, 2H);
3
3
6.82 (d, JHH ) 7.3 Hz, 1H); 6.63 (t, JHH ) 7.4 Hz, 1H); 6.5 (t,
3JHH ) 7.6 Hz, 1H); 6.23 (d, 3JHH ) 7.6 Hz, 1H); 5.71 (d, 3JHH
)
7.8 Hz, 1H); 4.41 (s, 2H); 4.37 (s, 2H); 3.91 (b, 1H); 2.61 (s, 3H);
2.55 (s, 3H); 2.52 (s, 3H); 2.51 (s, 3H); 2.12 (s, 3H); 1.99 (s, 3H);
1.81 (d, 4JHH ) 1.4 Hz, 1H). 13C NMR (126 MHz, CDCl3, 298 K):
δ 163.5; 149.9; 148.6; 144.7; 144.5; 138.7; 138.6; 138.0; 137.7;
137.4; 137.0; 136.9; 135.3; 135.2; 135.1; 134.7; 133.5; 133.0; 132.9;
132.6; 130.9; 128.1; 127.9; 127.7; 127.4; 126.0; 124.6; 121.2; 117.3;
117.0; 115.8; 115.7; 115.6; 115.5; 114.6; 114.5; 114.4; 114.3; 114.2;
113.8; 113.3; 113.1; 112.9; 112.6; 112.0; 111.2; 111.1; 111.0; 110.9;
110.8; 110.6; 108.6; 98.4 (C21); 60.5; 60.0; 40.2; 39.8. HRMS
(ESI+): m/z 1499.599 (observed); 1499.594 (calculated for
[C104H81N8Ni]+, [M+1]+). Anal. calcd for C104H80N8Ni ·
CHCl3 ·hexane: %C, 78.14; %H, 5.61; %N, 6.57. Observed: %C,
78.50; %H, 5.38; %N, 6.64.
Selected data for 11. UV-vis (CH2Cl2) λ/nm (ꢀ·10-3): 251 (sh);
303 (49.2); 365 (71.3); 447 (155.2); 580 (12.0); 609 (12.8); 662
(15.3); 719 (17.2); 877 (sh). 1H NMR (500 MHz, CDCl3, 298 K):
δ 9.47 (s, 1H); 8.61 (d, JHH ) 4.6 Hz, 1H); 8.55 (d, JHH ) 5.1
Hz, 1H); 8.49 (d, JHH ) 4.2 Hz, 1H); 8.47 (d, JHH ) 4.2 Hz,
Selected data for 8b. UV-vis (CH2Cl2) λ/nm (ꢀ·10-3): 321
(62.5); 362 (sh); 405 (sh); 433 (sh); 455 (sh); 478 (238.0); 560
(73.8); 605 (8.8); 667 (9.8); 743 (21.6); 807 (21.8). 1H NMR (500
3
3
MHz, CDCl3, 298 K): δ 8.25 (d, JHH ) 4.6 Hz, dd, JHH ) 4.6
4
3
3
Hz, JCdH ) 4.1 Hz, 1Hy); 8.13 (d, JHH ) 4.4 Hz, dd, JHH ) 4.4
4
3
Hz, JCdH ) 4.3 Hz, 1Hx); 8.08 (d, JHH ) 8.0 Hz, 2Hy); 7.95 (d,
3JHH ) 4.8 Hz, dd, JHH ) 4.8 Hz, JCdH ) 4.9 Hz, 1Hx); 7.90 (d,
3
4
3JHH ) 7.6 Hz, 2Hx); 7.87 (d, JHH ) 5.0 Hz, 1Hy); 7.85 (d, JHH
3
3
3
3
3
) 5.0 Hz, 1Hy); 7.84 (d, JHH ) 4.6 Hz, 1Hy); 7.80 (s, 2Hx); 7.73
(d, 3JHH ) 4.6 Hz, 1Hy); 7.68 (b, 2Hx); 7.65 (d, 3JHH ) 4.6 Hz, dd,
3JHH ) 4.6 Hz, 4JCdH ) 4.7 Hz, 1Hx); 7.64 (d, 3JHH ) 4.6 Hz, 1Hy);
7.60 (d, 3JHH ) 4.6 Hz, 1Hx); 7.54 (b, 2Hy); 7.45 (m, 1Hy + 2Hx);
7.38 (m, 2Hy + 2Hx); 7.20 (b, 1Hy); 7.16 (b, 1Hx); 7.01 (b, 2Hy);
3
3
3
3
1H); 8.46 (d, JHH ) 4.8 Hz, 1H); 8.42 (d, JHH ) 4.6 Hz, 1H);
8.00 (b, 2H); 7.90 (d, 3JHH ) 4.6 Hz, 1H); 7.88 (d, 3JHH ) 4.6 Hz,
3
3
2H); 7.83 (b, 1H); 7.79 (d, JHH ) 8.0 Hz, 1H); 7.73 (d, JHH
)
3
4
8.0 Hz, 2H); 7.69 (d, 3JHH ) 8.0 Hz, 1H); 7.68 (d, 3JHH ) 4.3 Hz,
6.82 (d, JHH ) 7.3 Hz, 1Hx); 6.50 (d, JHH ) 1.2 Hz, 1Hy); 5.88
(b, 1Hx); 4.69 (d, JHH ) 16.2 Hz, 1Hx); 4.52 (d, JHH ) 17.4 Hz,
1Hy); 4.45 (d, JHH ) 15.2 Hz, 1Hx); 4.24 (d, JHH ) 17.0 Hz,
1Hy); 2.67 (s, 3Hy); 2.57 (s, 3Hx + 6Hy); 2.55 (s, 3Hx); 2.53 (s,
3Hx); 2.00 (s, 3Hx); 1.84 (s, 3Hy); -0.20 (d, JHH ) 1.4 Hz, dd,
2
2
3
3
1H); 7.66 (d, JHH ) 8.0 Hz, 2H); 7.65 (d, JHH ) 5.0 Hz, 1H);
7.62 (d, 3JHH ) 5.0 Hz, 1H); 7.53 (d, 3JHH ) 7.8 Hz, 2H); 7.47 (d,
2
2
3JHH ) 7.8 Hz, 2H); 7.43 (d, 3JHH ) 7.8 Hz, 2H); 7.42 (d, 3JHH
)
8.0 Hz, 1H); 7.38 (d, 4JHH ) 1.4 Hz, 1H); 7.36 (d, 3JHH ) 8.0 Hz,
4
Inorganic Chemistry, Vol. 48, No. 2, 2009 443