Organometallics
Article
was cooled to 0 °C using an ice−water bath before saturated aqueous
NaHCO3 was added slowly with stirring until the pH of the aqueous
layer was 8.0. The aluminum byproduct precipitate was removed by
filtration through a Celite filter aid. The product was extracted into
chloroform (5 × 75 mL) and dried over sodium sulfate, and the
solvent was removed under reduced pressure to leave the crude
product. Purification by column chromatography (ethyl acetate/
hexane, 2:1) yielded a pale yellow crystalline solid. Yield = 1.38 g, 8.0
mmol, 80%.
Anal. Found (calcd for C90H96Mn2N6Na2O12): C 66.77 (67.16), H
6.38 (6.01), N 5.32 (5.22). IR (cm−1): 2925 vs, 2854 vs, 1602 w, 1584
m, 1464 vs, 1377 vs, 1282 m, 1196 m, 1172 w, 1095 w, 1044 m, 988 w,
905 m, 880 m, 795 w, 754 m, 730 s, 699 m, 681 w. UV in THF (λ/nm;
ε/M−1 cm−1): 244 (76 000), 302 (125 000).
[Na(THF)4][(MnL3 )Na(L3 Mn)]·2THF·Et2O. HL3 (0.516 g, 3.0
3
3
mmol) was stirred with NaH (0.086 g, 3.6 mmol) in dry THF (20
mL) for 15 min. The resulting yellow solution was transferred via
cannula into a solution of MnCl2 (0.126 g, 1.0 mmol) in dry THF (20
mL) at room temperature. After stirring overnight, the yellow mixture
was heated to reflux until the yellow solid dissolved. The resulting
solution was filtered hot via cannula and allowed to cool. Diethyl ether
was added to the onset of crystallization, and the mixture left to stand,
giving yellow single crystals (0.25 g, 30%).
Anal. Found (calcd for C88H100Mn2N12Na2O13): C 62.37 (62.55), H
5.78 (5.97), N 9.62 (9.95). IR (cm−1): 3083 w, 3062 w, 1603 w, 1561
s, 1525 vs, 1498 m, 1479 m, 1437 m, 1428 m, 1406 m, 1319 w, 1271
vs, 1214 w, 1192 s, 1071 w, 1063 w, 1045 s, 1031 vs, 985 m, 906 m,
893 s, 881 m, 837 s, 749 vs, 732 vs, 683 vs, 666 w. UV in THF (λ, nm;
ε, M−1 cm−1): 266 (27 000), 312 (44 000), 365 (24 000).
1H NMR (400 MHz, 298 K, CDCl3): δH 9.88 (br s, 1H, Pyr-NH),
8.80 (2H, dd, 4.5, 1.5 Hz), 7.69 (2H, dd, 4.5, 1.5 Hz), 7.22 (1H, m),
6.89 (1H, m), 6.37 (1H, m). 13C{1H} NMR (100 MHz, 298 K,
CDCl3): δC 182.9 (CO), 150.3, 145.0, 130.5, 126.6, 122.3, 120.3,
111.6. MS (ESI): m/z 171.2 (M − H)−. IR: ν cm−1 3115 w, 3063 w,
3026 w, 2989 w, 2921 w, 2875 w, 2801 w, 2683 w, 1612 m, 1600 m,
1542 m, 1465 w, 1427 m, 1412 m, 1392 s, 1342 m, 1320 m, 1263 w,
1220 m, 1197 w, 1140 m, 1093 m, 1064 w, 1045 m, 1002 m, 986 w,
962 w, 887 m, 866 m, 834 m, 792 s, 757 m, 738 s, 723 s. Anal. Found
(calcd for C10H8N2O): C 69.67 (69.76), H 4.38 (4.68), N 16.32
(16.27).
[MnL1 ]. HL1 (0.516 g, 3.14 mmol) was stirred with NaH (0.086 g,
3
Crystallography. C88H100Mn2N12Na2O13, M = 1689.66, triclinic, a
= 12.4104(6) Å, b = 13.3080(6) Å, c = 15.0872(6) Å, α = 104.434(3)°,
β = 102.056(4)°, γ = 111.251(4)°, V = 2121.9(2) Å3, T = 100(2) K,
3.6 mmol) in dry THF (20 mL) for 15 min. The resulting yellow
solution was transferred via cannula into a solution of MnCl2 (0.126 g,
1.0 mmol) in dry THF (20 mL) at room temperature. The solution
turned gray immediately. The reaction mixture was stirred overnight at
ambient temperature. The solution was filtered, and the volume of the
solution was reduced by half before Et2O (5 mL) was added to induce
crystallization. A few crystals of the complex were isolated by filtration
and washed with a little cold THF. Single crystals were grown from the
solution of THF/Et2O (3:1).
space group P1, Z = 1, 16 045 reflections measured, 8012 independent
̅
reflections (Rint = 0.0345). The final R values were R1 = 0.0528 (I >
2o(I)), wR(F2) = 0.1380 (I > 2o(I)), R1 (all data) = 0.0583, wR(F2)
(all data) = 0.1432.
[Na(MeCN)2][(MnL3 )Na(L3 Mn)]·MeCN. NaL3 (3.0 mmol) and
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MnCl2 (0.126 g, 1.0 mmol) were stirred overnight in dry THF (20
mL) as above. The solvent was removed in vacuo, and the product was
extracted into MeCN (30 mL) with heating. The volume of the red
MeCN solution was reduced by half to induce crystallization. Yield:
0.41 g, 63%. Further single crystals were grown from the solution upon
standing at 4 °C for 1 week.
Crystallography. C27H33MnN6O3, M = 544.53, monoclinic, a =
9.7037(12) Å, b = 17.001(2) Å, c = 15.6962(13) Å, α = 90.00°, β =
100.350(7)°, γ = 90°, V = 2547.4(5) Å3, T = 100(2) K, space group
P21/n, Z = 4, 19 043 reflections measured, 4910 independent
reflections (Rint = 0.0672). The final R values were R1 = 0.0907 (I >
2σ(I)), wR(F2) 0.1635 (I > 2σ(I)), R1 (all data) = 0.1372, wR(F2) (all
data) = 0.1901.
IR (cm−1): 3065 w, 1601 w, 1560 s, 1526 vs, 1495 m, 1480 m, 1429
m, 1407 w, 1318 w, 1270 vs, 1215 w, 1194 s, 1089 w, 1071 w, 1045 m,
1030 vs, 985 m, 905 w, 894 s, 836 s, 749 vs, 732 vs, 682 vs, 666 w.
Anal. Found (calcd for C66H51Mn2N15Na2O6): C 60.47 (60.69), H
4.18 (3.94), N 16.32 (16.09). UV in MeCN (λ, nm; ε, M−1 cm−1): 265
(24 000), 260 (40 000), 306 (22 600).
[FeL1 ]. This was prepared in the same manner as [MnL1 ], from
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3
anhydrous FeCl2. A few single crystals were grown from THF/Et2O
(3:1).
Crystallography. C27H33FeN6O3, M = 545.44, monoclinic, a =
9.99697(15) Å, b = 31.4459(4) Å, c = 16.9520(2) Å, α = 90.00°, β =
103.4800(15)°, γ = 90°, V = 5182.28(13) Å3, T = 100(2) K, space
group P21/n, Z = 8, 58 787 reflections measured, 9984 independent
reflections (Rint = 0.0619). The final R values were R1 = 0.0413 (I >
2o(I)), wR(F2) = 0.0985 (I > 2o(I)), R1 (all data) = 0.0498, wR(F2)
(all data) = 0.1038.
Crystallography. C66H51Mn2N15Na2O6, M = 1306.08, triclinic, a =
10.3060(4) Å, b = 12.9626(4) Å, c = 13.0826(6) Å, α = 63.489(4)°, β
=80.865(4)°, γ = 80.113(3)°, V = 1534.05(11) Å3, T = 100(2) K,
space group P1, Z = 1, 15 296 reflections measured, 5867 independent
̅
reflections (Rint = 0.0365). The final R values were R1 = 0.0403 (I >
2o(I)), wR(F2) = 0.0992 (I > 2o(I)), R1 (all data) = 0.0433, wR(F2)
(all data) = 0.1020.
[Na(THF)6][(FeL2 )Na(L2 Fe)]. HL2 (0.513 g, 3.0 mmol) was
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[FeL3 ]. HL3 (0.344 g, 2.0 mmol) was stirred with MeOLi (0.091 g,
2
stirred with NaH (0.086 g, 3.6 mmol, 1.2 equiv) in dry THF (20 mL)
for 15 min. The resulting yellow solution was transferred via cannula
into a solution of FeCl2 (0.127 g, 1.0 mmol) in dry THF (20 mL) at
ambient temperature. The deep red solution was stirred overnight and
was filtered via cannula. Large red blocks grew at 4 °C over 1 week
(0.259 g, 32%).
2.4 mmol) in dry MeOH (20 mL) for 15 min. This resulted in a
yellow solution, to which was added a solution of FeCl2 (0.127 g, 1.0
mmol) in dry MeOH (15 mL) via canuula. The solution turned blue
and then purple after 1 h. The mixture was stirred overnight at
ambient temperature. The purple product was collected by filtration
and dried in vacuo for 4 h (0.378 g, 95%). Single crystals were grown in
an NMR tube from a slow diffusion of two layered solutions of starting
materials in MeOH solution (ca. 1.0 M).
Anal. Found (calcd for C20H14FeN4O2: C 60.37 (60.33), H 3.38
(3.54), N 14.32 (14.07). IR (cm−1): 3058 w, 1610 m, 1559 s, 1524 vs,
1497 m, 1434 m, 1415 w, 1388 vs, 1317 w, 1278 m, 1221 w, 1196 m,
1139 w, 1046 m, 993 m, 909 m, 880 m, 852 m, 748 s, 726 vs, 693 vs.
Due to the insolubility of the material, we were unable to collect UV
data.
Crystallography. C20H14FeN4O2, M = 398.20, monoclinic, a =
7.7538(2) Å, b = 13.6404(4) Å, c = 8.2758(3) Å, α = 90.00°, β =
98.581(3)°, γ = 90.00°, V = 865.49(5) Å3, T = 100(2) K, space group
P2(1)/n, Z = 2, 3844 reflections measured, 1525 independent
reflections (Rint = 0.0249). The final R values were R1 = 0.0412 (I >
2σ(I)), wR(F2) = 0.1147 (I > 2σ(I)), R1 (all data) = 0.0441, wR(F2)
(all data) = 0.1189.
IR (cm−1): 2911 vs, 2850 vs, 1601 w, 1581 w, 1463 vs, 1377 vs,
1282 m, 1126 m, 1040 m, 905 m, 880 m, 794 w, 754 m, 731 s, 700 m.
Anal. Found (calcd for C90H96Fe2N6Na2O12): C 67.37 (67.08), H 6.38
(6.00), N 5.32 (5.22). UV in THF (λ/nm; ε/M−1 cm−1): 244
(30 000), 302 (48 000).
Crystallography. C90H96Fe2N6Na2O12, M = 1611.41, hexagonal, a =
13.11870(10) Å, b = 13.11870(10) Å, c = 28.3181(5) Å, α = 90.00°, β
= 90.00°, γ = 120.00°, V = 4220.62(9) Å3, T = 100(2) K, space group
P3 c, Z = 2, 48 829 reflections measured, 2708 independent
̅
1
reflections (Rint = 0.0513). The final R values were R1 = 0.0843 (I >
2σ(I)), wR(F2) = 0.2421 (I > 2σ(I)), R1 (all data) = 0.0937, wR(F2)
(all data) = 0.2536.
[Na(THF)6][(MnL2 )Na(L2 Mn)]. This was synthesized from MnCl2
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in a similar manner to the Fe analogue. Large yellow blocks were
grown from diethyl ether at room temperature over 2 h and were
isolated by decantation (0.420 g, 52%).
F
Organometallics XXXX, XXX, XXX−XXX