Solidꢀstate thermolysis of metal pivalate complexes
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 6, June, 2010
1183
3228 m, 2980 m, 2960 m, 2932 m, 2868 m, 1644 s, 1620 s, 1584 m,
1564 s, 1536 s, 1520 s, 1494 s, 1484 s, 1452 s, 1420 s, 1376 s, 1360 s,
1336 m, 1268 m, 1228 m, 1156 m, 1092 w, 1056 w, 1028 w, 1008 m,
940 w, 900 m, 856 m, 808 m, 792 m, 772 s, 744 m, 660 w, 644 w,
608 m, 520 m, 452 m, 400 w, 364 w, 356 w, 320 w.
IR, ν/cm–1: 3408 m, 3364 s, 3228 m, 2960 s, 2928 m, 2864 m,
2832 w, 1632 s, 1616 s, 1600 m, 1596 s, 1568 s, 1528 s, 1480 s,
1456 s, 1424 s, 1396 m, 1360 s, 1348 m, 1260 m, 1228 m, 1164 w,
1084 m, 1044 m, 960 m, 904 m, 892 m, 808 m, 800 m, 776 m, 744 w,
684 w, 768 w, 608 m, 560 m, 532 m, 504 w, 488 w, 464 w, 432 m,
412 m, 352 w, 324 w, 312 w.
B. A mixture of Ni2(μꢀH2O)(OOCBut)4(HOOCBut)4 (0.3 g,
0.316 mmol) and 2,6ꢀdiaminopyridine (0.069 g, 0.632 mmol) in
MeCN (40 mL) was heated at 70 °C until the starting reagents
were completely dissolved. The reaction solution was concenꢀ
trated to 10 mL at 0.1 Torr and 20 °C and the residue was crysꢀ
tallized at 20 °C. The brightꢀgreen crystals that precipitated after
24 h were separated by decantation, washed with cold MeCN,
and dried under argon. The yield was 0.275 g (96%). The specꢀ
troscopic characteristics of the product are similar to those of the
sample prepared according to the method A.
The crystallographic data for complex 6 (monoclinic space
group P21/c, a = 11.2306(5) Å, b = 23.6445(7) Å, c = 8.5436(4) Å,
α = 90°, β = 102.668(4)°, γ = 90°; V = 2213.46(16) Å3, Z = 4)
correspond to the parameters determined previously28 by the
Xꢀray diffraction study of the molecular structure of the complex
2
[(2ꢀNH2)C5H4N]2Co(η ꢀOOCBut)2.
2
Di(2ꢀaminopyridino)di(η ꢀO,O´ꢀtrimethylacetato)monoꢀ
2
nickel(II), [(2ꢀNH2)C5H4N]2Ni(η ꢀOOCBut)2 (7). A mixture of
Ni6(μ ꢀOOCBut)6(μ ꢀOOCBut)6 (2) (0.3 g, 0.192 mmol) and
2
3
2ꢀaminopyridine (0.216 g, 2.3 mmol) in benzene (70 mL) was
heated at 80 °C until the starting reagents were completely disꢀ
solved. The reaction solution was concentrated to 50 mL at
0.1 Torr and 20 °C and the residue was crystallized at 20 °C. The
green fineꢀcrystalline precipitate that formed after 24 h was sepꢀ
arated by decantation, washed with cold benzene, and dried
under argon. The yield was 0.495 g (96%). Found (%): C, 53.54;
H, 6.75; N, 12.48. C20H30NiN4O4. Calculated (%): C, 53.48;
H, 6.73; N, 12.47. IR, ν/cm–1: 3432 s, 3412 s, 3340 s, 3272 m,
3228 m, 2976 m, 2960 m, 2932 m, 2868 m, 2836 w, 1644 s,
1616 s, 1592 m, 1568 s, 1536 s, 1520 s,1492 s, 1484 s, 1452 s,
1432 s, 1380 s, 1360 s, 1336 m, 1264 m, 1228 m, 1156 m, 1096 m,
1056 m, 1028 m, 1008 m, 940 w, 904 m, 856 w, 812 m, 792 m,
772 s, 744 m, 660 w, 648 w, 608 m, 516 m, 452 m, 404 w, 324 w.
The crystallographic data for complex 9 (monoclinic space
group P21/n, a = 12.221(3) Å, b = 12.150(4) Å, c = 16.367(5) Å,
α = 90°, β = 111.017(6)°, γ = 90°; V = 2268.7(12) Å3, Z = 4)
correspond to the parameters determined previously27 by the Xꢀ
ray diffraction study of the molecular structure of the complex
2
[H2N(C5H3N)N(H)C(Me)=NH]Ni(η ꢀOOCBut)2•MeCN.
Di(2ꢀaminoꢀ6ꢀmethylpyridino)tetra(μ ꢀO,O´ꢀtrimethylaceꢀ
2
tato)dicobalt(II) acetonitrile tetrasolvate, [(2ꢀNH2)(6ꢀCH3)ꢀ
C5H3N]2Co2(μ ꢀOOCBut)4•4MeCN (10•4MeCN). A mixture
2
of the polymer [Co(OOCBut)2]n (1) (0.4 g, 1.53 mmol; per forꢀ
mula unit Co(OOCBut)2) and 2ꢀaminoꢀ6ꢀmethylpyridine (0.332 g,
3.06 mmol) in MeCN (50 mL) was heated at 80 °C until the
starting reagents were completely dissolved. The reaction soluꢀ
tion was concentrated to 10 mL at 0.1 Torr and 20 °C and the
residue was crystallized at 20 °C. The darkꢀgreen crystals that
precipitated after 24 h were separated by decantation, washed
with cold MeCN, and dried under argon. The yield was 0.378 g
(82%). Found (%): C, 53.25; H, 7.19; N, 12.43. C40H64Co2N8O8.
Calculated (%): C, 53.21; H, 7.15; N, 12.41. IR, ν/cm–1: 3380 s,
3218 m, 2964 s, 2908 m, 2868 m, 1664 m, 1632 m, 1608 m, 1580 s,
1536 s, 1484 m, 1456 m, 1416 s, 1380 m, 1360 m, 1276 w, 1260 m,
1224 s, 1176 w, 1032 w, 938 m, 902 m, 809 m, 792 m, 728 w,
672 m, 612 m, 606 m, 554 w, 532 s, 448 w, 426 m, 408 w, 356 w.
The crystallographic data for 10•4MeCN (monoclinic space
group P21/n, a = 15.43(1) Å, b = 18.58(1) Å, c = 11.17(1) Å,
α = 90°, β = 130.74(1)°, γ = 90°; V = 2426(2) Å3, Z = 2) correꢀ
spond to the parameters determined previously33 by the Xꢀray
diffraction study of the molecular structure of the complex
(2,6ꢀNH2)2Mn2(OOCBut)4•4MeCN.
1
Complex [H2N(C5H3N)N(H)C(Me)=NH]Co(η ꢀOOCBut)2
(8). A mixture of the polymer [Co(OOCBut)2]n (1) (0.4 g,
1.53 mmol; per formula unit Co(OOCCMe3)2) and 2,6ꢀdiaminoꢀ
pyridine (0.167 g, 1.53 mmol) in MeCN (70 mL) was heated at
80 °C until the starting reagents were completely dissolved. The
reaction solution was concentrated to 50 mL at 0.1 Torr and
20 °C and the residue was crystallized at 20 °C. The pink crystals
that precipitated after 12 h were separated by decantation, washed
with cold MeCN, and dried under argon. The yield was 0.63 g
(98%). Found (%): C, 49.69; H, 6.88; N, 13.68. C17H28CoN4O4.
Calculated (%): C, 49.64; H, 6.86; N, 13.63. IR, ν/cm–1: 3424 m,
3224 m, 2956 s, 2928 m, 2868 m, 1644 s, 1636 s, 1616 s,1600 s,
1572 s, 1552 s, 1536 s, 1464 s, 1400 s, 1356 s, 1256 s, 1220 s, 1172 m,
1124 m, 1092 m, 1048 m, 1024 m, 1008 m, 960 m, 936 m, 892 m,
796 s, 772 s, 732 m, 696 w, 668 w, 612 m, 580 w, 560 m, 492 w,
428 m, 356 w, 328 w, 316 w.
The crystallographic data for complex 8 (monoclinic space
group P21/c, a = 15.108(13) Å, b = 13.458(10) Å, c = 10.310(8) Å,
α = 90°, β = 103.630(19)°, γ = 90°; V = 2037(3) Å3, Z = 4)
correspond to the parameters determined previously27 by the
Xꢀray diffraction study of the molecular structure of the complex
(2ꢀAminoꢀ6ꢀmethylpyridino)tri(μ ꢀO,O´ꢀtrimethylacetato)ꢀ
2
2
mono(η ꢀO,O´ꢀtrimethylacetato)dicobalt(II) hydrate, [(2ꢀNH2)ꢀ
(6ꢀCH3)C5H3N]Co2(μ ꢀOOCBut)3(η ꢀOOCBut)•1.5H2O
2
2
(11•1.5H2O). A mixture of the polymer [Co(OOCCMe3)2]n (1)
(0.4 g, 1.53 mmol; per formula unit Co(OOCBut)2) and 2ꢀamiꢀ
noꢀ6ꢀmethylpyridine (0.166 g, 1.53 mmol) in MeCN (50 mL)
was heated at 80 °C until the starting reagents were completely
dissolved. The reaction solution was concentrated to 40 mL at
0.1 Torr and 20 °C and the residue was crystallized at 20 °C. The
blue crystals that precipitated after 2 h were separated by decanꢀ
tation, washed with cold MeCN, and dried under argon. The
yield was 0.443 g (88%). Found (%): C, 47.58; H, 7.29; N, 4.25.
C26H47Co2N2O9.50. Calculated (%): C, 47.50; H, 7.20; N, 4.26.
IR, ν/cm–1: 3383 s, 3218 m, 2963 s, 2904 m, 2872 m, 1662 m,
1608 s, 1590 w, 1548 m, 1533 s, 1528 m, 1485 s, 1460 m, 1419 s,
1378 m, 1363 m, 1295 w, 1227 s, 1032 w, 938 s, 902 m, 809 m,
1
[H2N(C5H3N)N(H)C(Me)=NH]Co(η ꢀOOCBut)2.
2
Complex [H2N(C5H3N)N(H)C(Me)=NH]Ni(η ꢀOOCBut)2•
•MeCN (9•MeCN). A. A mixture of Ni6(μ ꢀOOCBut)6(μ ꢀ
2
3
OOCBut)6 (2) (0.3 g, 0.192 mmol) and 2,6ꢀdiaminopyridine
(0.126 g, 1.16 mmol) in MeCN (70 mL) was heated at 80 °C
until the starting reagents were completely dissolved. The reacꢀ
tion solution was concentrated to 50 mL at 0.1 Torr and 20 °C
and the residue was crystallized at 20 °C. The brightꢀgreen crysꢀ
tals that precipitated after 12 h were separated by decantation,
washed with cold MeCN, and dried under argon. The yield
was 0.499 g (96%). Found (%): C, 50.48; H, 6.94; N, 15.52.
C19H31NiN5O4. Calculated (%): C, 50.47; H, 6.91; N, 15.49.