PREPARATION OF AMORPHOUS WATER-SOLUBLE COMPLEXES
1123
Manganese(II) (1-hydroxyethylidene)diphosphonate
bis[1,3-dihydroxy-2-(hydroxymethyl)propan-2-
aminium] dihydrate (IX) was prepared similarly from
4.13 g (1.32 × 10–2 mol) of the MnH2L·2H2O manga-
nese complex, 50 mL of distilled water, and 3.35 g
(2.77 × 10–2 mol) of 2-amino-2-(hydroxymethyl)-
propane-1,3-diol. Yield 6.47 g (1.17 × 10–2 mol, 87%),
coarsely dispersed light-grey powder. IR spectrum, ν,
cm–1: 3600–3020 br, 2750–2200 br, 2077, 1609, 1527,
1056, 994, 950, 905 sh, 819, 721, 657, 559, 479.
Found, %: С 21.31; H 6.05; Mn 9.82; P 11.07.
C10H34N2MnO16P2. Calculated, %: C 21.63; H 6.17;
Mn 9.89; P 11.16.
rate (XII) was prepared similarly form 11.01 g (2.05 ×
10–2 mol) of the Mn(H3L)2·4H2O complex, 100 mL of
water, and 4 mL (4.08 g, 6.69 × 10–2 mol) of 2-
aminoethanol. Yield 11.37 g (1.58·10–2 mol, 77%),
light-brown powder. IR spectrum, ν, cm–1: 3600–2100
br, 1624, 1509, 1302, 1272, 1139, 1071, 1021, 988,
929 sh, 893, 787, 725, 663, 642, 580, 538. Found, %:
С 17.04; H 6.55; Mn 7.66; P 17.27. C10H43N3MnO21P4.
Calculated, %: С 16.67; H 6.02; Mn 7.63; P 17.20.
Solubility 1.94 g in 100 mL of the solution.
ACKNOWLEDGMENTS
The studies were performed at Analytical Center of
Institute of Organometallic Chemistry, Russian Academy
of Sciences.
Tris[1,3-dihydroxy-2-(hydroxymethyl)propan-2-
aminium] (1-hydroxyethylidene)diphosphonate (Х).
5.3 mL of 0.72 M of (1-hydroxyethylidene)diphos-
phonic acid solution in ethanol (0.86 g, 3.82 ×
10–3 mol) was added dropwise at stirring to a hot solu-
tion of 1.39 g (1.15 × 10–2 mol) of 2-amino-2-(hydroxy-
methyl)propane-1,3-diol in 10 mL of ethanol. 12 h
later the solvent was decanted; the residue was dried in
air during 7 h at 115°С and in vacuum at 200°С. Yield
1.89 g (2.74 × 10–3 mol, 72%), colorless glassy mass.
IR spectrum, ν, cm–1: 3650–3000 br, 2800–2000 br,
1617, 1528, 1293, 1125, 1057, 968, 905, 807, 724, 643,
539, 464. Found, %: С 31.87; H 7.97; P 9.03. C18H52N4O19P2.
Calculated, %: С 31.31; H 7.59; P 8.97.
This work was financially supported by Presidium
of Russian Academy of Sciences in the frame of the
“Targeted synthesis of compounds with desired
properties and development of functional materials
based thereof” program.
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The reactions in mixed solvents were performed
similarly, adding ethanolic solution of (1-hydroxy-
ethylidene)diphosphonic acid to a hot solution or
suspension of compound II in methanol, acetone,
toluene, or DMSO. Compound II was completely
dissolved in СН3ОН and DMSO and partially
dissolved in acetone and toluene.
Iron(III) tris[(1-hydroxyethylidene)diphospho-
nate] hexa(2-hydroxyethanaminium) dihydrate
(XI). 10.22 g (1.67 × 10–1 mol) of 2-aminoethanol was
added upon stirring to a suspension of 18.62 g (2.50 ×
10–2 mol) of the finely ground Fe(H3L)3·4H2O complex
in 200 mL of water. 15 min later the mixture was
evaporated; the residue was heated in air during 15 h
and in vacuum at 220°С. Yield 24.50 g, light-green
powder. IR spectrum, ν, cm–1: 3600–2200 br, 1627,
1527, 1272, 1030 br, 914 sh, 804, 725, 660, 570.
Found, %: С 19.57; H 6.50; Fe 5.20; P 16.32.
C18H71N6FeO31P6. Calculated, %: С 19.48; H 6.45; Fe
5.03; P 16.75.
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Manganese(II) bis[(1-hydroxyethylidene)diphos-
phonate] tris (2-hydroxyethanaminium) tetrahyd-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 85 No. 5 2015