1008
V.A. Trush et al. / Polyhedron 24 (2005) 1007–1014
prepared by reacting phosphorus pentachloride with tri-
chloroacetamide, followed by addition of methanol in
accordance with the literature method [8].
3JPH = 11.2 Hz, Lꢀ]; 31P NMR: (D2O) 23.48
(PPh4)+, 16.03 [3JPH 11.3 Hz, PO(OCH3)2].
m
Metal salts Na[L] (1), Rb[L] (2), Tl[L] (3) were syn-
thesized in aqueous-alcoholic media.
2.1.4. (PPh4)2[L]Br Æ H2O (5)
To a solution of Na[L], that was prepared as above,
PPh4Br (0.838 g, 2 mmol in 15 ml CH3CN) was added
in the ratio 1:2. The white precipitate of NaBr was fil-
tered off, the solvent was removed in vacuo and the
off-white product was recrystallized from an isopropa-
nol–hexane mixture. Yield: 0.941 g, 90%. Anal. Calc.
for C52H48BrCl3NO5P3: C, 59.7; H, 4.63; N, 1.34.
Found: C, 60.0; H, 4.63; N, 1.30%. 1H NMR (CD3)2CO:
7.93 m [20H, (PPh4)+], 3.25 d [3H, JPH = 11.2 Hz, Lꢀ];
31P NMR: ((CD3)2CO) 24.05 m (PPh4)+, 13.05 [3JPH
11.3 Hz, PO(OCH3)2].
2.1.1. Na[L] (1)
Sodium carbonate (0.106 g, 1 mmol) was added in
several portions to a solution of H[L] (0.541 g, 2 mmol)
in 10 ml of aqueous 2-propanol (1:3). The solution was
stirred with heating until total dissolution of Na2CO3
was observed. The solvent was removed in vacuo and
the colorless product recrystallized from isopropanol.
Yield: 0.573 g, 98%. Anal. Calc. for C4H6Cl3NNaO4P:
C, 16.43; H, 2.07; N, 4.79. Found: C, 16.47; H, 2.1; N,
3
3
4.67%. 1H NMR (D2O): 3.55 d [6H, JPH 11.2 Hz,
PO(OCH3)2]; 31P NMR (D2O): 16.09 h [3JPH 11.3 Hz,
PO(OCH3)2]. Na[L-d6] (1a). The compound was ob-
tained as 1. NaHCO3 and D[L-d6] were used as starting
materials. Yield: 0.585 g, 98%.
2.1.5. (PPh4)2[Na4L6] (6)
To a solution of 0.8772 g (3 mmol) Na[L], 0.419 g
PPh4Br (1 mmol in 10 ml CH3CN) was added. The
white precipitate of NaBr was filtered off, the solvent
was removed in vacuum and the colourless product
was recrystallized from isopropanol and hexane. Yield:
1.015 g, 85%. Anal. Calc. for C72H76Cl18N6Na4O24P8:
C, 36.22; H, 3.21; N, 3.52. Found: C, 36.54; H, 3.32;
2.1.2. Rb[L] (2)
Rubidium carbonate (0.231 g, 1 mmol) was added in
parts to 10 ml of an aqueous-alcoholic (1:3) solution of
[HL] (0.541 g, 2 mmol). A solution of the product was
allowed to stand at room temperature in a vacuum des-
iccator over CaCl2 for 20 days, after which the colorless
well-faceted crystals that were deposited were filtered
out, washed with few drops of isopropanol and dried
over CaCl2. Yield: 0.653 g, 92%. Anal. Calc. for
C4H6Cl3NRbO4P: C, 13.54; H, 1.70; N, 3.95. Found:
N, 3.41%. 1H NMR ((CD3)2CO): 7.9
m [10H,
3
(PPh4)+], 3.53 d [9H, JPH 11.2 Hz, PO(OCH3)2]; 31P
NMR ((CD3)2CO): 22.35 m (PPh4)+, 12.64 h (3JPH
11.2 Hz, PO(OCH3)2).
=
All the compounds are soluble in water, DMFA,
DMSO, acetone, sparingly soluble in isopropanol, 1,4-
dioxane and insoluble in non-polar aprotic solvents.
1
C, 13.2; H, 1.76; N, 3.64%. H NMR (D2O): 3.57 d
3
2.1.6. [SbPh4L] (7)
[6H, JPH 11.2 Hz, PO(OCH3)2]; 31P NMR: (D2O)
To a solution of Na[L] (0.293 g 1 mmol) in 10 ml ace-
tonitrile was added SbPh4Br (0.511 g, 1 mmol) in 15 ml
acetonitrile. After 15 min, a white precipitate of NaBr
was filtered off and the solution was allowed to stand
in a vacuum desiccator over CaCl2. After a while color-
less crystals of 7 precipitated from the solution, that
were recrystallized from isopropanol. The compound
is soluble in polar protic solvents, insoluble in water,
ethers, benzene and alkanes. Yield: 0.569 g, 85%. Anal.
Calc. for C4H6Cl3NTlO4P: C, 47.73; H, 4.43; N, 1.99.
Found: C, 47.70; H, 4.65; N, 1.74%. 1H NMR
((CD3)2CO): 7.88 dd [8H, 3JHH = 8.4 Hz, 4JHH = 1.6 Hz,
(SbPh4)+ – ortho], 7.61 m [12H, (SbPh4)+ – meta + para],
3.25 d [6H, 3JPH = 11.2 Hz, Lꢀ]; 31P NMR ((CD3)2CO):
12.08 h (3JPH = 11.2 Hz, Lꢀ).
3
16.11 h JPH 11.3 Hz, PO(OCH3)2].
The thallium compound Tl[L] (3) was synthesized in a
similar fashion by reacting HL (0.584 g, 2 mmol) and
Tl2CO3 (0.4688 g, 1 mmol) in aqueous 2-propanol.
Yield: 0.824 g, 87%. Anal. Calc. for C4H6Cl3NTlO4P:
C, 10.14; H, 1.28; N, 2.96. Found: C, 10.14; H, 1.42;
1
3
N, 2.93%. H NMR (D2O): 3.57 d [6H, JPH 11.2 Hz,
3
PO(OCH3)2]; 31P NMR: (D2O) 16.09 h JPH 11.3 Hz,
PO(OCH3)2].
2.1.3. PPh4[L] (4)
To a solution of 1 (0.584 g, 2 mmol) in 10 ml acetoni-
trile, a solution of 0.838 g PPh4Br (2 mmol) in 15 ml
CH3CN was added under stirring. Then, the reaction
mixture was cooled to room temperature. The white pre-
cipitate of NaBr was filtered off, and the solvent was re-
moved in vacuo and the yellow product was
recrystallized from isopropanol and hexane. Yield:
1.132 g, 93%. Anal. Calc. for C28H26Cl3NO4P2: C,
55.24; H, 4.30; N, 2.3. Found: C, 55.0; H, 4.15; N,
2.2. Methods
2.2.1. NMR, IR-spectroscopy
IR spectra of the compounds were recorded on an
UR-10 spectrometer in the range 400–4000 cmꢀ1 (sam-
ples as KBr pellets or nujol mulls). H and 31P NMR
spectra were recorded on a Varian AMX 400 spec-
1
1
2.16%. H NMR (D2O): 7.74 m [8H (PPh4)+ – ortho,
7.56 m [12H (PPh4)+ – meta + para], 3.55 d [6H,