Z. Pikramenou et al.
FULL PAPER
the resultant material was identified as the desired compound by 1H and 31
P
filtered, washed with methanol (2 Â 2 mL) and dried under vacuum
(0.054 g, 78%). Single crystals, suitable for an X-ray diffraction analysis,
were grown by slow evaporation from a CHCl3 solution. 1H NMR
(250 MHz, CDCl3): d 7.16 7.15 (m, 24H; Ar), 6.31 6.10 (m, 24H; Ar),
3.06 (s, 36H; CH3); 31P{1H} NMR (101 MHz, CDCl3): d 25.7 (s); IR
(KBr): nÄ 1224, 1195 (PNP) and 1098, 1071 cmÀ1 (PO); FAB-MS: m/z:
NMR spectroscopy. Because of the sensitivity of the material, the THF/
toluene solution of this compound was used without further purification.
1H NMR (250 MHz, CDCl3): d 2.47 (d, 6H, 4J(P,H) 2.7 Hz, CH3);
31P{1H} NMR (101 MHz, CDCl3): d 74.4 (s).
N-(P,P-Di-2-methylphenylphosphinoyl)-P,P-di-2-methylphenyl-phosphini-
midic acid (Metpip): Hexamethyldisilazane (1.59 g, 9.85 mmol) was
dissolved in dry toluene (2 mL) and added dropwise to a solution of
chlorodi-2-methylphenylphosphine in toluene/THF under nitrogen
(25 mmol, assuming 100% yield of preparation described above). This
solution was refluxed for 4.5 h, after which time Me3SiCl and THF were
distilled off. The solution was cooled in an ice bath for 30 minutes. H2O2
(1.7 mL, 35 wt.% in H2O) in THF (2 mL) was added dropwise, and the
solution stirred for 18 h. This solution was added to diethyl ether (50 mL),
resulting in the immediate precipitation of a white solid. The solid was
filtered and washed with water and MeOH to give the desired product
(0.71 g, 15%, based on hexamethyldisilazane). 1H NMR (250 MHz,
CDCl3): d 7.82 7.74 (m, 4H; Ar), 7.33 7.27 (m, 4H; Ar), 7.14 7.00 (m,
8H; Ar), 2.18 (s, 12H; CH3); 31P{1H} NMR (101 MHz, CDCl3): d 25.4 (s);
IR (KBr): nÄ 1196, 1215 and 1229 (PNP) and 1068, 1094 cmÀ1 (PO); FAB-
1571 [MH] , 1097 [M À Metpip] ; UV/Vis (CH3CN): lmax
(e [dm3 molÀ1 cmÀ1]) 278 (6800), 271 nm (6200); elemental analysis calcd
(%) for C84H84EuN3O6P6: C 64.29, H 5.39, N 2.68; found: C 63.95, H 5.55, N
2.52.
[Tb(Metpip)3]: TbCl3 ¥ 6H2O (0.014 g, 0.037 mmol) dissolved in methanol
(1 mL) was added dropwise to a solution of KMetpip (0.053 g, 0.10 mmol)
in methanol (8 mL). The white solid that immediately precipitated was
filtered, washed with methanol (2 Â 2 mL) and dried under vacuum
(0.050 g, 86%). 31P{1H} NMR (101 MHz, CDCl3): d 142 (brs); IR
(KBr): nÄ 1224, 1195 (PNP) and 1098, 1071 cmÀ1 (PO); FAB-MS: m/z:
1576 [MH] , 1103 [M À Metpip] ; elemental analysis calcd (%) for
C84H84TbN3O6P6: C 64.00, H 5.37, N 2.67; found: C 63.62, H 5.47, N 2.57.
Crystal structure analysis: Single-crystal X-ray diffraction data were
collected on a Stoe Stadi-4 diffractometer equipped with an Oxford
Cryosystems low-temperature device operating at 220 K. CuKa radiation
was used for the potassium complex, and the structure was solved by direct
methods (SIR92).[39] MoKa radiation was used for the Eu complex, and its
structure was solved by Patterson methods (DIRDIF).[40] Absorption
corrections based on y scans were applied to both data sets. Both structures
were refined by full-matrix least-squares against F2 (Shelxtl),[41] with H
atoms in idealised positions. Further analysis was performed with Platon.[42]
MS: m/z: 474 [MH] ; elemental analysis calcd (%) for C28H29NO2P2 ¥
0.5H2O: C 69.70, H 6.27, N 2.90; found: C 69.89, H 6.10, N 2.77.
Potassium tetraphenylimidodiphosphinate (Ktpip): Htpip (0.30 g,
0.72 mmol) was dissolved in a 2% methanolic KOH solution (10 mL).
The solvent volume was decreased to 2 mL under reduced pressure and
diethyl ether was added (20 mL). The resultant solid was recrystallised
from ethanol to give the desired product (0.187 g, 58%). 1H NMR
(360 MHz, D2O): d 7.79 7.73 (m, 8H; Ar), 7.52 7.41 (m, 12H; Ar);
Crystallographic data of [K(Metpip)(MeOH)2(H2O)]n: C30H38KNO5P2,
M 593.65, orthorhombic, space group Pna21, a 16.956(7), b 22.495(5),
c 8.0303(19) ä, V 3063.0(16) ä3, Z 4, 1calcd 1.287 gcmÀ3, F(000)
31P{1H} NMR (146 MHz, D2O): d 17.0 (s); FAB-MS: m/z: 456 [MH] .
KMetpip: Metpip (0.615 g, 1.30 mmol) was heated at reflux for 1 h in a
10% methanolic KOH solution (30 mL). The solvent was removed under
reduced pressure and the resultant white solid was washed with water
(5 mL). This solid was recrystallised from ethanol to give the desired
product (0.390 g, 59%). Single crystals of KMetpip suitable for an X-ray
diffraction analysis were grown by slow evaporation from a methanolic
solution. 1H NMR (200 MHz, CD3OD): d 8.31 8.20 ((m, 4H; Ar), 7.29
6.99 (m, 12H; Ar), 2.12 (s, 12H; CH3); 31P{1H} NMR (81 MHz, CD3OD):
1256, m 2.817 mmÀ1
,
R1 0.0709 [qmax 708, 1556 data F > 4s(F)],
wR2 0.1716 for 2854 independent reflections, GOF 0.977.
Crystallographic data of [Eu(Metpip)3] ¥ CHCl3: Single crystals of [Eu-
(Metpip)3], suitable for X-ray diffraction analysis, were grown by slow
evaporation from a CHCl3 solution. C85H85Cl3EuN3O6P6, M 1688.69,
≈
rhombohedral, space group R3, a b 15.2788(6), c 30.532(5) ä, V
6172.5(10) ä3, Z 3, 1calcd 1.363 gcmÀ3, F(000) 2604, m 1.029mmÀ1
,
d 9.1 (s); FAB-MS: m/z: 512 [MH] , 550 [MK] ; UV/Vis (MeOH):
lmax (e [dm3 molÀ1 cmÀ1]) 270 (2700), 277 nm (2500); elemental analysis
calcd (%) for C28H28KNO2P2 ¥ 3.5H2O: C 58.53, H 6.14, N 2.44; found:
C 58.19, H 6.30, N 2.25.
R1 0.0549 [qmax 258, 2217 data F > 4s(F)], wR 0.1296 for 2418 inde-
pendent reflections, GOF 1.113. The point group of this complex is 3;
however, it is disordered about at crystallographic À3 special position.
Similarity and rigid bond restraints were applied to all light-atom
anisotropic displacement parameters. The chloroform of solvation was
also disordered, its geometry was controlled during refinement by the
application of explicit restraints.
Ln(tpip)3 (Ln Eu, Tb, Sm, Dy): To a solution of Ktpip (3 equiv, 0.187 g,
0.41 mmol) in H2O, was added dropwise LnCl3 ¥ xH2O (1 equiv) dissolved
in H2O. The white solid that immediately precipitated was filtered, washed
with H2O several times and dried under vacuum to give the corresponding
[Ln(tpip)3] in 70 80% yield.
CCDC-187661 and -187662 contain the supplementary crystallographic
data for this paper. These data can be obtained free of charge via
tallographic Data Centre, 12 Union Road, Cambridge CB21EZ, UK; fax:
(44)1223-336033; or deposit@ccdc.cam.uk).
[Eu(tpip)3]: 1H NMR (360 MHz, CDCl3): d 7.54 7.48 (m, 24H; Ar), 7.21
(t, 12H; 3J(H,H) 7.4 Hz, Ar), 6.95 6.99 (m, 24H; Ar); 13C{1H} NMR
(91 MHz, CDCl3): d 129.8 (d, 1J(P,C) 137 Hz, quart. C), 129.4 (s), 128.9
(d, J(P,C) 10 Hz), 127.0 (d, J(P,C) 13 Hz); 31P{1H} NMR (146 MHz,
CDCl3): d 37.7 (s); FAB-MS: m/z: 1400 [MH] , 983 [M À tpip] ; UV/
Vis (CHCl3): lmax (e [dm3 molÀ1 cmÀ1]) 273 nm (5000); elemental analysis
calcd (%) for C72H60EuN3O6 ¥ 3H2O: C 59.43, H 4.57, N 2.89; found:
C 59.16, H 4.24, N 2.83.
Acknowledgement
Support for this work from EPSRC (S.W.M) is gratefully acknowledged.
The authors gratefully acknowledge the assistance of Ross Blackwood in
preparing the [Sm(tpip)3] and [Dy(tpip)3] samples.
[Tb(tpip)3]: 1H NMR (360 MHz, CDCl3): d 7.97 (brs, 24H; Ar), 7.35 (s,
12H; p-Ar), 6.28 (s, 24H; Ar); 13C{1H} NMR (91 MHz, CDCl3): d 159.3
(quart. C), 134.5 (s), 130.4 (s), 128.6 (s); 31P{1H} NMR (146 MHz, CDCl3):
d 200.7 (s); FAB-MS: m/z: 1408 [MH] , 991 [M À tpip] .
[Sm(tpip)3]: 1H NMR (250 MHz, CDCl3): d 7.66 7.58 (m, 24H; Ar),
7.26 7.19 (m, 12H; p-Ar), 7.08 7.03 (m, 12H; Ar); 13C{1H} NMR (63 MHz,
CDCl3): d 131.1, 131.0, 130.9, 129.8, 127.5, 127.4, 127.3 [s, d, d, d]; 31P{1H}
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NMR (101 MHz, CDCl3) 25.1 (s); FAB-MS: m/z: 1403 [MH] , 985 [M À
tpip] .
[Dy(tpip)3]: 1H NMR (250 MHz, CDCl3): d 8.1 (brs, 24H; Ar), 7.45 (brs,
12H; p-Ar ), 6.57 (brs, 24H; Ar); 13C{1H} NMR (63 MHz, CDCl3): d 154
(brs), 132.6 (s), 130.2 (s), 128.3 (s); 31P{1H} NMR (101 MHz, CDCl3): d
147.9 (s); FAB-MS: m/z: 1414 [MH] , 997 [M À tpip] .
[Eu(Metpip)3]: EuCl3 ¥ 6H2O (0.016 g, 0.044 mmol) dissolved in methanol
(1 mL) was added dropwise to a solution of KMetpip (0.067 g, 0.13 mmol)
in methanol (5 mL). The white solid that immediately precipitated was
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5770
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Chem. Eur. J. 2002, 8, No. 24