8.67 mmol) followed by diethoxy(methyl)phosphine (1.18 g,
8.67 mmol) were added. The solution was boiled at reflux over
molecular sieves. After 15 h, the excess paraformaldehyde was
Calcd for C23H37O7N5F3P3159Tb 804.1111. Found 804.1110. ; t
(H2O) 3.14 ms, t (D2O) 3.46 ms; q = 0; HPLC: tR = 10.6 min.
[L2bHo]
(0.06 g, 0.18 mmol) as a white solid (0.09 g); 19F NMR (188 MHz,
D2O) d -61.2 (CF3); ESI/MS m/z 834.2 [M+Na]+, 810.2 [M-H]-;
MS Calcd for C23H37O7N5F3P3165Ho 810.1161. Found 810.1136.
[L2bEr]
(0.06 g, 0.18 mmol) as a white solid (0.06 g); 19F NMR (188 MHz,
D2O) d -72.8 (CF3); ESI/MS+ m/z 815.1 [M+H]+, 837.1 [M+Na]+;
MS Calcd for C23H39O7N5F3P3168Er 815.1445. Found 815.1395.
removed by filtration and the solvent removed under reduced
pressure. The resulting orange oil was purified by alumina gel
column chromatography, eluting with a gradient starting from
100% CH2Cl2 to 1.7% CH3OH–CH2Cl2 to yield a pale yellow oil
(0.96 g); 1H NMR (400 MHz, CDCl3) d 1.15 (9H, m, CH3), 1.36
(9H, m, CH3), 2.41–3.98 (22H, br m, cyclen CH2 and CH2P), 3.16
(2H, s, CH2CO), 3.91 (6H, m, CH2CH3), 7.07 (1H, t, J = 7 Hz,
Ar), 7.41 (1H, t, J = 8 Hz, Ar), 7.46 (1H, d, J = 8 Hz, Ar), 8.11
(1H, d, J = 7 Hz, Ar), 9.61 (1H, s, NH); 13C NMR (176 MHz,
[L2bTm]
(0.11 g); 19F NMR (188 MHz, D2O) d -90.6 (CF3); ESI/MS+
m/z 816.1 [M+H]+; MS Calcd for C23H39O7N5F3P3169Tm 816.1357.
Found 816.1348.
[L2bDy]
(0.10 g); 19F NMR (188 MHz, D2O) d -63.7 (CF3); ESI/MS-
m/z 805.1 [M-H]-; MS Calcd for C23H37O7N5F3P3160Dy 805.1110.
Found 805.1142.
1
3
CDCl3) d 13.4 (d, J = 90 Hz, PCH3), 16.95 (CH3), 53.4 (d, J =
84, CH2P), 54.5, 54.6, 55.2 (br, 8C, cyclen CH2), 60.5 (CH2CO),
2
1
121.0 (q, JCF = 30 Hz, CCF3), 124.2 (q, JCF = 273 Hz, CF3),
125.4, 126.4, 127.6, 133.2, 135.8 (4C, Ar), 169.3 (C O); 31P NMR
(162 MHz, CDCl3) d +52.33 (1P, s, PCH3), +52.47 (2P, s, PCH3);
19F NMR (376 MHz, CDCl3) d -60.98 to -60.94 (isomer mixture,
CF3); ESI/MS+ m/z 734.3 [M + H]+, 756.3 [M+Na]+; MS Calcd
for C29H54N5O7P3F3 734.3188. Found 734.3200.
Acknowledgements
We thank EPSRC and ESF-COST D38 for support.
References
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azacyclodecan-1-yl)methyl](methyl)phosphinate
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1
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pD 5.4) d 1.12 (9H, d, J = 13 Hz, PCH3), 2.56–3.83 (22H, br m,
cyclen CH2 and CH2P), 3.20 (2H, s, CH2CO), 7.14 (1H, m, Ar),
7.24 (1H, m, Ar), 7.48 (1H, m, Ar), 7.60 (1H, m, Ar), 9.50 (1H, s,
NH); 31P NMR (162 MHz, D2O pD 5.4) d +40.62 (3P, s, PCH3);
19F NMR (376 MHz, D2O pD 5.4) d -61.28 (s, CF3).
[L2bTb]
An analogous procedure to that described for [L1bTb] was
followed using H3L2b (0.10 g, 0.15 mmol) and TbIII(OAc)3 (0.06 g,
0.18 mmol) . The complex was purified by chromatography on
a short column of alumina (eluting with dichloromethane/10%
MeOH) to yield a white solid (0.10 g); 19F NMR (188 MHz, D2O)
d -45.9 (CF3); ESI/MS m/z 828.2 [M+Na]+, 804.2 [M-H]-; MS
912 | Dalton Trans., 2011, 40, 904–913
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