Table 1 Reaction conditions and selected spectroscopic data of the macrocycles 2–6
Concentration
of phosphine/
Reaction time/h
Yield (%)
δP/ppmc
MS, m/z (Irel. (%), ion)
2
3
4
0.206
0.291
0.25
4
40
43
42
18
21
Ϫ50.5 (br.)
Ϫ47.8
Ϫ51.7
968 (100, [M]ϩ)a
1032 (100, [M]ϩ)b, 1049 (64, [MϩOϩH]ϩ)
988 (30, [M]ϩ)b, 1004 (85, [MϩO]ϩ), 1020 (100, [Mϩ2O]ϩ),
1036 (65, [Mϩ3O]ϩ), 1052 (10, [Mϩ4O]ϩ)
1041 (64, [MϩOϩH]ϩ)b, 1057 (100, [Mϩ2OϩH]ϩ), 1073
(82, [Mϩ3OϩH]ϩ)
5
0.328
41
21
Ϫ46.3
6
0.084
60
60
Ϫ41.5
1136 (100, [M]ϩ)a
a FAB mass spectrum. b MALDI-TOF mass spectrum (matrix: 3-nitroaniline). c In DMF.
2
of only poor quality due to low solubility; the most indicative
signals (those of the CH2 groups) had only very low intensity.
The IR spectra were recorded as nujol mulls on a Specord M-80
spectrometer in the range 400–4000 cmϪ1. The FAB mass
2JHH = 14.7 Hz, JPH = 5.0 Hz, 8H, P–CHa–N), 3.97 (dd,
2
2JHH = 14.7 Hz, JPH = 11.6 Hz, 8H, P–CHe–N), 6.08 (d,
3JHH = 8.9 Hz, 8H, o-H in N–C6H4), 7.11 (d, 3JHH = 8.9 Hz, 8H,
m-H in N–C6H4), 7.20–7.40 (m, 20H, C6H5). Anal. calc. for
C60H60N4P4S2 [1024]: C 70.31, H 5.86, N 5.46, P 12.11, S 6.25.
Found: C 69.82, H 6.11, N 5.23, P 11.86, S 6.01%.
spectra were obtained on
a ZAB-HSQ-VG Analytical
Manchester. The MALDI-TOF mass spectra were obtained on
a MALDI-TOF-DYNAMO spectrometer. The melting points
were determined on a Boetius apparatus and are uncorrected.
1,1Ј,5,5Ј-Bis[thio-bis(p-phenylene)]bis(3,7-dimesityl-1,5-diaza-
3,7-diphosphacyclooctane) (6). Yield: 1.02 g, 60%; mp 220 ЊC.
1H NMR (DMF-d7): δ 2.60 (s, 24H, o-CH3 in Mes), 2.83 (s,
Preparations
2
2
12H, p-CH3 in Mes), 4.25 (dd, JHH = 15.2 Hz, JPH = 7.8 Hz,
General procedure for the synthesis of 2–6. Solid paraform-
aldehyde (12 mmol) was added to the corresponding primary
phosphine (6 mmol) and the reaction mixture was heated
at 100–110 ЊC until the mixture became homogeneous. The
resulting bis(hydroxymethyl)organylphosphine was dissolved in
dry, degassed DMF (15–35 mL), and then a solution of the
corresponding diamine (3 mmol) in DMF (15–35 mL) was
added. The reaction mixture was stirred at 100–120 ЊC for 4–60
h (see Table 1). The precipitate formed was filtered off, washed
carefully with DMF and MeCN and dried at 0.1 Torr for 2–4 h.
31P{1H} NMR and FAB MS data are given in Table 1.
2
2
8H, P–CHe–N), 5.07 (dd, JHH = 15.2 Hz, JPH = 4.1 Hz, 8H,
P–CHa–N), 6.34 (d, 3JHH = 8.8 Hz, 8H, o-H in N–C6H4), 7.03 (s,
8H, m-H in Mes), 7.43 (d, 3JHH = 8.8 Hz, 8H, m-H in N–C6H4).
Anal. calc. for C68H76N4P4S2 [1136]: C 71.83, H 6.69, N 4.92, P
10.92, S 5.63. Found: C 71.19, H 7.01, N 4.65, P 11.14, S 5.87%.
X-ray crystallography
X-ray data collection, structure determination, and refinement.
Crystal data: C62H64N4P4ؒ4C3H7NO (4); M = 1281.51, mono-
clinic, space group P21/c, a = 10.045(1), b = 22.78(1), c =
15.661(3) Å, β = 96.50(1)Њ, V = 3560(1) Å3, T = 20 ЊC; Z = 2,
Dcalc = 1.20 (g cmϪ3); µ(Cu-Kα) = 1.387 mmϪ1; 3058 reflections
measured, 1691 were observed (I ≥ 2σ(I )). Final R = 0.084, Rw =
0.090 for 1184 reflections with F 2 ≥ 3σ(I ).
C60H60N4P4S2ؒ4C3H7NO (5); M = 1317.58, monoclinic, space
group P21/c, a = 9.983(1), b = 22.972(4), c = 15.777(2) Å, β =
96.94(1)Њ, V = 3592(1) Å3, T = 20 ЊC; Z = 2, Dcalc = 1.22 (g cmϪ3);
µ(Mo-Kα) = 0.208 mmϪ1; 7442 reflections measured, 2577 were
observed (I ≥ 2σ(I )). Final R = 0.056, Rw = 0.065 for 2543
reflections with F 2 ≥ 3σ(I ). One of the DMF molecules in 5 is
disordered between two positions with the equal occupancies
0.5.
1,1Ј,5,5Ј-Bis[thio-bis(p-phenylene)]bis(3,7-diphenyl-1,5-diaza-
3,7-diphosphacyclooctane) (2). Yield: 0.60 g, 42%; mp 220–
222 ЊC. 1H NMR (DMF-d7): δ 4.26 (dd, 2JHH = 15.0 Hz, 2JPH
=
2
2
13.4 Hz, 8H, P–CHe–N), 4.69 (dd, JHH = 15.0 Hz, JPH = 4.7
3
Hz, 8H, P–CHa–N), 6.73 (d, JHH = 8.7 Hz, 8H, o-H in
3
N–C6H4), 7.53 (d, JHH = 8.7 Hz, 8H, m-H in N–C6H4), 7.55–
7.90 (m, 20H, C6H5). Anal. calc. for C56H52N4P4S2 [968]: C
69.42, H 5.37, N 5.79, P 12.81, S 6.61. Found: C 68.96, H 5.61,
N 5.66, P 12.33, S 6.30%.
1,1Ј,5,5Ј-Bis[sulfo-bis(p-phenylene)]bis(3,7-diphenyl-1,5-diaza-
3,7-diphosphacyclooctane) (3). Yield: 0.28 g, 18%; mp 254–
Compounds 4 and 5 are isostructural.
C68H76N4P4S2ؒ3C3H7NO (6); M = 1356.62, hexagonal, space
257 ЊC. 1H NMR (DMF-d7,): δ 4.37 (dd, 2JHH = 15.6 Hz, 2JPH
=
2
2
3
¯
11.6 Hz, 8H, P–CHe–N), 4.81 (dd, JHH = 15.6 Hz, JPH = 4.7
group R3, a = 29.456(3), c = 22.728(5) Å, V = 17078(4) Å , T =
3
Ϫ50 ЊC; Z = 9, Dcalc = 1.19 (g cmϪ3); µ(Mo-Kα) = 0.205 mmϪ1
;
Hz, 8H, P–CHa–N), 6.96 (d, JHH = 9.1 Hz, 8H, o-H in
N–C6H4), 7.50–7.90 (m, 20H, C6H5), 7.78 (d, 3JHH = 9.1 Hz, 8H,
m-H in N–C6H4). Anal. calc. for C56H52N4O4P4S2 [1032]:
C 65.12, H 5.04, N 5.42, P 12.02, S 6.20. Found: C 64.81, H
5.59, N 5.34, P 11.63, S 6.11%.
33048 reflections measured, 7756 independent reflections. Final
R1 = 0.0552, Rw = 0.1583 for reflections with I ≥ 2σ(I ).
X-ray diffraction data were obtained with an Enraf-Nonius
CAD4 four-circle diffractometer [graphite monochromator,
Cu-Kα (4) and Mo-Kα (5) radiation, ω/2θ scan method, θ ≤
74.3Њ (4) or θ ≤ 26.4Њ (5)] or with a SMART CCD diffractometer
using ω scan rotation (6). Twenty-five centered reflections gave
the refined unit cell parameters. The structures of 4 and 5 were
solved in the uniquely assignable space group P21/c by direct
methods using SIR29 and difference Fourier syntheses. The
structure of 6 was solved by direct methods using SHELXS-97
and SHELXL-9730 for structure refinement. For 5 and 6, all
non-hydrogen atoms were refined anisotropically; for 4, only
the P and N atoms were refined anisotropically, and all other
non-hydrogen atoms were refined isotropically while the
thermal and positional parameters of hydrogen atoms were
fixed. The calculations for 4 and 5 were carried out on a DEC
Alpha Station 200 computer with the MolEN31 system.
1,1Ј,5,5Ј-Bis[methylene-bis(p-phenylene)]bis(3,7-dibenzyl-1,5-
diaza-3,7-diphosphacyclooctane) (4). Yield 0.31 g, 21%; mp
189 ЊC. 1H NMR (DMF-d7): δ 3.58 (s, 4H, CH2), 4.10 (dd, 2JHH
2
3
= 15.1 Hz, JPH = 10.9 Hz, 8H, P–CHe–N), 6.10 (d, JHH = 8.4
3
Hz, 8H, o-H in N–C6H4), 6.87 (d, JHH = 8.4 Hz, 8H, m-H in
N–C6H4), 7.24–7.50 (m, 20H, C6H5). P–CH2–Ph and P–CHa–N
are obscured by the solvent. Anal. calc. for C62H64N4P4 [988]: C
75.30, H 6.48, N 5.67, P 12.55. Found: C 74.92, H 6.79, N 5.16,
P 12.23%.
1,1Ј,5,5Ј-Bis[thio-bis(p-phenylene)]bis(3,7-dibenzyl-1,5-diaza-
3,7-diphosphacyclooctane) (5). Yield: 0.32 g, 21%; mp 200 ЊC.
1H NMR (DMSO-d6): δ 2.88 (s, 8H, P–CH2–Ph), 3.74 (dd,
D a l t o n T r a n s . , 2 0 0 4 , 4 4 2 – 4 4 7
443