Z. Shariatinia et al. / Journal of Organometallic Chemistry 715 (2012) 82e92
83
2.2. X-ray measurements
(d6-DMSO):
d
¼ 14.54 (s, CH3), 29.40 (d, 3J(P,C) ¼ 4.5 Hz, CH2), 29.51
(d, 3J(P,C) ¼ 4.7 Hz, CH2), 41.96 (s, CH), 44.87 (d, 2J(P,C) ¼ 3.2 Hz,
CH2), 45.15 (d, 3J(P,C) ¼ 3.3 Hz, CH2), 61.06 (s, OCH2), 129.21 (s),
129.38 (s), 133.26 (s), 134.98 (d, 3J(P,C) ¼ 9.7 Hz, ipso-C), 169.39 (s,
C]O), 175.50 (s, C]O). IR (KBr, cmꢁ1): 3433 (NH), 3073 (CH), 2935
(CH), 2869 (CH), 1727 (C]O), 1448, 1282, 1186 (P]O), 1039 (PeN),
956 (PeN), 716, 540.
X-ray data of compound 1 were collected on a Bruker SMART
1000 CCD [22] single crystal diffractometer with graphite mono-
ꢀ
chromated Mo K
a
radiation (
l
¼ 0.71073 A). The structures were
refined with SHELXL-97 [23] by full-matrix least-squares on F2. The
positions of hydrogen atoms were obtained from the difference
Fourier map. Routine Lorentz and polarization corrections were
applied and an absorption correction was performed using the
SADABS program [24].
2.3.4. Bis[N-benzoyl-N0,N00-bis(N-4-phenylpiperazinyl) phosphoric
triamide] stannate(IV) tetrachloride pentahydrate (4)
N-benzoyl-N0,N00-bis(N-4-phenylpiperazinyl) phosphoric tri-
amide (1 mmol, 0.489 g) was added to a solution of tin tetrachloride
pentahydrate (5 mmol, 0.175 g) in dry methanol at 25 ꢀC. After 48h
stirring, the solution was evaporated and the white powder was
washed with ethylacetate. M.p. ¼ 162e164 ꢀC. Yield: 61%; Anal.
Calc. for C54H74Cl4N10O9P2Sn: C, 48.78; H, 5.61; N, 10.53%. Found: C,
2.3. Synthesis
2.3.1. N-benzoyl-N0,N00-bis(4-phenylpiperazinyl) phosphoric
triamide (1)
To a solution of N-benzoylphosphoramidic dichloride (5 mmol,
1.19 g) in dry acetonitrile, 4-phenylpiperazine (20 mmol, 3.24 g)
was added dropwise at 0 ꢀC and the mixture stirred for 24 h. Then
the solution was evaporated and the white precipitate was filtered,
washed with CHCl3 and recrystallized in MeOH/CH3CN mixture.
M.p. ¼ 144e145 ꢀC. Yield: 59%. Anal. Calc. for C27H32N5O2P: C,
66.24; H, 6.59; N, 14.31%. Found: C, 66.22; H, 6.58; N, 14.30%. 31P
48.76; H, 5.60; N, 10.54%. 31P{1H} NMR (CD3OD):
d
¼ 10.77 (s). 1H
NMR (CD3OD):
d
¼ 3.61 (m, 16H, CH2), 3.72 (m, 16H, CH2), 7.40 (t,
3J(H,H) ¼ 6.8 Hz, 4H, Ar-H, N-benzoyl), 7.51e7.66 (m, 20H, Ar-H,
phenylpiperazinyl), 7.97 (t, 3J(H,H) ¼ 6.8 Hz, 2H, Ar-H, N-benzoyl),
7.99 (d, 3J(H,H) ¼ 6.8 Hz, 4H, Ar-H, N-benzoyl). 13C NMR (CD3OD):
d
¼ 44.42 (s, CH2), 55.25 (s, CH2), 118.16 (s), 121.06 (s), 129.46 (s),
{1H} NMR (d6-DMSO):
d
¼ 9.37 (s). 1H NMR (d6-DMSO):
¼ 3.10 (m,
d
129.83 (s), 130.40 (s), 131.36 (s), 134.26 (s), 146.00 (s), 171.86 (s, C]
O). FT-IR (KBr, cmꢁ1): 3409 (NH), 3055 (CH), 2923 (CH), 2363, 1670
(C]O), 1597, 1495, 1447, 1258, 1198 (P]O), 1074 (PeNamine), 959
(PeNamide), 693, 538 (SneC)s.
8H, CH2), 3.30 (m, 8H, CH2), 6.78 (t, 3J(H,H) ¼ 7.9 Hz, 2H, Ar-H), 6.92
(d, 3J(H,H) ¼ 7.9 Hz, 4H, Ar-H), 7.20 (d, 3J(H,H) ¼ 7.9 Hz, 4H, Ar-H),
7.46 (d, 3J(H,H) ¼ 7.8 Hz, 2H, Ar-H), 7.58 (t, 3J(H,H) ¼ 7.8 Hz, 1H, Ar-
H), 7.94 (d, 3J(H,H) ¼ 7.8 Hz, 2H, Ar-H), 9.42 (b, 1H, NH). 13C NMR
(d6-DMSO):
d
¼ 44.21 (s, CH2), 48.87 (d, 2J(P,C) ¼ 5.1 Hz, CH2),115.68
2.3.5. Bis[N-benzoyl-N0,N00-bis(N-4-ethoxypiperazinyl) phosphoric
triamide] dimethyl stannate(IV) dichloride (5)
(s), 119.11 (s), 128.23 (s), 128.30 (s), 128.91 (s), 132.21 (s), 133.61 (d,
3J(P,C) ¼ 8.6 Hz, ipso-C), 151.16 (s), 168.39 (d, 2J(P,C) ¼ 1.7 Hz, C]O).
IR (KBr, cmꢁ1): 3425 (NH), 3067 (CH), 2856 (CH), 1675 (C]O), 1596,
1445, 1205 (P]O), 1134 (PeN), 972 (PeN), 719, 534.
N-benzoyl-N0,N00-bis(N-4-ethoxypiperazinyl) phosphoric tri-
amide (1 mmol, 0.457 g) was added to a solution of dimethyltin(IV)
dichloride (5 mmol, 0.110 g) in dry methanol at 25 ꢀC and the
mixture stirred for two days. Then the solution was evaporated and
the precipitate was washed with diethylether. M.p. ¼ 102e104 ꢀC.
Yield: 55%; Anal. Calc. for C40H70Cl2N10O12P2Sn: C, 42.34; H, 6.22;
N, 12.35%. Found: C, 42.33; H, 6.21; N, 12.34%. 31P{1H} NMR
2.3.2. N-benzoyl-N0,N00-bis(4-ethoxy carbonylpiperazinyl)
phosphoric triamide (2)
To a solution of N-benzoylphosphoramidic dichloride (5 mmol,
1.19 g) in dry acetonitrile, 4-ethoxy carbonylpiperazine (20 mmol,
3.16 g) was added dropwise at 0 ꢀC and the mixture stirred for 30 h.
Then the solution was evaporated and the residue was washed with
ethylacetate and diethylether. M.p. ¼ 124e125 ꢀC. Yield: 62%; Anal.
Calc. for C21H32N5O6P: C, 52.39; H, 6.70; N, 14.55%. Found: C, 52.37;
(CD3OD):
H)
d
¼ 11.36 (s). 1H NMR (CD3OD):
d
¼ 0.84 (d, 2J(119Sn,
¼
35.0 Hz, SneCH3), 0.98 (s, 6H, SneCH3), 1.24 (t,
3J(H,H) ¼ 7.2 Hz, 6H, CH3), 1.26 (t, 3J(H,H) ¼ 7.2 Hz, 6H, CH3), 3.20
(m, 8H, ring-CH2), 3.22 (m, 8H, ring-CH2), 3.47 (m, 8H, ring-CH2),
3.71 (m, 8H, ring-CH2), 4.12 (m, 4H, OCH2), 4.14 (m, 4H, OCH2), 7.50
H, 6.71; N, 14.56%. 31P{1H} NMR (d6-DMSO):
d
¼ 9.38 (s). 1H NMR
3
(t, J(H,H) ¼ 7.5 Hz, 4H, Ar-H, N-benzoyl), 7.60 (t, 3J(H,H) ¼ 7.5 Hz,
(d6-DMSO):
d
¼ 1.16 (t, 3J(H,H) ¼ 7.1 Hz, 6H, CH3), 3.09 (m, 8H, CH2),
2H, Ar-H, N-benzoyl), 7.89 (d, 3J(H,H) ¼ 7.5 Hz, 4H, Ar-H, N-
3.32 (m, 8H, CH2), 4.03 (q, 3J(H,H) ¼ 7.1 Hz, 4H, CH2), 7.46 (d,
3J(H,H) ¼ 7.3 Hz, 1 H, Ar-H), 7.58 (t, 3J(H,H) ¼ 7.3 Hz, 2 H, Ar-H), 7.89
(d, 3J(H,H) ¼ 7.3 Hz, 2H, Ar-H), 9.26 (b, 1H, NH). 13C NMR (d6-
benzoyl). 13C NMR (CD3OD):
d
¼ 14.80 (s, CH3), 14.88 (s, CH3), 41.81
(s, OCH2), 44.36 (s, ring-CH2), 45.31 (s, OCH2), 45.66 (s, ring-CH2),
62.87 (s, ring-CH2), 63.42 (s, ring-CH2), 129.22 (s), 129.72 (s), 133.91
(s), 157.24 (s), 169.98 (s, C]O). FT-IR (KBr, cmꢁ1): 3418 (NH), 2924
(CH), 2859 (CH), 2479, 2360, 1703 (C]O), 1430, 1246, 1196 (P]O),
1137 (PeNamine), 977 (PeNamide), 720.
DMSO):
d
¼ 14.49 (s), 44.42 (s), 45.27 (s), 60.85 (s),127.38 (s),128.22
(s), 133.54 (d, 3J(P,C) ¼ 8.5 Hz, ipso-C), 154.60 (s), 168.56 (s, C]O). IR
(KBr, cmꢁ1): 3433 (NH), 3072 (CH), 2985 (CH), 2877 (CH), 1694 (C]
O), 1446, 1236 (P]O), 1129 (PeN), 969 (PeN), 716, 534.
2.3.3. N-benzoyl-N0,N00-bis(4-ethoxy carbonylpiperidinyl)
phosphoric triamide (3)
2.3.6. Bis[tris (N-phenyl hydrazinyl) phosphoric triamide]
stannate(IV) tetrachloride (6)
To a solution of N-benzoylphosphoramidic dichloride (5 mmol,
1.19 g) in dry acetonitrile, 4-ethoxy carbonylpiperidine (20 mmol,
3.12 g) was added dropwise at 0 ꢀC and the mixture stirred for 48 h.
Then the solution was evaporated and the residue was washed with
CCl4 and diethylether. M.p. ¼ 116e117 ꢀC. Yield: 67%; Anal. Calc. for
C23H34N3O6P: C, 57.61; H, 7.15; N, 8.76%. Found: C, 57.59; H, 7.14; N,
A solution of tin(IV) tetrachloride (5 mmol, 1.30 g) in dry
methanol (20 ml) was added dropwise to a solution of tris(N-
phenyl hydrazinyl) phosphoric triamide (10 mmol, 3.68 g) at
room temperature and under nitrogen atmosphere. After two days
stirring, the solution was evaporated and the yellow powder was
purified by washing with acetone. M.p. ¼ 228e229 ꢀC. Yield: 47%;
Anal. Calc. for C36H42Cl4N12O2P2Sn: C, 43.36; H, 4.24; N, 16.86%.
8.75%. 31P{1H} NMR (d6-DMSO):
d
¼ 10.49 (s). 1H NMR (d6-DMSO):
d
¼ 1.59 (t, 3J(H,H) ¼ 7.1 Hz, 6H, CH3), 1.83 (dd, 3J(H,H) ¼ 7.6 Hz, 4H,
Found: C, 43.34; H, 4.25; N, 16.85%. 31P{1H} NMR (CDCl3):
d
¼ 0.00
CH2), 1.96 (m, 4H, CH2), 2.44 (m, 2H, CH), 2.80 (m, 4H, CH2), 3.56
(dd, 3J(H,H) ¼ 7.6 Hz, 4H, CH2), 4.08 (q, 3J(H,H) ¼ 7.1 Hz, OCH2), 7.48
(d, 3J(H,H) ¼ 7.8 Hz, 2H, Ar-H), 7.59 (t, 3J(H,H) ¼ 7.8 Hz, 1H, Ar-H),
8.00 (d, 3J(H,H) ¼ 7.8 Hz, 2H, Ar-H), 8.88 (b, 1H, NH). 13C NMR
(s). 1H NMR (CDCl3):
d
¼ 6.93 (m, 3H, Ar-H), 7.30 (m, 2H, Ar-H), 8.23
(b, 1H, NH), 10.07 (b, 1H, NH). IR (KBr, cmꢁ1): 3423 (NH), 3296 (NH),
3202 (NH), 2999 (CH),1606,1494,1206 (P]O), 887 (PeN), 855, 764,
679, 493 (SneO).