i
3
13
119/117
5
91 Hz), 26.7 (s, Sn-Bu , J( C–
Sn): 102 Hz), 27.9 (s,
i
2
13
119/117
Sn-Bu , J( C–
Sn): 25 Hz), 31.5 (s, CH ), 103.1, (s, C ),
2
4
1
1
20.7, 125.4, 128.5, 138.4 (s, C ), 148.5 (s, C ), 163.2 (s, C ),
arom
3
5
119
91.9 (s, CO). Sn NMR (CDCl , 111.9 MHz): δ, Ϫ342.7.
3
Fig. 1 The Q2QH proligand used in this work.
Bis[(1,4-bis(5-hydroxy-1-phenyl-3-methyl-1H-pyrazol-4-yl)-
2
butane-1,4-dionate)dioctyltin(IV)] [SnOt (Q2Q)] (2). Com-
2
2
soluble dinuclear octahedral species [Sn-cis-R (Q2Q)] and
pound 2 was obtained as for 1 by using 1.0 mmol of dichloro-
dioctyltin() (SnOt Cl ). Yield 75ꢀ. Mp: 220–222 ЊC. Anal.
2
2
the bimetallic trigonal bipyramid [(SnR ) (Q2Q)] respectively.
3
2
2
2
i
The reaction of Q2QH with SnR Cl (R = Bu , Ot, Do) is also
Calc. for C H N O Sn: C, 62.11; H, 7.04; N, 7.24. Found: C,
40 54 4 4
Ϫ3
2
2
2
described.
61.78; H, 7.16; N, 7.25ꢀ. Λm (CH Cl , 1 × 10 M): 0.2. IR
2 2
Ϫ1
(
cm ): 1597vs ν(C᎐O), 443vs, 390m ν(Sn–O), 570m, 497s ν(Sn–
1
C). H NMR (CDCl , 200 MHz): δ, 0.84 (t, 6H, CH ), 1.06 (t,
3
3
Experimental
4
H, CH ), 1.25 (m br, 20H, CH ), 1.55 (m, 4H, CH ) 2.04 (s, 6H,
2
2
2
Materials and methods
C
3
-CH
3
), 2.92 (dd, 4H, CH , JAAЈ = 15.7 Hz, JAX = 240 Hz), 7.22
2
13
(
t, 2H, CHarom), 7.47 (t, 4H, CHarom), 8.02 (d, 4H, CHarom).
C
1
-Phenyl-3-methyl-pyrazolin-5-one, succinyl chloride and
NMR (CDCl , 50 MHz) δ, 14.6 (s, CH ), 17.8 (s, C -CH ),
3
3
3
3
potassium hydroxide were purchased from Aldrich (Milwaukee)
and used as received; organotin() halides were obtained from
Aldrich. Solvent evaporations were always carried out under
vacuum using a rotary evaporator. The samples for micro-
analysis were dried in vacuo to constant weight (20 ЊC, ca.
2
3.1(s, CH ), 26.2 (s, CH ), 26.5 (s, CH ), 29.7 (s, CH ), 29.9 (s,
2 2 2 2
CH ), 32.0 (s, CH ), 32.4 (s, CH ), 34.3 (s, CH ), 103.15 (s, C ),
2
2
2
2
4
1
1
1
21.2 (s, Carom), 125.8 (s, Carom), 129.0 (s, C ), 138.9 (s, Carom),
48.9 (s, C ), 163.6 (s, C ), 192.3 (s, CO). Sn NMR (CDCl3,
11.9 MHz): δ, Ϫ342.6.
arom
119
3
5
0
.1 Torr). All syntheses were carried out under a nitrogen
atmosphere. Hydrocarbon solvents were dried by distillation
from sodium–potassium; dichloromethane was distilled from
calcium hydride. All solvents were degassed with dry nitrogen
prior to use. Elemental analyses (C, H, N) were performed
in-house with a Fisons Instruments 1108 CHNS-O Elemental
Bis[(1,4-bis(5-hydroxy-1-phenyl-3-methyl-1H-pyrazol-4-yl)-
butane-1,4-dionate)didodecyltin(IV)] [SnDo (Q2Q)] (3).
2
2
Compound 3 was obtained as for 1 by using 1.0 mmol dichloro-
didodecyltin(). Yield 89ꢀ. Mp: 160–163 ЊC. Anal. Calc. for
C H N O Sn: C, 65.09; H, 7.97; N, 6.33. Found: C, 65.12; H,
Ϫ1
48 70
4
4
analyser. IR spectra were recorded from 4000 to 100 cm with
Ϫ3
Ϫ1
7
.46; N, 6.20ꢀ. Λ (CH Cl , 1 × 10 M): 0.1. IR (cm ): 1595vs
m 2 2
1
1
13
1
a Perkin-Elmer System 2000 FT-IR instrument. H, C{ H}
ν(C᎐O), 445vs, 393m ν(Sn–O), 556m, 497s ν(Sn–C). H NMR
119
1
᎐
and Sn{ H} NMR spectra were recorded on a VXR-300
Varian instrument and on a Bruker AC 200 spectrometer
operating at room temperature (respectively at 300 and 200
(
CDCl , 300 MHz): δ, 0.86 (t, 6H, CH ), 1.06 (m), 1.18 (m), 1.52
3
3
(
m), 1.65 (m) (46H, CH (CH ) CH ), 2.02 (s, 6H, C -CH ),
2 2 10 3 3 3
2
.89 (dd, 4H, CH , J
= 15 Hz, JAX = 363 Hz), 7.23 (t, 2H,
AAЈ
13
1
13
119
2
MHz for H, 75 and 50 MHz for C and 111.8 MHz for Sn).
CHarom), 7.43 (t, 4H, CHarom), 8.00 (d, 4H, CHarom). C NMR
The chemical shifts (δ) are reported in parts per million (ppm)
(
(
(
CDCl , 75 MHz) δ, 14.1 (s, CH ), 17.3 (s, C -CH ), 22.7
1
13
3
3
3
3
from SiMe4 ( H and C calibration by internal deuterium
s, CH ), 25.7 (s, CH ), 26.0 (s, CH ), 29.4 (s, CH ), 29.5
2
2
2
2
solvent lock) and SnMe . Peak multiplicities are abbreviated:
4
s, CH ), 29.6 (s, CH ), 29.7 (s, CH ), 29.8 (s, CH ), 31.5 (s,
2
2
2
2
singlet, s; doublet, d; triplet, t; multiplet, m. Melting points are
uncorrected and were taken on an SMP3 Stuart scientific
instrument and on a capillary apparatus. The electrical con-
CH ), 33.8 (s, CH ), 103.0 (s, C ), 120.7, 125.3, 128.5, 138.4 (s,
2
2
4
119
Carom), 148.4 (s, C ), 163.2, (s, C ), 191.8 (s, CO). Sn NMR
3
5
(
CDCl , 111.9 MHz): δ, Ϫ342.6.
Ϫ1
2
Ϫ1
3
ductivity measurements (Λ , reported as Ω cm mol ) of
m
dichloromethane solutions of complexes 1–8 were taken with a
Crison CDTM 522 conductimeter at room temperature. The
Bis[(1,4-bis(5-hydroxy-1-phenyl-3-methyl-1H-pyrazol-4-yl)-
butane-1,4-dionate)dimethyltin(IV)] [SnMe (Q2Q)] (4). To a
2
2
donor Q2QH was synthesised by the procedure reported by
2
toluene solution (50 ml) of Q2QH (0.430 g, 1 mmol) Me SnO
34
2
2
Jensen and re-crystallized from hot methanol. Molecular
weight (MW) determinations, carried out on selected com-
pounds, were performed at 40 ЊC with a Knauer KNA0280
vapour pressure osmometer calibrated with benzil. The solvent
was Baker Analysed Spectrophotometric grade methanol. The
results were reproducible to ±2ꢀ.
(
2
0.164 g, 1 mmol) was added. The clear solution was stirred for
4 h. The solvent was removed under reduced pressure and
diethyl ether was then added to obtain a colourless precipitate.
Re-crystallisation from chloroform–diethyl ether gave the
pale-yellow derivative 4. Yield 80ꢀ. Mp: 314–315 ЊC. Anal.
Calc. for C H N O Sn: C, 54.10; H, 4.54; N, 9.71. Found: C,
2
6
26
4
4
Ϫ3
5
(
4.43; H, 4.84; N, 9.52ꢀ. Λm (CH Cl , 1 × 10 M): 0.1. MW
2 2
Ϫ3 Ϫ1 Ϫ1
Syntheses
CHCl , c = 1.5 × 10 mol l ): 1100. IR (cm ): 1614s, 1591vs
3
1
Bis[(1,4-bis(5-hydroxy-1-phenyl-3-methyl-1H-pyrazol-4-yl)-
ν(C᎐O), 443vs, 420m ν(Sn–O), 583m ν(Sn–C). H NMR
i
2
2 1
butane-1,4-dionate)diisobutyltin(IV)] [SnBu (Q2Q)] (1). To a
(CDCl , 200 MHz): δ, 0.41 (s, 6H, Sn–CH , J(Sn– H): 71.8
3 3
2
methanol solution (30 ml) of Q2QH2 (0.430 g, 1 mmol)
potassium hydroxide (0.112 g, 1.0 mmol) and dichloro-
diisobutyltin() (0.303 g, 1 mmol) were added. The mixture
was stirred overnight. A colourless precipitate formed which
was filtered off and washed with methanol (10 ml), then
re-crystallized from chloroform–methanol. Yield 86ꢀ. Mp:
Hz), 2.08 (s, 6H, C -CH ), 2.96 (dd, 4H, CH , J = 16 Hz, JAX
3 3 2 AAЈ
= 240 Hz), 7.26 (t, 2H, CHarom), 7.47 (t, 4H, CHarom), 8.02 (d,
1
3
4H, CH ). C NMR (CDCl , 75 MHz) δ, 6.9 (s, Sn-CH3
arom
1
3
1
119
J( Sn– H: 623 Hz), 14.1 (s, CH ), 17.3 (s, C -CH ), 31.7 (s,
3
3
3
CH ), 103.0 (s, C ), 120.7, 125.4, 128.6, 138.4 (s, Carom), 148.6 (s,
2
4
119
C ), 163.2, (s, C ), 191.9 (s, CO). Sn NMR (CDCl , 111.9
3
5
3
2
56–259 ЊC. Anal. Calc. for C H N O Sn: C, 58.11; H, 5.79;
MHz): δ, Ϫ309.6.
32
38
4
4
N, 8.47. Found: C, 58.45; H, 5.85; N, 8.75ꢀ. Λ (CH Cl , 1 ×
m
2
2
Ϫ3
Ϫ3
Ϫ1
1
(
0
M): 0.1. MW (CHCl , c = 1.5 × 10 mol l ): 1310. IR
cm ): 1597vs ν(C᎐O), 442vs, 399m ν(Sn–O), 613s ν(Sn–C). H
Bis[(1,4-bis(5-hydroxy-1-phenyl-3-methyl-1H-pyrazol-4-yl)-
3
Ϫ1
1
n
butane-1,4-dionate)di-n-butyltin(IV)] [SnBu (Q2Q)] (5). Com-
2
2
NMR (CDCl , 300 MHz): δ, 0.86 (t, 6H, CH ), 1.08 (t, 4H,
pound 5 was obtained as for 4. Yield 80ꢀ. Mp: 224–226 ЊC.
3
3
CH ), 1.35 (m, 4H, CH ), 1.54 (m, 4H, CH ), 2.05 (s, 6H,
Anal. Calc. for C H N O Sn: C, 58.11; H, 5.79; N, 8.47.
2
2
2
32 38
4
4
Ϫ3
C -CH ), 2.93 (dd, 4H, CH , J
= 15 Hz, JAX = 240 Hz),
Found: C, 58.35; H, 5.86; N, 8.34ꢀ. Λm (CH Cl , 1 × 10 M):
2 2
Ϫ3 Ϫ1 Ϫ1
3
3
2
AAЈ
7
.25 (t, 2H, CHarom), 7.45 (t, 4H, CHarom), 8.03 (d, 4H, CHarom).
0.05. MW (CHCl , c = 1.5 × 10 mol l ): 1320. IR (cm ):
3
13
i
C NMR (CDCl , 75 MHz) δ, 13.8 (s, Sn-Bu ), 17.3 (s,
1603vs ν(C᎐O), 442vs, 395m ν(Sn–O), 619s, 611s, 570m
3
᎐
i
1
13
119
1
13
117
1
C -CH ), 25.6 (s, Sn-Bu , J( C– Sn): 610 Hz, J( C– Sn):
ν(Sn–C). H NMR (CDCl , 300 MHz): δ, 0.86 (t, 6H, CH ),
3
3
3
3
J. Chem. Soc., Dalton Trans., 2002, 188–194
189