Job/Unit: I20686
/KAP1
Date: 10-09-12 10:45:39
Pages: 12
A Chelating Agent for Lead(II) and Diorganonolead(IV) Compounds
1
trated. A similar procedure with silver nitrate gave diphenyllead
nitrate. Dimethyllead acetate was also prepared in a similar way
with dimethyllead bromide[38] and silver acetate by stirring for 2 h.
Dimethyllead nitrate was obtained by the reaction of the bromide
with AgNO3 in methanol. Lead(II) acetate trihydrate (Aldrich) and
diisopropylamine (Merck) were used as supplied.
= 531 (14) [PbPh2(fspa) + H]. H NMR ([D6]DMSO): δ = 7.52 (s,
3
3
1 H, 3-H), 7.19 (d, JH,H = 3.4 Hz, 1 H, 5-H), 6.61 (dd, JH,H
=
3.2 Hz, 3JH,H = 1.9 Hz, 1 H, 6-H), 7.70 (d, JH,H = 1.7 Hz, 1 H, 7-
3
H), 7.87 (d, 3J1H,207 = 173.0 Hz, 3JH,H = 7.2 Hz, 4 H, Ph Ho), 7.56
Pb
3
3
(t, JH,H = 7.6 Hz, 4 H, Ph Hm), 7.43 (t, JH,H = 7.4 Hz, 2 H, Ph
Hp) ppm. 13C NMR ([D6]DMSO): δ = 172.4 (C-1), 133.1 (C-2),
121.4 (C-3), 152.7 (C-4), 111.8 (C-5), 112.2 (C-6), 142.2 (C-7),
163.6 (Ci), 134.1 (Co), 130.0 (Cm), 129.9 (Cp) ppm. 207Pb NMR
([D6]DMSO/DMSO, ca. 10–2 m): δ = –430 ppm. Single crystals of
[PbPh2(fspa)(DMSO)]·DMSO were grown by slow evaporation of
Elemental analyses were performed with a Carlo–Erba 1108 micro-
analyser. Melting points were determined with a Büchi apparatus.
IR spectra (KBr pellets) were recorded with a Bruker IFS66V
FTIR spectrophotometer. Mass spectra were recorded in methanol
a
[D6]DMSO
solution
of
[PbPh2(fspa)].
Those
of
using positive ESI with a Bruker Microtof spectrometer. The
FAB(+) spectrum (Xe, 8 eV) of one of the diphenyllead(IV) deriva-
tives was recorded with a Micromass Autospec spectrometer with
[PbPh2(fspa)(DMSO)] crystallized from the direct reaction of
H2fspa and PbPh2(OAc)2 in [D6]DMSO.
1
3-nitrobenzyl alcohol as a liquid matrix. H, 13C and 207Pb NMR
[HQ]2[Pb(fspa)2]: A solution of H2fspa (0.2 g, 1.2 mmol) in ethanol
(10 mL) was added to a mixture of lead(II) acetate (0.22 g,
0.6 mmol) and diisopropylamine (Q, 0.33 mL, 2.4 mmol) in the
spectra were obtained with Bruker DPX-250, Varian Mercury-300
and Bruker AMX-500 spectrometers operating at 250.13, 300.14 or
500.14 (1H), 75.46 or 125.76 (13C) and 104.57 MHz (207Pb), in [D6]- same solvent (20 mL). The resulting mixture was stirred for 2 h,
DMSO or [D7]DMF using 5 mm o.d. tubes; chemical shifts are
and the solid formed was separated by centrifugation and vacuum
dried. This first isolated solid, once analysed, was found to be
reported relative to TMS using the solvent signals [δ(1H) =
2.50 ppm, δ(13C) = 39.50 ppm; and δ(1H) = 8.02 ppm, δ(13C) = [Pb(fspa)]. When the mother liquor was left to stand, it afforded a
162.70 ppm, respectively] as reference, or reported (207Pb) relative
to an external saturated Ph4Pb solution [δ(207Pb) = –178 ppm] in
CDCl3.
new solid that was separated by centrifugation and vacuum dried;
yield 11%. C26H40N2O6PbS2 (747.93): calcd. C 41.75, H 5.39, N
3.75, S 8.57; found C 41.03, H 5.59, N 3.72, S 7.81. IR (KBr): ν =
˜
–
–
1520 [vs, νas(CO2 )], 1327 [vs, νs(CO2 )], 1610 [s, δ(NH2+)]. ESI-MS
[Pb(fspa)]: A solution of H2fspa (0.2 g, 1.2 mmol) in ethanol
(20 mL) was added to a solution of lead(II) acetate trihydrate
(0.45 g, 1.2 mmol) in water (20 mL), and a yellow solid formed im-
mediately. The reaction mixture was stirred for 1 h, and the solid
separated by centrifugation was vacuum dried; yield 95%.
(+): m/z (%) = 545 (2) [Pb(fspa)2 + H], 420 (11) [Pb(fspa) + CO2],
1
377 (100) [Pb(fspa) + H]. H NMR [D6]DMSO: δ = 7.32 (s, 2 H,
3-H), 7.19 (d, 3JH,H = 3.3 Hz, 2 H, 5-H), 6.47 (sept, 3JH,H = 2.4 Hz,
3
3
2 H, 6-H), 7.47 (d, JH,H = 1.9 Hz, 2 H, 7-H), 1.16 (d, JH,H
=
6.5 Hz, 24 H, NCH3), 3.26 (sept, JH,H = 6.5 Hz, 4 H, NCH). 13C
NMR ([D6]DMSO): δ = 178.6 (C-1), 140.1 (C-2), 120.3 (C-3), 154.5
(C-4), 109.9 (C-5), 111.6 (C-6), 141.1 (C-7), 19.2 (NCH3), 45.8
(NCH) ppm.
3
C7H4O3PbS (375.37): calcd. C 22.40, H 1.07, S 8.54; found C 22.27,
–
H 0.83, S 8.32. IR (KBr): ν = 1513 [vs, ν (CO )], 1328 [vs,
˜
as
2
–
νs(CO2 )]. ESI-MS (+): m/z (%) = 377 (46) ([Pb(fspa)] + H), 253
(100) [PbCO2 + H]. 1H NMR ([D6]DMSO): δ = 7.34 (s, 1 H, 3-H],
3
3
3
7.18 (d, JH,H = 3.4 Hz, 1 H, 5-H), 6.66 (dd, JH,H = 3.5 Hz, JH,H
[HQ]2[PbPh2(fspa)2]: A suspension of diphenyllead acetate (0.28 g,
= 1.8 Hz, 1 H, 6-H), 7.75 (d, JH,H = 1.8 Hz, 1 H, 7-H) ppm. 13C 0.6 mmol) in methanol (30 mL) was added to a solution of H2fspa
3
NMR ([D6]DMSO): δ = 181.6 (C-1), 137.2 (C-2), 123.4 (C-3), 153.5
(C-4), 111.8 (C-5), 112.1 (C-6), 141.1 (C-7) ppm.
(0.2 g, 1.2 mmol) and diisopropylamine (0.16 mL, 1.2 mmol) in
ethanol (15 mL). The mixture was stirred for 2 h, and the solid
formed was separated by centrifugation, dried under vacuum and
identified as [PbPh2(fspa)]. The mother liquor then afforded a sec-
ond solid of beige colour that was also separated by centrifugation
and vacuum-dried; yield 24%. C38H50N2O6PbS2 (902.14): calcd. C
50.59, H 5.59, N 3.11, S 7.11; found C 49.65, H 5.56, N 3.05, S
[PbMe2(fspa)]: A solution of H2fspa (0.07 g, 0.41 mmol) in absolute
ethanol (10 mL), neutralized with sodium hydroxide, was added to
a solution of PbMe2(OAc)2 (0.15 g, 0.41 mmol) in 15 mL of the
same solvent cooled in an ethanol/liquid nitrogen bath. After 1 h
of stirring, the mixture was concentrated to one third of its volume,
and the beige solid formed was separated by centrifugation and
vacuum dried; yield 47%. C9H10O3PbS (405.44): calcd. C 26.66, H
–
–
7.04. IR (KBr): ν = 1541 [vs, ν (CO )], 1342 [vs, ν (CO )], 1612 [s,
˜
as
2
s
2
δ(NH2+)]. FAB: m/z (%) = 531 (48) ([PbPh2(fspa) + H]), 377 (12)
1
[Pb(fspa) + H]), 285 (44) [PbPh]. H NMR ([D6]DMSO): δ = 7.39
2.49, S 7.91; found C 26.78, H 2.30, S 8.20. IR (KBr): ν = 1529
˜
(s, 2 H, 3-H), 7.21 (br. s, 2 H, 5-H), 6.53 (br. s, 2 H, 6-H), 7.55 (br
–
–
[vs, νas(CO2 )], 1356 [vs, νs(CO2 )]. ESI-MS (+): m/z (%) = 813 (15)
[2(PbMe2(fspa)) + H], 407 (76) [PbMe2(fspa) + H], 377 (59)
[Pb(fspa) + H], 283 (36) [PbC3H7O2], 254 (44) [Pb(CH3)3 + H], 239
(6) [Pb(CH3)2 + H], 223 (47) [PbCH3]. H NMR ([D7]DMF): δ =
7.66 (s, 1 H, 3-H), 7.36 (d, JH,H = 3.2 Hz, 1 H, 5-H), 6.66 (br. s,
3
s, 2 H, 7-H), 1.11 (d, JH,H = 6.5 Hz, 24 H, NCH3), 3.20 (sept,
3
3JH,H = 6.5 Hz, 4 H, NCH), 7.97 (br. s, J1H,207Pb = 168.0 Hz, 4 H,
Ph Ho), 7.32 (br. s, 4 H, Ph Hm), 7.22 (br. s, 2 H, Ph Hp) ppm. 13C
NMR ([D6]DMSO): δ = 171.2 (C-1), 139.6 (C-2), 117.0 (C-3), 154.3
(C-4), 110.0 (C-5), 111.7 (C-6), 140.6 (C-7), 18.7 (NCH3), 45.8
(NCH), 165.9 (Ci), 134.7 (Co), 128.5 (Cm), 127.8 (Cp) ppm. 207Pb
NMR ([D6]DMSO/DMSO, 1.2ϫ10–1 m): δ = –516 ppm.
1
3
2
1H,207Pb
1 H, 6-H), 7.75 (br. s, 1 H, 7-H), 2.17 [s, J
= 129.4 Hz, 6
H, Me] ppm. 13C NMR ([D7]DMF): δ = 175.4 (C-1), 135.2 (C-2),
122.3 (C-3), 154.4 (C-4), 113.2 (C-5), 113.2 (C-6), 143.2 (C-7), 33.1
(Me) ppm. Once [PbMe2(fspa)] was isolated, the mother liquor af-
forded some small crystals identified as Na[PbMe2(OAc)3] by X-
ray diffraction (vide infra).
X-ray Crystal Structure Determination Studies: Single crystals were
mounted on glass fibres in a Bruker APEXII automatic dif-
fractometer. Data were collected at 100 K {for Na[PbMe2(OAc)3]
and [PbPh2(fspa)(DMSO)]·DMSO} and 293 K {for [PbPh2(fspa)-
(DMSO)]} using Mo-Kα radiation (λ = 0.71073 Å). The crystal
data, experimental details and refinement results are summarized
in Table 1.
[PbPh2(fspa)]: A solution of H2fspa (0.2 g, 1.2 mmol) in ethanol
(20 mL) was added to a suspension of PbPh2(OAc)2 (0.56 g,
1.2 mmol) in methanol (40 mL). The mixture immediately afforded
a yellow solid that, after 1 h of stirring, was separated by centrifu-
gation and vacuum dried; yield 90%. C19H14O3PbS (529.58): calcd.
C 43.09, H 2.66, S 6.05; found C 42.92, H 2.27, S 5.65. IR (KBr):
Corrections for Lorentz effects, polarization[39] and semi-empirical
(ψ scan)[40,41] absorption were carried out. The structures were
solved by direct methods.[42] In the refinement, the non-H atoms
–
–
ν = 1517 [vs, ν (CO )], 1356 (vs, ν (CO ). ESI-MS (+): m/z (%)
˜
as
2
s
2
Eur. J. Inorg. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
9