Methyllead(IV) derivatives stabilized by DAPTSC2-: Synthesis and structures of new diorganolead(IV) complexes

Article abstract of DOI:10.1002/ejic.200700096

The reaction of the bis(thiosemicarbazone) of dimethyl pyridine-2,6-diyl diketone, H₂DAPTSC, with PbMe₂(OAc)₂, PbMePh(OAc)₂ or PbPh₂(OAc)₂ in MeOH afforded the complexes [PbMe₂(DAPTSC)], [PbMePh(DAPTSC)] or [PbPh ₂-(DAPTSC)] (in the first two cases together with [Pb(DAPTSC)]). X-ray crystallography of the Pb(IV) complexes showed that the metal has a pentagonal bipyramidal coordination sphere. The N₃,S ₂-bound DAPTSC^2- anion occupied the eguatorial plane and the organic groups were in the apical positions. These compounds retain the same coordination mode in DMSO solution. DAPTSC^2- is also N ₃,S₂-bound in [Pb(DAPTSC)], a complex with a stereochemically active Pb^II lone pair. The reaction of PbPh ₂Cl₂ with H₂DAPTSC, also in methanol at room temperature, afforded [PbPh₂(H₂DAPTSC)] ₂[PbPh₂Cl₄]Cl₂·6CH ₃OH. X-ray crystallography of this centrosymmetric complex showed it to consist of two [PbPh₂(H₂DAPTSC)]²⁺ cations of similar structure to the neutral [PbR₂(DAPTSC)] complexes, together with a trans-octahedral [PbPh₂Cl₄]^2- anion and two Cl^- anions. This compound decomposes in DMSO solution, probably evolving to H₂DAPTSC and PbPh₂Cl ₂(DMSO)_n. In order to evaluate the changes undergone by H₂DAPTSC under metallation, the X-ray structure of the free molecule was also determined. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.

Full text of DOI:10.1002/ejic.200700096

FULL PAPER
DOI: 10.1002/ejic.200700096
Methyllead(IV) Derivatives Stabilized by DAPTSC2–: Synthesis and Structures
of New Diorganolead(IV) Complexes
José S. Casas,*[a] Eduardo E. Castellano,[b] Javier Ellena,[b] María S. García-Tasende,[a]
Facundo Namor,[a] Agustín Sánchez,[a] José Sordo,[a] and María J. Vidarte[a]
Dedicated to Professor Joachim Strähle on the occasion of his 70th birthday
Keywords: Lead / Diorganolead(IV) complexes / Metallation
The reaction of the bis(thiosemicarbazone) of dimethyl pyr-
idine-2,6-diyl diketone, H2DAPTSC, with PbMe2(OAc)2,
PbMePh(OAc)2 or PbPh2(OAc)2 in MeOH afforded the com-
plexes [PbMe2(DAPTSC)], [PbMePh(DAPTSC)] or [PbPh2-
(DAPTSC)] (in the first two cases together with
[Pb(DAPTSC)]). X-ray crystallography of the Pb(IV) com-
plexes showed that the metal has a pentagonal bipyramidal
coordination sphere. The N3,S2-bound DAPTSC2– anion oc-
cupied the equatorial plane and the organic groups were in
the apical positions. These compounds retain the same coor-
dination mode in DMSO solution. DAPTSC2– is also N3,S2-
bound in [Pb(DAPTSC)], a complex with a stereochemically
active PbII lone pair. The reaction of PbPh2Cl2 with
H2DAPTSC, also in methanol at room temperature, afforded
[PbPh2(H2DAPTSC)]2[PbPh2Cl4]Cl2·6CH3OH. X-ray crystal-
lography of this centrosymmetric complex showed it to con-
sist of two [PbPh2(H2DAPTSC)]2+ cations of similar structure
to the neutral [PbR2(DAPTSC)] complexes, together with a
trans-octahedral [PbPh2Cl4]2– anion and two Cl– anions. This
compound decomposes in DMSO solution, probably evolving
to H2DAPTSC and PbPh2Cl2(DMSO)n. In order to evaluate
the changes undergone by H2DAPTSC under metallation,
the X-ray structure of the free molecule was also determined.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2007)
2 PbMe2X2 Ǟ PbMe3X + PbMeX3
(1)
Introduction
Structural information on methyllead(IV) coordination
This is followed by a reduction-elimination step carried
compounds is rather scarce. Apart from a small number of out by the monomethyl derivative, see Equation (2).
compounds with lead–metal bonds or with relatively simple
PbMeX3 Ǟ MeX + PbX2
(2)
anions (tetramethyllead,[1] trimethyllead chloride,[2] trimeth-
yllead iodide,[3] trimethyllead acetate,[4] trimethyllead 2-fur-
This evolution seems to be stimulated by the presence of
Lewis bases such as DMSO, possibly because these bases
stabilize the decomposition products.
ate,[5] trimethyllead diphenylphosphinate[6] or trimethyllead
methylthiolato[7]), the only such structure in the CSD[8] is
that of the complex bis(tetraphenylimidodiphosphanato)di-
methyllead(IV), which was obtained in the recrystallization
of the corresponding trimethyllead compound.[6] This pauc-
ity of information is probably related to the intrinsic insta-
bility of methyllead(IV) compounds, which are more un-
stable than the corresponding phenyl derivatives.
As the redistribution process probably involves short dis-
tance between the lead centres,[10] we speculated that the
starting organolead compound might be more stable, the
bulkier the ligand X. We have investigated this idea using
the potentially pentadentate bis(thiosemicarbazone) ligand
(H2DAPTSC, Figure 1) as X2. This Schiff base coordinates
well, in both neutral and deprotonated forms, to a variety
of metal and organometal ions.[11] Coordination usually oc-
curs through N(3), N(4), N(5), S(1) and S(2), and results in
the occupation of a significant part of the volume around
the metal centre.
According to the classic papers of Huber et al.,[9] the
decomposition of dimethyllead(IV) compounds occurs
through redistribution of the methyl groups as shown in
Equation (1).
Herein we describe the synthesis and structures of new
complexes obtained using this strategy, including the first
methylphenyllead(IV) and only the second dimethyllead-
(IV) coordination compounds to have been studied by X-
ray diffractometry.
[a] Departamento de Química Inorgánica, Facultad de Farmacia,
Universidad de Santiago de Compostela,
15782 Santiago de Compostela, Spain
E-mail: qiscasas@usc.es
[b] Instituto de Física de São Carlos, Universidade de São Paulo,
CEP 13560 São Carlos, Brazil
3742
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2007, 3742–3750

Methyllead(IV) Derivatives Stabilized by DAPTSC2–
FULL PAPER
tion data were not of high quality, the conformations and
relative orientations of the thiosemicarbazide chains are un-
questionable, and this information is relevant to the analysis
of the changes that occur upon deprotonation and coordi-
nation. The bond lengths and angles in these chains
(Table 1) are unexceptional.[14] The chain bearing S(1) is
roughly parallel to the line through C5 and N4 (named the
“closed-arm” orientation in this article), and places the
methyl group C(10)H3 trans to N(4). By contrast, the chain
bearing S(2) is roughly orthogonal to the line C5–N4 (the
“open-arm” orientation), and places the methyl group
C(11)H3 cis to N(4). These orientations, together with the
(Z) configuration about C(2)=N(3) in the closed arm, the
(E) configuration about C(8)=N(5) in the open arm, and
Figure 1. Molecular structure of H2DAPTSC·MeOH. Ellipsoids the mutually trans orientations of the N–N and C=S bonds
are drawn at the 50% probability level.
in both chains, allow the stabilization of the molecule by
three intramolecular hydrogen bonds (Figure 1 and
Table 2). That the same structure has been observed in the
Results and Discussion
dimethylthallium(III) complex [TlMe2(HDAPTSC)][15] sug-
gests that it holds in methanol solutions of H2DAPTSC as
well as in the solid state.
Synthesis
H2DAPTSC was combined in methanol with
Interestingly, the above structure differs from the struc-
tures of the three N1- or N2-substituted bis(thiosemicarba-
zones) derived from dimethyl pyridine-2,6-diyl diketone
that were studied previously by X-ray diffractometry,
namely the bis(3-hexamethyleneiminylthiosemicarbazone)
PbMe2(OAc)2, PbMePh(OAc)2, PbPh2(OAc)2, PbPh3(OAc)
and PbPh2Cl2. The reaction of the diacetates evolved as ex-
pected: the bis(thiosemicarbazone) replaced the acetate
anions, the basicity of which favoured the observed depro-
tonation of the incoming ligand.
(H2L1·H2O),[13a]
the
bis(1-ethylthiosemicarbazone)
(H2L2)[13b] and the bis(1-methylthiosemicarbazone)
(H2L3),[13c] although these compounds differ composition-
ally only concerning the substituents at N(1) and N(7)
(H2L1 and H2L1) or N(2) and N(5) (H2L3). Note that the
lattices of H2L2 and H2L3 contain only the bis(thiosemi-
carbazone) molecules, whereas those of H2L1·H2O and
H2DAPTSC·MeOH also feature molecules of solvent. Al-
though there is a thiosemicarbazide chain with open-arm
orientation in all four molecules, the other arm is open in
H2L2 and H2L3, closed in H2DAPTSC·MeOH and “semi-
closed” in H2L1·H2O (Scheme 1). Such variety is not unex-
pected given the flexibility of thiosemicarbazide chains,
which readily adapt their conformations to minimize weak
intra- and intermolecular forces. Together with the differ-
ences in composition and in the number and nature of inter-
molecular hydrogen bonds, it leads to these compounds
PbR2(OAc)2 + H2DAPTSC Ǟ [PbR2(DAPTSC)] + 2 HOAc
However, the additional isolation of [Pb(DAPTSC)]
when the organometallic moiety had methyl groups showed
that hindrance of the redistribution reaction, Equation (1),
was not complete. [PbPh2(DAPTSC)] was also the product
of the reaction between H2DAPTSC and PbPh3(OAc),
probably through a protodephenylation (acidic decomposi-
tion) reaction. Reaction of H2DAPTSC with PbPh2Cl2 gave
a product, the stoichiometry of which suggested that the
bis(thiosemicarbazone) ligand was neutral and only re-
placed the chloride ligands of two-thirds of the PbPh2Cl2
molecules, the remaining third accepting half of the dis-
placed Cl– anions, see Equation (3).
3 PbPh2Cl2 + 2 H2DAPTSC Ǟ 2 [PbPh2(H2DAPTSC)]2+
+
(3)
[PbPh2Cl4]2– + 2 Cl–
This explains why unreacted H2DAPTSC was recovered
in spite of the reaction having being carried out in a 1:1
mol ratio. A somewhat related process has been observed[12]
when PbPh2Cl2 was combined with certain monothiosem-
icarbazones (HTSCs), although in these cases only one
chloride ligand was displaced from the coordination sphere
of the metal, giving [PbPh2Cl(HTSC)]+.
Solid-State Structures
Figure 1
shows
the
molecular
structure
of
H2DAPTSC·MeOH, which, unlike those of certain similar
compounds (see paragraph below),[13] has not hitherto been
determined by X-ray crystallography. Although the diffrac- Scheme 1.
Eur. J. Inorg. Chem. 2007, 3742–3750
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
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J. S. Casas et al.
FULL PAPER
Table 1. Selected bond lengths [Å] and angles [°] in the ligand and complexes.
Parameter
H2DAPTSC·MeOH
[PbMe2(DAPTSC)][a]
[PbPhMe(DAPTSC)]·0.45H2O
Pb–C
2.205(12)
2.207(11)
2.533(6)
2.509(9)
2.170(12) (Me)
2.212(13) (Ph)
2.540(9)
2.473(10)
2.561(9)
Pb–N(3)
Pb–N(4)
Pb–N(5)
Pb–S(1)
Pb–S(2)
2.769(2)
1.725(7)
2.734(3)
2.736(3)
S(1)–C(1)
S(2)–C(9)
N(1)–C(1)
N(2)–C(1)
N(3)–C(2)
N(3)–N(2)
N(4)–C(7)
N(4)–C(3)
N(5)–C(8)
N(5)–N(6)
N(6)–C(9)
C(2)–C(3)
C(7)–C(8)
C–Pb–C
1.674(4)
1.694(4)
1.336(5)
1.367(4)
1.296(5)
1.367(5)
1.341(4)
1.353(5)
1.288(4)
1.383(4)
1.361(4)
1.494(5)
1.489(5)
1.763(13)
1.726(12)
1.358(14)
1.285(18)
1.256(16)
1.395(13)
1.351(13)
1.367(14)
1.266(16)
1.403(13)
1.280(16)
1.515(16)
1.378(14)
168.7(5)
1.346(9)
1.317(10)
1.293(10)
1.378(9)
1.351(8)
1.496(9)
172.9(5)
69.58(15)
64.14(15)
S(1)–Pb–N(3)
N(3)–Pb–N(4)
N(4)–Pb–N(5)
N(5)–Pb–S(2)
S(1)–Pb–S(2)
70.0(3)
65.0(3)
64.9(3)
69.9(3)
90.36(10)
[PbPh2(DAPTSC)]·MeOH
[PbPh2(H2DAPTSC)]2[PbPh2Cl4]Cl2·6CH3OH[b]
[Pb(DAPTSC)][c]
Pb–C
2.215(3)
2.218(4)
2.530(3)
2.474(3)
2.543(3)
2.6598(9)
2.6954(9)
1.733(4)
1.737(4)
1.351(4)
1.337(5)
1.296(4)
1.386(4)
1.351(4)
1.349(4)
1.303(5)
1.387(4)
1.326(5)
1.493(5)
1.483(5)
169.57(12)
70.78(7)
65.56(9)
65.56(9)
70.86(7)
88.29(3)
2.189(4), 2.191(4) (Pb1)
2.201(4), 2.8023(10) (Pb2)
2.546(3)
2.531(3)
2.580(3)
2.7684(10)
2.7973(11)
1.703(4)
1.699(4)
1.307(6)
1.361(5)
1.281(5)
1.368(5)
1.347(5)
1.347(5)
1.297(6)
1.373(5)
1.364(6)
Pb–N(3)
Pb–N(4)
Pb–N(5)
Pb–S(1)
2.612(18)
2.48(2)
2.67(2)
2.848(7)
2.825(8)
1.73(4)
1.76(3)
1.31(3)
1.36(5)
1.32(4)
1.40(3)
1.38(3)
1.39(3)
1.31(3)
1.38(3)
1.25(4)
1.43(3)
1.51(4)
Pb–S(2)
S(1)–C(1)
S(2)–C(9)
N(1)–C(1)
N(2)–C(1)
N(3)–C(2)
N(3)–N(2)
N(4)–C(7)
N(4)–C(3)
N(5)–C(8)
N(5)–N(6)
N(6)–C(9)
C(2)–C(3)
C(7)–C(8)
C–Pb–C
1.485(6)
1.489(6)
174.67(15)
70.70(8)
63.75(11)
63.73(11)
69.62(8)
S(1)–Pb–N(3)
N(3)–Pb–N(4)
N(4)–Pb–N(5)
N(5)–Pb–S(2)
S(1)–Pb–S(2)
65.1(4)
62.5(6)
60.7(6)
65.2(4)
72.6(2)
93.33(3)
[a] S(1)–Pb–S(1)i 93.25(11) (i = –x, y, z). [b] Pb(2)–Cl(2) 2.7005(10); Pb(2)–Cl(1) 2.8023(10); C–Pb(2)–Ci 180.0, Cl(1)–Pb(2)–Cl(1)i 180.0,
Cl(2)–Pb(2)–Cl(2)i 180.0 (i = –x + 2, –y, –z). [c] Pb–S(1)i = 3.312(8), Pb–S(2)i 3.385(8), (i = 1 + x, y, z).
having very different supramolecular structures: dimers in two chains bind the lead atom symmetrically, and together
H2L1·H2O and H2L3, chains in H2L2 and two-dimensional with the nitrogen atom of the pyridine ring occupy the
sheets in H2DAPTSC·MeOH.
equatorial plane of a pentagonal bipyramidal coordination
The molecular structure of [PbMe2(DAPTSC)] is shown, polyhedron in which the two methyl groups of the almost
2+
together with its numbering scheme, in Figure 2. The dide- linear PbMe2 unit [C–Pb–C 172.9(5)°] are apical. The re-
protonated ligand coordinates to the dimethyllead(IV) unit sulting [PbC2N3S2] kernel has not hitherto been observed.
through S1, S(1)i, N(3), N(3)i and N(4) (i = –x, y, z). The The strongest Pb–N interaction is with the pyridine nitro-
3744
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Eur. J. Inorg. Chem. 2007, 3742–3750

Methyllead(IV) Derivatives Stabilized by DAPTSC2–
FULL PAPER
Table 2. Intra- and intermolecular hydrogen bonds in the ligand
and complexes [Å, °].
D–H
H···A
D···A
D–H···A
H2DAPTSC·MeOHA[a]
N(1)–H(1A)···N(3)
N(1)–H(1B)···S(2)i
N(2)–H(2)···N(4)
0.86
0.86
0.86
0.86
0.86
0.86
0.86
0.69(5)
2.26
2.53
1.96
2.65
2.30
2.29
2.57
2.56(5)
2.623(4)
3.385(3)
2.639(4)
3.499(3)
2.650(4)
3.032(4)
3.431(3)
3.236(4)
105.6
172.8
134.6
170.9
104.3
144.6
177.9
167(5)
N(6)–H(6A)···S(2)ii
N(7)–H(7A)···N(5)
N(7)–H(7A)···O(1)iii
N(7)–H(7B)···S(1)iv
O(1)–H(11)···S(1)v
[PbMe2(DAPTSC)][b]
N(1)–H(1A)···S(1)ii
N(1)–H(1B)···N(2)iii
0.8600
0.8600
2.8374
2.1109
3.5630(7)
2.9546(9)
143.13
166.76
[PbPhMe(DAPTSC)]·0.45H2O[c]
Figure 2. Molecular structure of [PbMe2(DAPTSC)]. Ellipsoids are
drawn at the 50% probability level.
N(1)–H(1A)···N(6)i
N(7)–H(7A)···N(2)ii
0.8800
0.8800
2.1635 3.0368(13)
202461 3.1194(12)
171.63
171.63
That DAPTSC2–, as expected, embraces the organome-
tallic moiety, and must hamper intermolecular approach,
but the observed formation of [Pb(DAPTSC)] shows that it
is still possible to approach the Pb centre from above or
below the equatorial coordination plane. We are currently
investigating whether more enveloping ligands provide bet-
ter stabilization of their methyllead(IV) complexes, so re-
ducing the formation of lead(II) derivatives.
The structures of [PbPhMe(DAPTSC)]·0.45H2O (Fig-
ure 3) and [PbPh2(DAPTSC)]·MeOH (see Figure S1 in the
electronic supplementary information) are similar to that
of [PbMe2(DAPTSC)], showing only minor differences in
certain bond lengths and angles and the expected packing
differences deriving from their solvent molecules. Analysis
of these small structural differences is difficult, because the
esd values are not always similar and because the intermo-
lecular forces can influence the intramolecular ones. For ex-
ample, the Pb–S bonds of [PbMe2(DAPTSC)] are slightly
longer than those of [PbPh2(DAPTSC)]·MeOH (see
Table 1), but this could be due either to an intrinsically
smaller acceptor capacity of the Me2Pb2+ moiety or to the
lessening of the donor ability of the sulfur as a consequence
of its intermolecular N(1)–H(1)···S bond. Also, in the di-
phenyllead(IV) complex the two arms of the ligand are no
longer equivalent, showing small differences in the Pb–N
and Pb–S bond lengths.
[PbPh2(DAPTSC)]·MeOH[d]
N(1)–H(1A)···O(1S)
N(1)–H(1B)···N(6)i
O(1S)–H(1S)···N(7)
N(7)–H(7A)···O(1S)ii
N(7)–H(7B)···N(2)ii
0.8800
0.8800
0.8400
0.8800
0.8800
2.2570
2.2558
2.3681
2.1632
2.2244
2.9220(4)
3.1229(4)
3.1760(4)
2.9283(4)
3.0997(4)
132.23
168.46
161.51
145.06
172.95
[PbPh2(H2DAPTSC)]2[PbPh2Cl4]Cl2·6CH3OH[e]
N(1)–H(1A)···Cl(3)ii
N(1)–H(1B)···O(31)iii
N(2)–H(2)···Cl(3)ii
N(6)–H(6)···Cl(1)
N(7)–H(7A)···Cl(1)
N(7)–H(7B)···Cl(3)iv
O(31)–H(31)···Cl(3)iii
O(41)–H(41)···O(51)iii
O(51)–H(51)···Cl(3)
0.8800
0.8800
0.8800
0.8800
0.8800
0.8800
0.8400
0.8400
0.8400
2.4405
1.9695
2.4104
2.5243
2.4429
2.4029
2.4629
1.9029
2.3474
3.2540(4)
2.8222(5)
3.2116(4)
3.3107(4)
3.2686(4)
3.2438(4)
3.2598(3)
2.7405(6)
3.1822(4)
153.92
162.80
151.55
149.16
156.45
160.07
158.69
174.81
172.57
[Pb(DAPTSC)][f]
N(1)–H(1A)···N(6)ii
N(7)–H(7A)···N(1)iii
N(7)–H(7B)···N(2)iv
0.880
0.880
0.880
2.3178
2.5993
2.3379
3.0966(3)
3.1230(3)
3.1254(3)
147.55
119.07
149.03
Symmetry operations: [a] i = x – 1, –y + 0.5, z – 0.5; ii = –x + 2, –y
+ 1, –z; iii = –x + 2, –y + 0.5, –z + 0.5; iv = x + 1, –y + 0.5, z + 0.5;
v = x, –y + 0.5, z + 0.5. [b] ii = 0.5 – x, – 1 – y, –0.5 + z; iii = 0.2 –
x, – 1 – y, 0.5 + z. [c] i = x – 0.5, –y + 0.5, z + 0.5; ii = x + 0.5, –y +
0.5, z – 0.5. [d] i = 0.5 + x, 0.5 – y, –0.5 + z; ii = 0.5 – x, 0.5 + y,
0.5 – z. [e] ii = 0.5 + x, 0.5 – y, –0.5 + z; iii = 0.5 – x, 0.5 + y, 0.5 –
z; iv = 0.5 – x, 0.5 + y, 0.5 – z. [f] ii = –1 + x, y, –1 + z; iii = 1 + x,
y, 1 + z; iv = x, y, 1 + z.
Figure 4 shows the molecular structure and numbering
scheme of [PbPh2(H2DAPTSC)]2[PbPh2Cl4]Cl2·6CH3OH.
This complex is centrosymmetric, consisting of two
gen [Pb–N(4) 2.509(9)], although this bond is longer than [PbPh2(H2DAPTSC)]2+ cations, a [PbPh2Cl4]2– anion and
the sum of the covalent radii, 2.35 Å.[16] The identical thio- the two chloride anions. As in the [PbR2(DAPTSC)]
semicarbazone chains adopt E conformation around C(2)– complexes (see also ref.[11c,17–20]), in the cation
N(3) and Z around C(1)–N(2). The conformational changes [PbPh2(H2DAPTSC)]2+ the thiosemicarbazone ligand binds
with respect to free H2DAPTSC are summarized in to the diphenyllead(IV) fragment through its two sulfur and
Scheme 2. The C–S bond is longer in the complex three nitrogen atoms. However, there are two major differ-
[1.725(7) Å] than in H2DAPTSC [1.674(4) and 1.694(4) Å], ences with respect to [PbPh2(DAPTSC)]·MeOH: i) all the
showing the expected thione-to-thiol evolution upon metal- metal–ligand bonds are longer, and ii) both the C–S bond
lation. Two hydrogen bonds involving the N(1)H2 groups lengths suggest scant evolution of the ligand to the thiol
and the S and N(2) atoms of neighbouring molecules (see form. Both these differences reflect weaker interaction with
Table 2) give rise to a 2D network in the xz plane.
the organometallic cation.
Eur. J. Inorg. Chem. 2007, 3742–3750
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3745

J. S. Casas et al.
FULL PAPER
Scheme 2.
that case it interacted with the [PbPh2(BPyTSC)] moiety
through chloro bridges, while in the present case it is only
linked to the [PbPh2(H2DAPTSC)]2+ cation by the hydro-
gen bonds N(6)–H(6)···Cl(1) and N(7)–H(7A)···Cl(1) (see
Table 2). In keeping with this, the Pb(2)–Cl(2) bond in the
present compound is shorter than any of the Pb–Cl bonds
in the BPyTSC complex, in which both Cl atoms are brid-
ges and one takes part in a hydrogen bond. By contrast, the
Pb(2)–Cl(1) bond is longer than any of the Pb–Cl bonds in
[{PbPh2(BPyTSC)}2(PbPh2Cl4)]·2MeOH, probably because
of the two hydrogen bonds of Cl(1). These interactions, to-
gether with others involving the isolated chloride ion Cl(3)
and the solvent molecules (Table 2), give rise to a compli-
cated two-dimensional network.
Figure 5
shows
the
molecular
structure
of
Figure 3. Molecular structure of [PbPhMe(DAPTSC)]·0.45H2O.
Ellipsoids are drawn at the 50% probability level.
[Pb(DAPTSC)]. In this case, the five donor atoms of the
ligand define the base of a pentagonal pyramid, and the
PbII cation is 1.1 Å from this plane. The location of all the
metal–ligand interactions on the same side of the metal cen-
tre suggests the presence of a stereochemically active lone-
In the anion [PbPh2Cl4]2–, the Pb(2) atom is octahedrally
coordinated. This fragment was previously found in
[{PbPh2(BPyTSC)}2(PbPh2Cl4)]·2MeOH,[12] although in-
Figure 4. Crystal structure of [PbPh2(H2DAPTSC)]2[PbPh2Cl4]Cl2·6CH3OH. All hydrogen atoms, except those on MeOH, and N atoms
have been omitted for clarity. Ellipsoids are drawn at the 30% probability level.
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Methyllead(IV) Derivatives Stabilized by DAPTSC2–
FULL PAPER
pair on the other side. Except for minor differences in bond [PbPh2Cl4]Cl2·6CH3OH and [PbPh2(DAPTSC)]. 1H and
lengths, this is the same molecular structure as when the 13C NMR spectra were interpreted by comparison with
ligand is N(1),N(7)-dimethylated,[21] but the crystal packing those of the ligand.[11a]
is different. In the lattice of [Pb(DAPTSC)] the molecules
The 1H and 13C NMR spectra of [PbPh2(H2DAPTSC)]2-
stack along the x axis, each Pb centre increasing its coordi- [PbPh2Cl4]Cl2·6CH3OH show signals in positions similar to
nation number to 7 by means of two weak Pb···Si interac- those found in the spectra of the free ligand and PbPh2Cl2
tions with the neighbouring molecule on the side opposite in [D6]DMSO. This suggests that Equation (3) has been
its own ligand (i = 1 + x, y, z) and giving rise to a polymeric shifted to the left, possibly because PbPh2Cl2 forms adducts
chain (Figure 6). These polymeric chains interact by N– with the solvent DMSO.[22] The 207Pb chemical shift and
H···N hydrogen bonds (see Table 2) to form two-dimen- 3J(13C-207Pb) coupling constant support this conclusion,
sional networks in the xz plane. In the N(1),N(7)-dimeth- their values being the same as those obtained for PbPh2Cl2
ylated complex[21] no secondary interactions are observed, in DMSO solution.[12] The value of the molar conductivity
and each monomer links to another two through π–π inter- in DMSO, 8.0 S·cm2·mol–1 (10–3 ), rules out any ionic be-
actions between their pyridine rings and the resulting poly- haviour,[23] and is likewise in accordance with the proposed
meric chains are linked in 2D networks by NH···S hydrogen evolution.
bonds.
The 1H spectra of [PbMe2(DAPTSC)], [PbPh2-
(DAPTSC)], [PbMePh(DAPTSC)] and [Pb(DAPTSC)] are
all similar. With respect to the spectrum of the free ligand,
the signals corresponding to the N(2,6)H protons disappear
because of the formation of DAPTSC2– in the complexes;
the signals of the N(1,7)H2 groups shift to higher fields and
merge to form just one signal; the C(5)H protons become
slightly deshielded and C(4,6)H is shielded. The 13C NMR
spectra of [PbPh2(DAPTSC)] and [PbPhMe(DAPTSC)] are
also similar: in both complexes, C(1,9), C(2,8) and C(3,7)
are all more shielded than in the free ligand, while C(4,6),
C(5) and C(10,11) become deshielded. The shielding of
C(1,9) by about 3 ppm is in accordance with evolution of
the C=S group to the thiol form when S coordinates to the
metal. The shielding of C(2,8) and deshielding of C(10,11)
testify to the persistence of Pb–N(3) and Pb–N(5) interac-
tions when the complexes are dissolved in DMSO, while the
deshielding of the pyridine ring carbons C(4,6) and C(5)
suggests that the Pb–N(4) interaction also perdures. This
behaviour is similar to that of the analogous dimethyl and
diphenyltin(IV) complexes, [SnR2(DAPTSC)],[11a] which in
the solid state show the same coordination scheme as in the
lead complexes.
Figure 5. Molecular structure of [Pb(DAPTSC)]. Ellipsoids are
drawn at the 50% probability level.
The above conclusions are also supported by the avail-
able NMR spectroscopic data for the diorganolead(IV)
moieties. For [PbPh2(DAPTSC)], a coordination of at least
seven is suggested by the fact that the J and J(1H-207Pb)
coupling constants are larger than in compounds with a
coordination number of six;[24] and although the chemical
shift of 207Pb for this compound, –608.9 ppm, is very close
to those found in the spectra of certain diaryllead(IV) ace-
tates, for which a coordination number of six has been pos-
tulated,[25] this chemical shift is probably not at odds with
heptacoordination to C, N and S atoms, as N and S atoms
exert a smaller shielding effect than O atoms.
3
4
Figure 6. Intermolecular Pb···S interactions in [Pb(DAPTSC)].
2
Similarly, the J(1H-207Pb) value for [PbMe2(DAPTSC)],
Solution Studies
190.0 Hz, is close to those found for other dimethyllead(IV)
The H, 13C and 207Pb NMR spectroscopic data for the complexes[26] with a coordination number of seven in
complexes are included in the Experimental Section. Only DMSO solution, and the 2J value for [PbPhMe(DAPTSC)],
1H spectra could be obtained for [PbMe2(DAPTSC)] (be- 209.2 Hz, is even larger. To the best of our knowledge, the
cause of the small amount of solid isolated) and only previously reported 2J value for a methylphenyllea-
[Pb(DAPTSC)] (because of its poor solubility). The 207Pb d(IV) complex is that of PbPhMeCl2, 105.4 Hz, for which
NMR signal was only located for [PbPh2(H2DAPTSC)]2- a coordination number of five was assumed.[27]
1
Eur. J. Inorg. Chem. 2007, 3742–3750
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3747

J. S. Casas et al.
FULL PAPER
2,6-diacetylpyridine and thiosemicarbazide. Crystals appropriate
for X-ray study were obtained by recrystallization from MeOH.
PbMe2Br2 was prepared using a published method,[29] by reaction
of PbI2 with IMe and LiMe in ether, and subsequent reaction of
Conclusions
The reactions of the diorganolead(IV) derivatives
PbMe2(OAc)2 and PbPhMe(OAc)2 with H2DAPTSC each
afford two products: the corresponding dimethyllead(IV) or the tetramethyllead formed with Br2. C2H6Br2Pb (397.1): calcd. C
6.05, H 1.52; found C 5.3, H 1.5. PbPhMeCl2 was prepared[27] by
methylphenyllead(IV) complex, and the lead(II) compound
reacting MeMgI and MeI with PbPh3Cl. The PbPh3Me thus
[Pb(DAPTSC)]. Isolation of the former confirms that this
formed was dissolved in chloroform and this solution was treated
bis(thiosemicarbazone) ligand can impede, albeit only par-
with a stream of HCl(g) until a solid formed. C7H8Cl2Pb (370.25):
tially, the decomposition of methyllead(IV) compounds to
calcd. C 22.71, H 2.18; found C 21.8, H 2.1. PbR2(OAc)2 (R = Me,
“inorganic” lead(II) derivatives. The reaction of
Ph), PbPhMe(OAc)2 and PbPh3(OAc) were prepared by reaction
H2DAPTSC with PbPh2(OAc)2 proceeds without any ap-
of the corresponding dihalides or monohalide with AgOAc in 1:2
preciable decomposition of the organometallic moiety to
or 1:1 mol ratio in methanol. The AgX formed was filtered out
form [PbPh2(DAPTSC)]2, which can also be prepared by
reacting H2DAPTSC with PbPh3(OAc) (probably through
a protodephenylation process).
and the solution containing the organolead(IV) acetate was used
immediately in the preparation of the complexes.
Synthesis of the Complexes: The complexes were prepared by re-
acting H2DAPTSC with PbMe2(OAc)2, PbPhMe(OAc)2 PbPh2Cl2,
PbPh2(OAc)2 or PbPh3(OAc) in methanol.
The deprotonation of the incoming ligand in the above
processes is attributable to the basicity of the outgoing ace-
tate groups. When H2DAPTSC reacts with PbPh2Cl2 it re-
mains neutral and is only able to displace chloride from
part of the substrate molecules, competing unsuccessfully
with the displaced Cl– ions for the remainder. The resulting
ionic compound, [PbPh2(H2DAPTSC)]2[PbPh2Cl4]Cl2,
comprises [PbPh2(H2DAPTSC)]2+ cations and [PbPh2Cl4]2–
and Cl– anions.
Caution! Lead is a highly toxic cumulative poison. Lead com-
pounds should be handled carefully.[30]
[PbMe2(DAPTSC)]: A freshly prepared solution of PbMe2(OAc)2
(0.22 g, 0.62 mmol) in MeOH (20 mL) was slowly stirred into a
yellow suspension of H2DAPTSC (0.156 g, 0.503 mmol) in the
same solvent (20 mL). The orange suspension obtained was stirred
for 1 h at room temperature, and the yellow-orange solid formed
was filtered out. The 1H NMR spectrum of this solid suggests a
The above complexes were studied by X-ray diffraction
1
in the solid state, and by H, 13C and 207Pb NMR spec- mixture consisting of the complex [Pb(DAPTSC)] [also formed
when the ligand reacts with PbMePh(OAc)2, vide infra] together
with a small amount of the free ligand. A few monocrystals of
[PbMe2(DAPTSC)] that were suitable for X-ray study were ob-
tained from the mother liquor after slow evaporation of the solvent.
M.p. 227 °C. 1H NMR ([D6]DMSO): δ = 6.9 [br. s, 2 H, N(1,7)H2],
7.8 [d, 2 H, C(4,6)H], 8.14 [t, 1 H, C(5)H], 2.50 [s, C(10,11)H3,
overlaps with solvent signal], 1.65 [s, 2J(1H-207Pb) = 190.2 Hz, 6 H,
CH3–Pb] ppm.
troscopy in DMSO solution. In the solid state, both neutral
H2DAPTSC and dianionic DAPTSC2– behave as pentad-
entate ligands, although the former establishes longer,
weaker bonds with the metal. The weaker donor capacity
of H2DAPTSC is corroborated by its displacement by the
solvent when [PbPh2(H2DAPTSC)]2[PbPh2Cl4]Cl2 is dis-
solved in dimethyl sulfoxide.
[PbPhMe(DAPTSC)]·0.45H2O and [Pb(DAPTSC)]: A solution of
freshly prepared PbPhMe(OAc)2 (0.10 g, 0.24 mmol) was slowly
added to a suspension of H2DAPTSC (0.07 g, 0.24 mmol) in the
same solvent (10 mL). The orange suspension obtained was stirred
for 12 h at room temperature. The orange solid formed was filtered
Experimental Section
Chemicals: 2,6-Diacetylpyridine (Aldrich), thiosemicarbazide
(Merck), dichlorodiphenyllead (Panreac), chlorotriphenyllead (Al-
drich), lead iodide (Aldrich), methyl iodide (Aldrich) and meth-
yllithium (Aldrich), all of reagent grade, were used without further
purification.
1
out and vacuum-dried. The H NMR spectrum of this solid indi-
cated a mixture of [Pb(DAPTSC)] and [PbPhMe(DAPTSC)]. Evap-
oration of the mother liquor gave crystals of these two complexes
that were suitable for X-ray diffractometry. [PbPhMe(DAPTSC)]·
0.45H2O. C18H21.9N7O0.45PbS2 (614.8): calcd. C 35.13, H 3.59, N
Physical Measurements: Elemental analyses for C, H, N and S were
performed with a Fisons 1108 microanalyzer. Melting points were
determined with a Gallenkamp electrically heated apparatus. NMR
spectra were recorded in DMSO using a Bruker AMX 300 spec-
trometer for 1H spectra (at 300.14 MHz) and 13C spectra
(75.4 MHz) (these are referred to TMS through the solvent signals:
1H, 2.50 ppm; 13C, 39.50 ppm), and a Bruker AMX 500 at
104.58 MHz for 205Pb spectra [using a saturated solution of PbPh4
in CDCl3 (δ = 178.0 ppm) ppm as external reference]. Conductance
measurements (S·cm2·mol–1) were performed at room temperature
using a Crison MicroMC 2202 conductivity meter and 10–3  sam-
ples prepared in dry DMSO (Aldrich) under N2 in a glovebox.
Elemental analyses and spectroscopic measurements were carried
out in the RIAIDT services of the University of Santiago de Com-
postela. X-ray data were collected at the RIAIDT services of the
University of Santiago de Compostela and at the São Carlos Insti-
tute of Physics of the University of São Paulo.
1
15.95, S 10.43; found C 34.90, H 3.51, N 16.25, S 10.57. H NMR
([D6]DMSO): δ = 7.02 [br. s, 4 H, N(1,7)H2], 7.78 [d, 2 H, C(4,6)
H], 8.06 [t, 1 H, C(5)H], 2.50 [s, C(10,11)H3, overlaps with the
solvent signal], 7.51 [d, 2 H, Ho(Ph-Pb)], 7.20 [t, 3 H, Hm,p(Ph-Pb)],
1.79 [s, 2J(1H-207Pb) = 209.2 Hz, 3 H, CH3-Pb] ppm. 13C NMR
([D6]DMSO): δ = 176.8 [C(1,9)], 150.7 [C(3,7)], 146.9 [C(2,8)],
122.1 [C(4,6)], 140.3[C(5)], 14.2 [C(10,11)], 130.7 [Co(Ph-Pb)], 129.1
[Cm(Ph-Pb)], 127.8 [Cp(Ph-Pb)] ppm. The signal for Me-Pb has not
been located. [Pb(DAPTSC)]. M.p. 270 °C. C11H14N7PbS2
(515.60): calcd. C 25.62, H 2.74, N 19.02, S 12.44; found C 26.20,
1
H 2.63, N 18.76, S 12.33. H NMR ([D6]DMSO): δ = 7.02 [br. s,
4 H, N(1,7)H2], 7.83 [d, 2 H, C(4,6)H], 8.18 [t, 1 H, C(5)H], 2.50
[s, C(10,11)H3, overlaps with solvent signal] ppm.
[PbPh2(DAPTSC)]: A freshly prepared solution of PbPh2(OAc)2
(0.36 g, 0.758 mmol) in MeOH (20 mL) was slowly stirred into a
suspension of H2DAPTSC (0.18 g, 0.578 mmol) in the same solvent
(20 mL). The mixture was stirred for 1 h at room temperature and
Synthesis of the Ligands and the Starting Organolead(IV) Com-
pounds: H2DAPTSC was prepared as described previously[28] from
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Methyllead(IV) Derivatives Stabilized by DAPTSC2–
FULL PAPER
the orange solid formed was filtered out. M.p. 230 °C.
[PbPh2(H2DAPTSC)]2[PbPh2Cl4]Cl2·6CH3OH: A suspension of
PbPh2Cl2 (0.1 g, 0.23 mmol) in MeOH (10 mL) was stirred into a
yellow suspension of H2DAPTSC (0.071 g, 0.23 mmol) in the same
C23H23N7PbS2 (668.8): calcd. C 41.31, H 3.47, N 14.66, S 9.59;
1
found C 40.48, H 3.90, N 14.02, S 9.74. H NMR ([D6]DMSO): δ
= 7.14 [br. s, 4 H, N(1,7)H2], 7.72 [d, 2 H, C(4,6)H], 7.98 [t, 1 H, solvent (10 mL). The deep yellow suspension obtained was stirred
C(5)H], 2.51 [s, C(10,11)H3], 7.56 [d, 3J(1H-207Pb) = 228.2 Hz, 4 H,
for 4 h at room temperature, after which the yellow solid in suspen-
Ho(Ph-Pb)], 7.20 [t, 4J(1H-207Pb) = 83.0 Hz, 4 H, Hm(Ph-Pb)], 7.13 sion was filtered out and discarded (its 1H NMR spectrum and
[t, 2 H, Hp(Ph-Pb)] ppm. 13C NMR ([D6]DMSO): δ = 176.8 elemental analysis corresponded to H2DAPTSC). Slow concentra-
[C(1,9)], 150.3 [C(3,7)], 147.2 [C(2,8)], 122.3 [C(4,6)], 40.3 [C(5)],
tion of the mother liquor afforded a yellow-green crystalline solid
that was suitable for X-ray study. M.p. 197 °C.
14.4 [C(10,11)], 173.0 [Cipso(Ph-Pb)], 130.7 [2J(13C-207Pb)
=
117.7 Hz, Co(Ph-Pb)], 129.1 [3J(13C-207Pb) = 217.0 Hz, Cm(Ph-Pb)],
127.8 [4J(13C-207Pb) = 36.3 Hz, Cp(Ph-Pb)] ppm. 207Pb NMR ([D6]-
DMSO): δ = –608.7 ppm.
C64H84Cl6N14O6Pb3S4 (2108.02): calcd. C 36.47, H 4.02, N 9.30, S
6.08; found C 35.80, H 3.90, N 10.03, S 6.94. Λm (DMSO, 10–3 )
1
= 8.0 S·cm2·mol–1. H NMR ([D6]DMSO): δ = 8.40 s, 8.13 [s, 4H
N(1,7)H2], 10.30 [s, 2 H, N(2,6)H], 8.41 [d, 2 H, C(4,6)H], 7.76 [t,
1 H, C(5)H], 2.43 [s, C(10,11)H3], 8.12 [d, 8 H, Ho(Ph-Pb)], 7.60
[t, 8 H, Hm(Ph-Pb)], 7.43 [t, 4 H, Hp(Ph-Pb)] ppm. 13C NMR ([D6]-
DMSO): δ = 179.0 [C(1,9)], 153.4 [C(3,7)], 148.0 [C(2,8)], 120.4
[C(4,6)], 136.6 [C(5)], 12.0 [C(10,11)], 170.5 [Cipso(Ph-Pb)], 133.5
[Co(Ph-Pb)], 129.6 [3J(13C-207Pb) ≈ 200, Cm(Ph-Pb)], 129.5 [Cp(Ph-
Pb)] ppm. 207Pb NMR ([D6]DMSO): δ = –507.3 ppm.
[PbPh2(DAPTSC)] was also obtained by reaction of H2DAPTSC
with PbPh3(OAc), as follows: a solution of PbPh3(OAc) (0.2 g,
0.42 mmol) in MeOH (20 mL) was added to a yellow suspension
of H2DAPTSC (0.13 g, 0.42 mmol) in the same solvent (20 mL).
The orange solution obtained was stirred overnight at room tem-
perature and filtered to remove a small amount of H2DAPTSC in
suspension. Slow concentration of the filtrate afforded orange crys-
tals of [PbPh2(DAPTSC)]·MeOH that were suitable for X-ray
study.
X-ray Crystallography: Crystal data were collected at room tem-
perature ([PbMe2(DAPTSC)]) or low temperature (all others) on
Table 3. Selected crystallographic data for the ligand and complexes.
H2DAPTSC·MeOH
[PbMe2(DAPTSC)]
C13H19N7PbS2
544.66
[PbPhMe(DAPTSC)]·0.45H2O
Empirical formula
C12H19N7OS2
341.46
C18H21.90N7O0.45PbS2
614.84
Formula mass
T/K
λ/Å
Crystal system
Space group
a/Å
b/Å
c/Å
α/°
β/°
120.00(10)
1.54180
monoclinic
P21/c
10.493(5)
10.590(5)
14.745(5)
90.000(5)
98.420(5)
90.000(5)
1620.8(12)
4
293(2)
120(2)
0.71073
monoclinic
P21/n
10.026(2)
11.996(2)
17.560(3)
1.54184
orthorhombic
Pmn21 (No. 31)
15.880(2)
7.9249(10)
7.5304(8)
90
90
90
947.7(2)
2
19.443
98.924(9)
γ/°
V/Å3
2086.4(6)
4
8.308
Z
µ/mm–1
3.096
Reflections collected
Independent reflections
Final R1, wR2 [I Ͼ 2σ(I)] 0.0748, 0.1928
10955
2734 [R(int) = 0.0636]
985
9672
965 [R(int) = 0.0208]
0.0241, 0.0651
1.071
3556 [R(int) = 0.0963]
0.0564, 0.1111
1.015
Gof
1.07
[PbPh2(DAPTSC)]·MeOH
[PbPh2(H2DAPTSC)]2[PbPh2Cl4]Cl2·6MeOH [Pb(DAPTSC)]
Empirical formula
Formula mass
C24H27N7OPbS2
700.84
C64H84Cl6N14O6Pb3S4
2107.96
C11H13N7PbS2
514.59
T/K
λ/Å
120(2)
0.71073
110(2)
0.71073
120(2)
0.71073
Crystal system
Space group
monoclinic
P21/n
triclinic
P
monoclinic
P21
¯
a/Å
b/Å
c/Å
α/°
10.1550(1)
15.9560(2)
15.9780(2)
90
91.632(1)
90
2587.92(5)
4
6.712
9.4450(1)
11.1110(2)
18.7520(3)
83.462(1)
77.782(1)
77.714(1)
1874.39(5)
1
4.9586(7)
14.015(2)
10.5900(10)
β/°
102.923(9)
γ/°
V/Å3
717.31(16)
2
12.055
Z
µ/mm–1
7.104
Reflections collected
Independent reflections
Final R1, wR2 [I Ͼ 2σ(I)] 0.0259, 0.0684
Gof 1.092
42027
4559 [R(int) = 0.0486]
52099
3746
6603 [R(int) = 0.1091]
0.0253, 0.0629
1.103
2177 [R(int) = 0.1079]
0.0719, 0.1495
1.052
Eur. J. Inorg. Chem. 2007, 3742–3750
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
3749

J. S. Casas et al.
FULL PAPER
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a CCD-2000 Bruker-Nonius (RIAIDT, University of Santiago de
Compostela) or on an Enraf-Nonius CAD4 or Enraf-Nonius
Kappa CCD (São Carlos Institute of Physics, University of São
Paulo). The data were corrected for absorption by numerical[31]
[PbMe2(DAPTSC)], empirical[32] (H2DAPTSC) or semi-empiri-
cal[33] (all others) methods. Structures were solved by direct meth-
ods for the ligand and the Patterson method for the complexes,
followed by normal difference Fourier techniques. Hydrogen atoms
were included in idealized positions and refined with isotropic dis-
placement parameters, except that the H bound to the oxygen atom
in H2DAPTSC·MeOH was located on the density map and refined
isotropically. The program used was SHELX97.[34]
[12] J. S. Casas, E. E. Castellano, J. Ellena, M. S. García-Tasende,
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Although the data for the ligand and the PbII complex were not of
very good quality, successive refinements allowed the full resolution
of both structures. In [PbPhMe(DAPTSC)]·0.45H2O the water
molecules are disordered, their O atoms occupying two positions,
O1W and O2W, with occupancy factors 3.5 and 0.1, respectively.
O2W was not refined anisotropically.
Molecular graphics were obtained with ORTEP[35] and PLA-
TON.[36] Crystal data, experimental details and refinement param-
eters are listed in Table 3.
CCDC-634589 (for H2DAPTSC·MeOH), -634590 (for [PbMe2-
(DAPTSC)]), -634591 (for [PbPhMe(DAPTSC)]·0.45H2O),
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-634592
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-634593
(for
[PbPh2(H2DAPTSC)]2[PbPh2Cl4]Cl2·6MeOH) and -634594 (for
[Pb(DAPTSC)]) contain the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
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Supporting Information (see also the footnote on the first page of
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[PbPh2(DAPTSC)]·MeOH.
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We thank the Secretariat General for Research and Development
of the Xunta de Galicia (Spain), project number PGID-
IT03PXIC20306PN, and the Spanish Ministerio de Ciencia y Tec-
nología (MCYT), project number CTQ2006-11805-BQU, for finan-
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Received: January 24, 2007
Published Online: June 18, 2007
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