Synthesis and structure of [An(RO)PS2]- complexes

Article abstract of DOI:10.1039/b406411a

Reaction of An(S)PS₂P(S)An with NaOR [R = Me, Et, ^t Pr] gives the non-symmetric phosphonodithioato anions [An(RO)PS ₂]^- which can be complexed to a range of metals. The group 10 metals (Ni, Pd and Pt) adopt square planar ML₂ complexes. The zinc and cadmium complexes adopt isostructural dimeric M₂L ₄ structures whilst mercury complexes adopt a subtly different dimeric motif. Two distinctly different lead complexes are reported, one consisting of PbL₂ units joined by Pb...S interactions to form distinct dimeric pairs, the other being a completely new structural motif for complexes of this type, PbL₂ units held together by covalently bonded bridging ligands to form an infinite polymeric chain structure. All new compounds have been characterised spectroscopically and nine demonstrative X-ray structures are reported.

Full text of DOI:10.1039/b406411a

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F U L L P A P E R
Synthesis and structure of [An(RO)PS2]− complexes
Ian P. Gray, Alexandra M. Z. Slawin and J. Derek Woollins*
School of Chemistry and University of St Andrews, St Andrews, Fife, UK KY16 9ST.
E-mail: jdw3@st-and.ac.uk
Received 28th April 2004, Accepted 10th June 2004
First published as an Advance Article on the web 2nd July 2004
Reaction of An(S)PS2P(S)An with NaOR [R = Me, Et, iPr] gives the non-symmetric phosphonodithioato anions
[An(RO)PS2]− which can be complexed to a range of metals. The group 10 metals (Ni, Pd and Pt) adopt square planar ML2
complexes. The zinc and cadmium complexes adopt isostructural dimeric M2L4 structures whilst mercury complexes adopt
a subtly different dimeric motif. Two distinctly different lead complexes are reported, one consisting of PbL2 units joined
by PbS interactions to form distinct dimeric pairs, the other being a completely new structural motif for complexes of
this type, PbL2 units held together by covalently bonded bridging ligands to form an infinite polymeric chain structure. All
new compounds have been characterised spectroscopically and nine demonstrative X-ray structures are reported.
Here we report further work on new and some of the few existing
Introduction
alkoxy(4-methoxyphenyl)dithiophosphato compounds, including
novel complexes of group 12 (Zn, Cd and Hg) and group 14 (Sn
and Pb) metals. Their full characterisation both spectroscopically
and structurally provide an excellent comparison to previous work
as well as providing a more comprehensive study in a potentially
important area of chemistry.
Organodithio derivatives of phosphorus have been widely studied
for many years.1 Phosphodithioates, their corresponding acids
and metal complexes have been shown to have many industrial
and agricultural applications e.g. as additives to lubricant oils,2
floatation reagents for the recovery of metals from their solutions,3
pesticides and for chemical warfare.4 More recently research has
been conducted on attempts to use these compounds to form liquid
transition metal complexes, for use in the preparation of thin layers
by chemical vapour deposition (CVD) or of polymer–inorganic
nanocomposites.5 Other recent papers have looked at the biological
and potential medicinal uses of dithiophosphate metal complexes
and their adducts,6,7 for example, it has been shown that tin diphenyl-
dithiophosphinato complexes exhibit considerable antiproliferation
activity towards certain leukaemia cells.6 Literature detailing the
synthesis, chemistry and structural behaviour of the complexes of
phosphorodithioate (1) and dithiophosphinodithioate (3) ligands is
plentiful and widely available.5,6,8
Results and discussion
The phosphonodithioate salt 1 was prepared using an adaption of
the literature procedure,10 Lawessons Reagent was refluxed with 2
molar equivalents of NaOMe in methanol. Phosphonodithioate salts
2 and 3 were also formed from the reaction of Lawessons Reagent
with the corresponding sodium alkoxide, but in these cases the so-
dium alkoxide was prepared from the reaction of sodium metal and
the corresponding alcohol and used directly in the alcohol solution,
[eqn. (1)].
Due to synthetic difficulties,9 compounds containing phosphono-
dithioate (2) substituents have received little attention.
(1)
Cleavage of the Lawessons Reagent dimeric ring generates the
sodium phosphonodithioate salts 1–3 as white powders in almost
quantitative yield. Salts 1–3 are soluble in polar solvents such as
alcohols and acetone but are insoluble in less polar solvents e.g.
dichloromethane, chloroform, hexane, etc. All of the above salts
were found to be air stable both as solids and in solution. The 31P
NMR spectra of 1–3 displayed sharp singlets at (P) 110.8, 107.7
Interest in phosphonodithioate (2) derivatives has increased in
recent years. Aragoni et al. have reported the synthesis and charac-
terisation of several monomeric structures involving two alkoxy(4-
methoxyphenyl)dithiophosphonate ligands attached to a group 10
metal centre (Ni2+, Pd2+and Pt2+) in a square planar conformation.10
They achieved this via a ring opening reaction of the well known and
well studied11 thionation compound Lawessons Reagent. A similiar
method was employed by Özcan et al. in the formation of bis[O-2,4-
di-tert-butylphenyl(4-methoxyphenyl)dithiophosphoato] nickel(II),
an analogous compound containing a bulky sterically protecting
substituent.12 In both cases X-ray studies unambiguously identified
the compounds though there is very little spectroscopic information
available.
We recently described the synthesis, full characterisation and
crystallographic structural study of alkoxy(ferrocenyl)dithiophosp
hato compounds.13 These were formed from Ferrocenyl Lawessons
Reagent, a less extensively studied analogue of Lawessons Re-
agent.14 Stable complexes were formed with a range of metals (Ni,
Pd, Pt, Zn, Cd, Hg, Sn and Pb) and were shown to exhibit several
different structural motifs.
1
and 105.7 ppm respectively. The H NMR and 13C NMR spectra
of these compounds were as expected confirming the presence of
both the anisyl and alkoxy moieties. The IR spectra show distinct
bands at 1185–1179 cm−1, 1028–1025 cm−1, 678–674 cm−1 and
559–557 cm−1, corresponding to [(P)–O–C], [P–O–(C)], (PS)asym
and (PS)sym absorptions respectively.15 Mass spectrometry showed
the expected parent ions as (M–Na)+ at m/z 233, 248 and 261. The
microanalysis of 1–3 was only average, however the purity of the
salts was deemed satisfactory for use in further reactions.
Group 10 metals (Ni, Pd, and Pt) in the oxidation state 2+ were
refluxed in the corresponding alcohol with two molar equivalents
of the phosphonodithioate salts 1–3 to yield complexes of the type
ML2 (L = [(p-CH3O)C6H4{OR}PS2]), (4–6) [eqn. (2)], with the ex-
ception of 6p which required the addition of H2O, to dissolve the
T h i s j o u r n a l i s
©
T h e R o y a l S o c i e t y o f C h e m i s t r y 2 0 0 4
D a l t o n T r a n s . , 2 0 0 4 , 2 4 7 7 – 2 4 8 6
2 4 7 7

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Table 1 Selected bond lengths and angles for 4m and 4p
K2PtCl4 starting material, before further reflux to yield the desired
product.
4m
4p
M(1)–S(1)
M(1)–S(2)
P(1)–S(1)
P(1)–S(2)
P(1)–O(1)
P(1)–C(1)
2.2330(6)
2.2413(6)
2.0048(7)
2.0043(8)
1.5856(13)
1.7904(18)
2.2298(6)
2.2327(6)
2.0042(8)
2.0082(8)
1.5855(15)
1.792(2)
S(1)–M(1)–S(2)
S(1)–P(1)–S(2)
88.87(2)
102.77(3)
88.50(2)
101.80(3)
(2)
The metal complexes were prepared in high yields, giving solids
exhibiting a range of colours from bright purple to yellow. All are
soluble in both chloroform and dichloromethane and found to be air
stable as solids and in solution. The 31P NMR of 4m, 4e and 4p gave
sharp singlets in the range (P) 99.1–105.7 ppm, showing no signifi-
cant deviation from the signals attributed to the sodium salts 1–3;
consistent with the ferrocenyl analogues of these compounds.13
In the cases of complexes 5 and 6 each spectrum contains a pair
of sharp singlets of varying intensity, usually close to equal, in the
range (P) 104.8–118.4 ppm. This result indicates the presence of
two distinct isomeric forms, we believe these to be cis and trans iso-
mers i.e. anisyl groups on the same side of the molecule—cis, on the
opposite—trans. The 1H and 13C NMR also provide good evidence
for these isomers, in each case the expected shifts are present with
coupling consistent with the proposed products. However these
spectra show each set of resonances to be accompanied by a second
set of matching peaks of approximately equal intensity indicating
that the proposed isomeric forms exist in solution. This hypothesis
is also reinforced by X-ray studies conducted on the similar com-
pound, bis[(methoxy)ferrocenylphosphonodithiato] nickel.13 Crys-
tals of the trans isomer were grown from the isolated product and
unambiguously identified. Upon attempts to form a pyridine adduct
of this complex, decomposition occurred and crystals obtained were
identified as the cis isomer. IR spectra showed distinct bands within
the expected ranges and in all cases mass spectroscopy found the
expected (M)+ ion.
The X-ray structures of 4m and 4p (Fig. 1, Table 1) show in each
case that the nickel atom resides on a crystallographic inversion
centre and is coordinated by four sulfur atoms in a square planar
geometry with symmetric NiS2P rings. The anisyl groups of the
two bound ligands are arranged in a trans arrangement, i.e. above
and below the metal coordination plane. The structures of 4e10a and
6m10d are known and are consistent with the above results and other
literature examples.13
Group 12 metals (Zn, Cd and Hg) in the oxidation state 2+ were
refluxed in the corresponding alcohol with two molar equivalents of
the phosphonodithioate salts 1–3 for 2 h to yield complexes of the
type M2L4 (L = [(p-CH3O)C6H4{OR}PS2]), (7–9), [eqn. (3)].
Fig. 1 Upper diagram, the X-ray structure of 4m; lower diagram, the X-
ray structure of 4p.
all cases.8,13 This structural motif consists of an eight membered
M2P2S4 ring with two terminal bidentate ligands each bound to one
metal atom via both sulfurs and the other two acting as bridging li-
gands with their sulfur atoms binding to two different metal atoms.
The metal complexes were isolated as white powders in high
yield. All complexes are soluble in chloroform and dichloro-
methane and air stable as solids and in solution. The 31P spectra
of the complexes display sharp singlets with chemical shifts in the
range (P) 98.5–109.8 ppm. The 1H and 13C NMR of all complexes
show the same pattern as their corresponding “free phosphonodi-
thioate salts”. The above NMR data would suggest that a simple
dimer is not the only species present in solution. The two types of
ligand present, terminal and bridging, would display two distinct
sets of signals, this is not the case and leads us to the conclusion
that a more complicated situation exists. Authors of earlier studies
(3)
Literature examples show that group 12 metal complexes of
phosphodithioate ligands exhibit dimeric structures in almost
2 4 7 8
D a l t o n T r a n s . , 2 0 0 4 , 2 4 7 7 – 2 4 8 6

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conducted on phosphorodithioate and phosphinodithioate com-
plexes of group 12 metals postulated that an equilibrium exists with
rapid exchange between a monomeric and a dimeric structure.16 IR
spectra showed distinct bands within the expected ranges, showing
similar signals to the free salts and complexes 4–6. In the mass
spectra, the expected (M)+ ions were found for 7m, 7p, 8m and
8p only. For all others the most prominent fragments were the loss
of one phosphonodithioate ligand, [(p-CH3O)C6H4{OR}PS2], and
(1/2M)+. The X-ray structures of 9e, 7p and 9p (Figs. 2 and 3) were
determined and confirmed the dimeric nature of the complexes in
the solid state, with the structures being closely related to those of
the symmetric Zn2[S2P(OBu)2]4, which we have described previ-
ously,17 and their ferrocenyl analogues,13 Cd2[S2P(Fc)OMe]4 and
Zn2[S2P(Fc)OMe]4.
The X-ray structures of 8e and 8p (Fig. 4, Table 2) were also
determined and as was the case for 7p and 9p were found to be of a
dimeric nature. Unlike 7p and 9p in which all M–S distances are ap-
proximately equal, 8e and 8p exhibit a different pattern. The Hg–S
Fig. 2 The X-ray structure of 9e.
Fig. 4 Upper diagram, the X-ray structure of 8e; lower diagram, the X-ray
structure of 8p.
bonds form two distinct pairs of long and short bonds. The bond
lengths of Hg(1)–S(1) and Hg(1)–S(11) are approximately equal
as are the lengths of Hg(1)–S(2) and Hg(1)–S(12A) with the latter
pair being significantly longer (ca. 0.3 Å). This pattern forms an
axis of symmetry through the molecule with an equal and opposite
effect occurring at the other Hg atom. This phenomenon has been
noted for similar examples of mercury dithiophosphoroate18–21 and
dithiophosphinoate22 complexes as well as in mercury xanthate18
and dithiocarbamate species.18
Similar reactions to those described above were carried out with
two of the group 14 metals (Sn and Pb), in the oxidation state 2+,
Fig. 3 The X-ray structure of 7p, the structure of 9p is isomorphous and
is not reproduced.
Table 2 Selected bond lengths and angles for 7p, 8e, 8p, 9e and 9p
7p
8e
8p
9e
9p
M(1)–S(1)
M(1)–S(2)
M(1)–S(11)
M(1)–S(12)
P(1)–S(1)
2.6610(8)
2.5249(7)
2.5767(7)
2.5210(7)
1.9964(8)
2.0239(9)
1.9991(9)
2.0409(8)
1.5905(16)
1.5842(15)
1.796(2)
2.4656(16)
2.7856(15)
2.4558(16)
2.6239(16)
2.042(2)
1.986(2)
2.032(2)
1.996(2)
1.591(4)
1.584(4)
1.791(6)
1.796(6)
2.4943(16)
2.7230(17)
2.4978(16)
2.5638(16)
2.029(2)
1.990(2)
2.013(2)
2.014(2)
1.585(4)
1.591(4)
1.798(6)
1.780(6)
2.3170(12)
2.4377(12)
2.3170(12)
2.3635(12)
2.0252(14)
2.0006(14)
2.0099(15)
2.0106(14)
1.589(3)
2.3382(17)
2.4541(18)
2.3145(18)
2.3610(17)
2.025(2)
2.001(2)
2.018(2)
2.005(2)
1.589(5)
1.586(5)
1.790(6)
1.787(6)
P(1)–S(2)
P(11)–S(11)
P(11)–S(12)
P(1)–O(1)
P(11)–O(11)
P(1)–C(1)
1.588(3)
1.788(4)
1.783(4)
P(11)–C(11)
1.786(2)
S(1)–M(1)–S(2)
S(1)–P(1)–S(2)
S(11)–M(1)–S(12)
S(12)–P(11)–S(11)
79.46(2)
111.15(4)
79.49(4)
111.62(4)
78.17(5)
111.03(9)
78.62(3)
79.49(5)
110.63(10)
78.53(4)
86.45(4)
108.65(6)
86.44(2)
85.93(6)
108.48(10)
86.06(6)
114.87(10)
115.26(9)
113.62(6)
112.88(10)
D a l t o n T r a n s . , 2 0 0 4 , 2 4 7 7 – 2 4 8 6
2 4 7 9

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yielding either white or pale yellow powders in high yield. As was
the case for 4–9, all complexes are soluble in chloroform and di-
chloromethane and are air stable. 31P, 1H and 13C spectra showed the
same pattern to that of complexes 4, 7, 8 and 9, with 31P chemical
shifts in the range (P) 89.1–100.9 ppm. IR spectra of compounds
10–11 showed distinct bands in the expected ranges.
Fig. 6 The X-ray structure of 11p. Additional PbAr interactions il-
lustrated.
(4)
In the mass spectra the most prominent fragments were the loss
of one phosphonodithioate ligand, [(p-CH3O)C6H4{OR}PS2], and
(1/2M)+, as was the case for many of the group 12 metal complexes.
This result would suggest that compounds 10–11 all exhibit similar
covalently bound dimeric structures but this has been found to be in-
correct. X-ray studies conducted on 11e and 11p (Figs. 5–7, Table 3)
show very different structural motifs indicating that for compounds
10–11 a more complicated situation than that proposed for group 12
metal complexes 7–9 may exist.
Fig. 7 The X-ray structure of 11e showing part of the infinite chain
structure.
11p adopts a similar molecular unit, the lead resides in the centre
of a distorted pyramid, 1.30 Å above the basal S4 plane and again
the ligands are bidentate. But instead of an infinite polymeric chain
structure, 11p adopts a structure consisting of distinct dimeric pairs.
In each monomeric building unit one ligand is bidentate chelating
(both S atoms bound to one Pb atom only); the other is bimetallic
triconnective and participates in the formation of the dimer. The
inter-unit secondary PbS distance (3.45(1) Å) is significantly
longer than the intra-unit PbS distances (Pb(1)–S(1) 2.736 Å,
Pb(1)–S(2) 2.895 Å), leading to the formation of an eight-mem-
bered quasicyclic species. Additional intradimeric interactions
occur between a lead atom of one monomeric unit and one of the
aromatic rings (Pb(1)–C(11A) 3.28(1) Å, Pb(1)–C(12A) 3.44(1) Å,
and Pb(1)–C(16A) 3.32(1) Å) belonging to the other monomer unit.
These PbAr interactions seem to stabilize the dimeric structure
and may be the reason why the structure is significantly different
from that adopted by its ferrocenyl analogue. Bis(diphenylphosph
orodithioato) lead has also been shown to adopt a closely related
structural motif exhibiting similar PbAr interactions.24
Fig. 5 The X-ray structure of 11p. Upper diagram, single monomeric unit;
lower diagram, pair of units forming dimeric structure.
Table 3 Selected bond lengths and angles for 11e and 11p
Very few tin compounds of this type have been investigated,
only one complex has been studied by single X-ray crystallo-
graphy, [Sn{(OPh)2PS2}2]2, exhibiting a dimeric structure simi-
lar to the complexes of group 12 metals.15a,23 Several structures
of lead phosphorodithioate complexes have been determined,
[Pb{(OR)2PS2}2]n, with various alkoxy substituants exhibiting a
rangeofstructuralmotifs.8d,e Onlyoneexampleofaleadphosphono-
dithioate complex has been studied crystallographically, bis[(is
opropoxy)ferrocenylphosphonodithioato] lead.13 The structure
of this complex is built up of distorted pyramids, with the apical
lead atom 1.41 Å above the basal S4 plane and the ligands anisobi-
dentate. The molecules are linked by PbS interactions (ca. 3.9 Å)
to form infinite polymeric chains. Despite this complex being the
exact ferrocenyl analogue, 11p was found to adopt a quite different
structural motif.
11e
11p
M(1)–S(1)
M(1)–S(2)
M(1)–S(1A)
M(1)–S(2B)
M(1)–S(2C)
P(1)–S(1)
P(1)–S(2)
P(1)–O(1)
P(1)–C(1)
2.8404(11)
—
2.7363(11)
2.8954(12)
—
—
—
2.0220(15)
1.9881(16)
1.589(3)
1.794(4)
2.8404(11)
3.0706(11)
3.0706(11)
2.0009(13)
1.9861(14)
1.612(3)
1.788(4)
S(1)–M(1)–S(2)
S(1)–M(1)–S(2B)
S(1)–M(1)–S(2C)
S(1)–P(1)–S(2)
—
72.44(3)
—
—
79.80(3)
79.80(3)
116.63(6)
112.28(7)
2 4 8 0
D a l t o n T r a n s . , 2 0 0 4 , 2 4 7 7 – 2 4 8 6

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The X-ray structure of 11e was also obtained and was shown to ex-
hibit a completely different motif. There have been several literature
examples of these lead complexes showing the formation of infinite
polymeric chains,8d,e in all cases the monomeric building blocks of
the polymers are linked by inter-unit long range PbS interactions.
Here we report a polymeric structure held together solely by covalent
bonding. To the best of our knowledge this type of structural motif
has not been seen for lead phosphodithiato complexes. Each lead
atom is bound to four sulfur atoms contributed from 4 different phos-
phonodithioate ligands to form a distorted trigonal bipyramid with a
vacant site. Each lead exhibits two long Pb–S bonds (3.0708(11) Å)
and 2 short Pb–S (2.8404(11) Å) bonds. All of the ligands within
the molecule are bidentate, bridging two lead centres leading to the
formation of a continuous array of 8-membered Pb2P2S4 rings.
This work clearly demonstrates the versatile coordination of the
[(p-CH3O)C6H4{OR}PS2] ligand towards various metals centres.
(Isopropoxy)-4-methoxyphenylphosphonodithioate sodium
salt (3). Small pieces of sodium (0.41 g, 17.9 mmol) were stirred in
propan-2-ol (50 cm3) at 0 °C until fully dissolved. To this solution
Lawessons Reagent (3.62 g, 8.96 mmol) was added and heated to
reflux for 1 h. The reaction mixture was allowed to cool to room
temperature and the resulting colourless solution was filtered
through a small celite pad. The solvent was removed under reduced
pressure to give a white solid (5.03 g, 98.7%). Found (Calc. For
C10H14NaO2PS2): C 42.46 (42.25), H 5.55 (4.97), S 22.07 (22.51)%.
1
31P NMR (methanol D3) : 105.7. H NMR (methanol D3) : 8.04
(dd, 2H, 3J(31P–1H) 13.4 Hz, 3J(1H–1H) 9.0 Hz, o-ArH, 6.88 (dd, 2H,
3
4J(31P–1H) 3.0 Hz, J(1H–1H) 9.0 Hz, m-ArH, 4.71 (dsept = septet
of doublets, 1H, 3J(31P–1H) 2.4 Hz, 3J(1H–1H) 6.0 Hz, CH), 3.82 (s,
3
3H, ArOMe), 1.20 (d, 6H, J(1H–1H) 6.0 Hz. 13C NMR (methanol
D3) : 162.8 (d, 4J (31P–13C) 3.0 Hz, p-ArC), 137.8 (d, 1J (31P–13C)
3
114.7 Hz, Ar C-1), 133.4 (d, J (31P–13C) 12.8 Hz, m-ArC), 114.0
(d, 2J (31P–13C) 15.1 Hz, o-ArC), 70.3 (d, 2J (31P–13C) 7.6 Hz, CH),
3
56.3 (s, ArOCH3), 25.0 (d, J (31P–13C) 3.8 Hz, CH3). Selected IR
Experimental
data (KBr) /cm−1: 1180 (s), 1028 (m), 648 (m), 557 (s). Mass Spec
General
(EI+): (M − Na)+ 261.
Unless otherwise stated, operations were carried out under an oxy-
gen-free nitrogen atmosphere using predried solvents and standard
Bis[(methoxy)-4-methoxyphenylphosphonodithioato]Ni
(4m). A mixture of NiCl2 (0.076 g, 0.585 mmol) and 1 (0.300 g,
1.71 mmol) in methanol (15 cm3) was refluxed for 2 h. The solvent
was removed under reduced pressure, the resulting purple solid was
redissolved in dichloromethane and filtered through a small celite
plug. The filtrate was concentrated under vacuum to ca. 10 cm3
and hexane was added to precipitate the product as purple crystals
(0.258 g, 84%). Purple crystals suitable for X-ray analysis were
grown by vapour diffusion of hexane into a dichloromethane solu-
tion. Found (Calc. For C16H20O4P2S4Ni): C 36.68 (36.65), H 3.80
25
26
Schlenk techniques. Pd(PhCN)2Cl2 and Pt(PhCN)2Cl2 were
prepared using literature procedures. All other reagents were used
as purchased from either Aldrich, Acros or Lancaster and used as
received. Infrared spectra were recorded as KBr discs in the range
4000–350 cm−1 on a Perkin-Elmer System 2000 Fourier-transform
1
spectrometer, H, 31P and 13C NMR spectra were recorded using
a Jeol GSX Delta 270 or Bruker Avance 300 MHz spectrometer.
Microanalyses were performed by the University of St. Andrews
microanalysis service. Mass spectra were recorded by both the Uni-
versity of St. Andrews mass spectrometry service and the Swansea
mass spectrometry service. We are grateful to Johnson Matthey
PLC for the loan of precious metals.
1
(3.85), S 24.19 (24.41)%. 31P NMR (CDCl3) : 105.7. H NMR
(CDCl3) : 7.92 (dd, 2H, 3J(31P–1H) 14.1 Hz, 3J(1H–1H) 9.0 Hz, o-
ArH), 6.93 (dd, 2H, 4J(31P–1H) 3.3 Hz, 3J(1H–1H) 9.0 Hz, m-ArH,
2
3.92 (d, 3H, J(1H–1H) 14.7 Hz, CH3), 3.81 (s, 3H, ArOMe). 13C
NMR (CDCl3) : 163.4 (s, p-ArC), 132.0 (d, 3J (31P–13C) 15.1 Hz, m-
ArC), 128.5 (d, 1J (31P–13C) 117.0 Hz, Ar C-1), 114.4 (d, 2J (31P–13C)
Synthesis
2
16.6 Hz, o-ArC), 55.9 (s, ArOCH3), 52.9 (d, J (31P–13C) 3.0 Hz,
(Methoxy)-4-methoxyphenylphosphonodithioate sodium salt
(1). Compound 1 was prepared as detailed in the literature10a as a
white solid (4.97 g, 98.9%). Found (Calc. For C8H10NaO2PS2): C
40.03 (37.50), H 3.67 (3.94), S 25.62 (24.98)%. 31P NMR (methanol
CH3). Selected IR data (KBr) /cm−1: 1179 (m), 1027 (s), 667 (m),
550 (s). Mass Spec (EI+): (M)+ 524.
1
3
D3) : 110.8. H NMR (methanol D3) : 8.04 (dd, 2H, J(31P–1H)
13.5 Hz, 3J(1H–1H) 9.0 Hz, o-ArH, 6.92 (dd, 2H, 4J(31P–1H) 2.7 Hz,
3J(1H–1H) 9.0 Hz, m-ArH, 3.79 (s, 3H, ArOMe), 3.54 (d, 3H, 2J(1H–
1H) 14.7 Hz, CH3). 13C NMR (methanol D3) : 163.0 (d, 4J (31P–13C)
3.0 Hz, p-ArC), 136.2 (d, 1J (31P–13C) 113.9 Hz,Ar C-1), 133.5 (d, 3J
(31P–13C) 13.6 Hz, m-ArC), 114.3 (d, 2J (31P–13C) 15.1 Hz, o-ArC),
Bis[(ethoxy)-4-methoxyphenylphosphonodithioato]Ni (4e). A
mixture of NiCl2 (0.072 g, 0.550 mmol) and 2 (0.300 g, 1.11 mmol)
in ethanol (15 cm3) was refluxed for 2 h. The solvent was removed
under reduced pressure, the resulting brown/purple solid was re-
dissolved in dichloromethane and filtered through a small celite
plug. The filtrate was concentrated under vacuum to ca. 10 cm3
and hexane was added to precipitate the product as a brown/purple
solid (0.205 g, 67%). Found (Calc. For C18H24O4P2S4Ni): C 39.17
(39.13), H 4.40 (4.38), S 23.33 (23.18)%. 31P NMR (CDCl3) :
56.6 (s, ArOCH3), 52.0 (d, J (31P–13C) 6.8 Hz, CH3). Selected IR
2
data (KBr) /cm−1: 1179 (s), 1026 (m), 672 (s), 559 (s). Mass Spec
(EI-): (M − Na)+ 233.
1
3
102.2. H NMR (CDCl3) : 7.94 (dd, 2H, J(31P–1H) 14.1 Hz,
3J(1H–1H) 9.0 Hz, o-ArH), 6.93 (dd, 2H, 4J(31P–1H) 3.0 Hz, 3J(1H–
(Ethoxy)-4-methoxyphenylphosphonodithioate sodium salt
(2). Small pieces of sodium (0.43 g, 18.7 mmol) were stirred in
ethanol (30 cm3) at 0 °C until fully dissolved. To this solution
Lawessons Reagent (3.78 g, 9.35 mmol) was added and heated to
reflux for 1 h. The reaction mixture was allowed to cool to room
temperature and the resulting colourless solution was filtered
through a small celite pad. The solvent was removed under reduced
pressure to give a white solid (4.98 g, 98.5%). Found (Calc. For
C9H12NaO2PS2): C 39.58 (40.00), H 3.99 (4.48), S 24.12 (23.68)%.
1H) 9.0 Hz, m-ArH), 4.36 (dq, 2H, J(31P–1H) 3.0 Hz, J(1H–1H)
7.2 Hz, CH2), 3.81 (s, 3H, ArOMe), 1.36 (t, 3H, 3J(1H–1H) 7.2 Hz,
CH3). 13C NMR (CDCl3) : 163.3 (s, p-ArC), 132.0 (d, 3J (31P–13C)
3
3
14.3 Hz, m-ArC), 128.9 (d, J (31P–13C) 117.0 Hz, Ar C-1), 114.3
1
(d, 2J (31P–13C) 16.6 Hz, o-ArC), 63.1 (d, 2J (31P–13C) 7.5 Hz, CH2),
55.9 (s, ArOCH3), 16.6 (d, J(31P–13C) 7.5 Hz, CH3). Selected IR
3
data (KBr) /cm−1: 1182 (s), 1027 (m), 654 (w), 551 (m). Mass Spec
(FAB): (M)+ 552.
1
31P NMR (methanol D3) : 107.7. H NMR (methanol D3) : 8.04
3
3
(dd, 2H, J(31P–1H) 13.7 Hz, J(1H–1H) 9.0 Hz, o-ArH), 6.90 (dd,
Bis[(isopropoxy)-4-methoxyphenylphosphonodithioato]Ni
(4p). A mixture of NiCl2 (0.076 g, 0.585 mmol) and 1 (0.300 g,
1.71 mmol) in propan-2-ol (15 cm3) was refluxed for 2 h. The
solvent was removed under reduced pressure, the resulting brown/
purple solid was redissolved in dichloromethane and filtered through
a small celite plug. The filtrate was concentrated under vacuum to
ca. 10 cm3 and hexane was added to precipitate the product as a
purple solid (0.223 g, 73%). Purple crystals suitable for X-ray anal-
ysis were grown by vapour diffusion of hexane into a chloroform
solution. Found (Calc. For C20H28O4P2S4Ni): C 41.22 (41.38), H
2H, 4J(31P–1H) 2.7 Hz, 3J(1H–1H) 9.0 Hz, m-ArH, 3.93 (dq = quartet
of doublets, 2H, J(31P–1H) 1.5 Hz, J(1H–1H) 7.2 Hz, CH2), 3.81
3
3
(s, 3H, ArOMe), 1.22 (t, 3H, J(1H–1H) 7.2 Hz, CH3). 13C NMR
3
(methanol D3) : 162.5 (d, 4J (31P–13C) 3.0 Hz, p-ArC), 136.7 (d, 1J
(31P–13C) 114.6 Hz, Ar C-1), 133.0 (d, 3J (31P–13C) 13.2 Hz, m-ArC),
113.7 (d, 2J (31P–13C) 14.8 Hz, o-ArC), 61.1 (d, 2J (31P–13C) 6.8 Hz,
CH2), 56.0 (s, ArOCH3), 16.7 (d, 3J (31P–13C) 9.1 Hz, CH3). Selected
IR data (KBr) /cm−1: 1185 (s), 1025 (m), 674 (m), 559 (m). Mass
Spec (EI+): (M − Na)+ 248.
D a l t o n T r a n s . , 2 0 0 4 , 2 4 7 7 – 2 4 8 6
2 4 8 1

View Online
4.76 (4.87), S 21.79 (22.05)%. 31P NMR (CDCl3) : 99.1. 1H NMR
(CDCl3) : 7.95 (dd, 2H, 3J(31P–1H) 14.0 Hz, 3J(1H–1H) 9.0 Hz, o-
ArH), 6.93 (dd, 2H, 4J(31P–1H) 3.6 Hz, 3J(1H–1H) 9.0 Hz, m-ArH),
as a brown solid (0.112 g, 67%). Found (Calc. For C20H28O4P2S4Pd):
C 38.06 (38.22), H 4.63 (4.49), S 20.71 (20.37)%.
Isomer (a): 31P NMR (CDCl3) : 111.7. 1H NMR (CDCl3) : 7.89
3
3
5.15 (dsept, 1H, J(31P–1H) 1.8 Hz, J(1H–1H) 6.2 Hz, CH), 3.81
(s, 3H, ArOMe), 1.35 (d, 6H, 3J(1H–1H) 6.2 Hz. 13C NMR (CDCl3)
: 163.2 (s, p-ArC), 132.1 (d, 3J (31P–13C) 15.1 Hz, m-ArC), 129.2
(dd, 2H, J(31P–1H) 14.0 Hz, J(1H–1H) 8.7 Hz, o-ArH), 6.91 (dd,
2H, 4J(31P–1H) 3.6 Hz, 3J(1H–1H) 8.7 Hz, m-ArH), 5.00 (dsept, 1H,
3J(31P–1H) 1.8 Hz, 3J(1H–1H) 6.2 Hz, CH), 3.80 (s, 3H,ArOMe), 1.34
(d, 6H, 3J(1H–1H) 6.3 Hz. 13C NMR (CDCl3) : 163.2 (d, 4J (31P–13C)
3.3 Hz, p-ArC), 132.2 (d, 3J (31P–13C) 16.6 Hz, m-ArC), 128.5 (d, 1J
(31P–13C) 118.9 Hz, Ar C-1), 114.3 (d, 2J (31P–13C) 17.4 Hz, o-ArC),
3
3
1
2
(d, J (31P–13C) 117.7 Hz, Ar C-1), 114.3 (d, J (31P–13C) 15.9 Hz,
o-ArC), 72.5 (s, CH), 55.9 (s, ArOCH3), 24.5 (s, CH3). Selected IR
data (KBr) /cm−1: 1183 (s), 1026 (m), 663 (m), 553 (s). Mass Spec
(FAB): (M)+ 580.
2
3
72.8 (d, J (31P–13C) 5.5 Hz, CH), 55.9 (s, ArOCH3), 24.8 (d, J
(31P–13C) 3.9 Hz, CH3).
Isomer (b): 31P NMR (CDCl3) : 111.4. 1H NMR (CDCl3) : 7.86
Bis[(methoxy)-4-methoxyphenylphosphonodithioato]Pd
(5m). A mixture of PdCl2(PhCN)2 (0.112 g, 0.293 mmol) and 1
(0.150 g, 0.585 mmol) in methanol (15 cm3) was refluxed for
20 min. An obvious brown precipitate was observed and collected
by suction filtration, washed with methanol (2 × 10 cm3) and dried
in vacuo to give a brown solid (0.117 g, 70%).
3
3
(dd, 2H, J(31P–1H) 14.0 Hz, J(1H–1H) 8.7 Hz, o-ArH), 6.88 (dd,
2H, 4J(31P–1H) 3.3 Hz, 3J(1H–1H) 8.7 Hz, m-ArH), 5.00 (dsept, 1H,
3J(31P–1H) 1.8 Hz, J(1H–1H) 6.2 Hz, CH), 3.78 (s, 3H, ArOMe),
3
1.36(d, 6H, 3J(1H–1H) 6.3 Hz. 13C NMR (CDCl3) : 163.2 (d, 4J (31P–
13C) 3.3 Hz, p-ArC), 132.2 (d, 3J (31P–13C) 16.6 Hz, m-ArC), 128.5
(d, J (31P–13C) 118.9 Hz, Ar C-1), 114.3 (d, J (31P–13C) 17.4 Hz,
o-ArC), 72.8 (d, 2J (31P–13C) 5.5 Hz, CH), 55.9 (s, ArOCH3), 24.8
(d, 3J (31P–13C) 3.9 Hz, CH3).
1
2
Found (Calc. For C16H20O4P2S4Pd): C 34.00 (33.57), H 3.84
(3.52), S 22.71 (22.36)%.
Isomer (a): 31P NMR (CDCl3) : 118.4. 1H NMR (CDCl3) : 7.89
(dd, 2H, 3J(31P–1H) 14.0 Hz, 3J(1H–1H) 8.7 Hz, o-ArH, 6.92 (dd, 2H,
4J(31P–1H) 3.0 Hz, 3J(1H–1H) 9.0 Hz, m-ArH, 3.88 (d, 3H, 2J(1H–1H)
14.7 Hz, CH3), 3.80 (s, 3H, ArOMe). 13C NMR (CDCl3) : 163.2
Selected IR data (KBr) /cm−1: 1180 (s), 1027 (m), 661 (m), 547
(s). Mass Spec (FAB): (M)+ 628.
3
1
(s, p-ArC), 131.8 (d, J (31P–13C) 15.8 Hz, m-ArC), 128.5 (d, J
(31P–13C) 118.3 Hz, Ar C-1), 114.0 (d, 2J (31P–13C) 18.1 Hz, o-ArC),
55.6 (s, ArOCH3), 52.8 (m, CH3).
Bis[(methoxy)-4-methoxyphenylphosphonodithioato]Pt
(6m). A mixture of PtCl2(PhCN)2 (0.138 g, 0.293 mmol) and 1
(0.150 g, 0.585 mmol) in methanol (15 cm3) was refluxed for
20 min. An obvious yellow precipitate was observed and collected
by suction filtration, washed with methanol (2 × 10 cm3) and dried
in vacuo to give a yellow solid (0.114 g, 59%).
Found (Calc. For C16H20O4P2S4Pt): C 29.51 (29.05), H 2.72
(3.05), S 19.77 (19.35)%.
Isomer (a): 31P NMR (CDCl3) : 115.8 (s, 2J 31P–195Pt 378.5 Hz).
Isomer (b): 31P NMR (CDCl3) : 118.3. 1H NMR (CDCl3) : 7.86
(dd, 2H, 3J(31P–1H) 14.1 Hz, 3J(1H–1H) 8.7 Hz, o-ArH, 6.90 (dd, 2H,
4J(31P–1H) 3.3 Hz, 3J(1H–1H) 9.0 Hz, m-ArH, 3.85 (d, 3H, 2J(1H–1H)
14.7 Hz, CH3), 3.79 (s, 3H, ArOMe). 13C NMR (CDCl3) : 163.2
3
1
(s, p-ArC), 131.8 (d, J (31P–13C) 15.8 Hz, m-ArC), 128.4 (d, J
(31P–13C) 119.4 Hz, Ar C-1), 114.0 (d, 2J (31P–13C) 18.1 Hz, o-ArC),
55.6 (s, ArOCH3), 52.8 (m, CH3).
3
3
1H NMR (CDCl3) : 7.95 (dd, 2H, J(31P–1H) 13.8 Hz, J(1H–1H)
Selected IR data (KBr) /cm−1: 1182 (m), 1027 (s), 666 (m), 546
(m). Mass Spec (FAB): (M)+ 572.
9.0 Hz, o-ArH, 6.91 (dd, 2H, 4J(31P–1H) 3.3 Hz, 3J(1H–1H)
9.0 Hz, m-ArH, 3.94 (d, 3H, J(1H–1H) 14.7 Hz, CH3), 3.80 (s,
2
3H, ArOMe). 13C NMR (CDCl3) : 163.4 (s, p-ArC), 132.1 (d,
3J (31P–13C) 15.8 Hz, m-ArC), 129.0 (d, J (31P–13C) 119.0 Hz, Ar
1
Bis[(ethoxy)-4-methoxyphenylphosphonodithioato]Pd (5e).
A mixture of PdCl2(PhCN)2 (0.106 g, 0.277 mmol) and 2 (0.150 g,
0.555 mmol) in ethanol (15 cm3) was refluxed for 2 h. The solvent
was removed under reduced pressure, the resulting brown solid was
redissolved in dichloromethane and filtered through a small celite
plug. The filtrate was concentrated under vacuum to ca. 10 cm3
and hexane was added to precipitate the product as a dark orange
solid (0.103 g, 62%). Found (Calc. For C18H24O4P2S4Pd): C 36.28
(36.01), H 3.75 (4.03), S 21.33 (21.32)%.
C-1), 114.4 (d, J (31P–13C) 16.6 Hz, o-ArC), 55.9 (s, ArOCH3),
2
53.6 (s, CH3).
Isomer (b): 31P NMR (CDCl3) : 113.2 (s, 2J31P–195Pt 379.3 Hz).
3
3
1H NMR (CDCl3) : 7.94 (dd, 2H, J(31P–1H) 14.1 Hz, J(1H–1H)
9.0 Hz, o-ArH, 6.90 (dd, 2H, 4J(31P–1H) 3.3 Hz, 3J(1H–1H)
9.0 Hz, m-ArH, 3.94 (d, 3H, J(1H–1H) 14.7 Hz, CH3), 3.79 (s,
2
3H, ArOMe). 13C NMR (CDCl3) : 163.4 (s, p-ArC), 132.1 (d,
3J (31P–13C) 15.8 Hz, m-ArC), 128.5 (d, J (31P–13C) 119.4 Hz, Ar
1
Isomer (a): 31P NMR (CDCl3) : 114.9. 1H NMR (CDCl3) : 7.89
C-1), 114.4 (d, J (31P–13C) 16.6 Hz, o-ArC), 55.9 (s, ArOCH3),
2
3
3
(dd, 2H, J(31P–1H) 14.1 Hz, J(1H–1H) 8.7 Hz, o-ArH), 6.91 (dd,
53.6 (s, CH3).
2H, J(31P–1H) 3.0 Hz, J(1H–1H) 8.9 Hz, m-ArH), 4.26 (dq, 2H,
4
3
Selected IR data (KBr) /cm−1: 1182 (m), 1027 (s), 666 (m), 546
(s). Mass Spec (FAB): (M)+ 661.
3J(31P–1H) 3.0 Hz, J(1H–1H) 7.2 Hz, CH2), 3.80 (s, 3H, ArOMe),
3
1.37 (t, 3H, J(1H–1H) 6.9 Hz, CH3). 13C NMR (CDCl3) : 163.4
3
(s, p-ArC), 132.2 (d, J (31P–13C) 16.6 Hz, m-ArC), 129.0 (d, J
(31P–13C) 121.3 Hz, Ar C-1), 114.3 (d, 2J (31P–13C) 17.3 Hz, o-ArC),
63.3 (s, CH2), 55.9 (s, ArOCH3), 16.6 (s, CH3).
3
1
Bis[(ethoxy)-4-methoxyphenylphosphonodithioato]Pt (6e).
A mixture of PtCl2(PhCN)2 (0.131 g, 0.277 mmol) and 2 (0.150 g,
0.555 mmol) in ethanol (15 cm3) was refluxed for 2 h. The solvent
was removed under reduced pressure, the resulting pale orange
solid was redissolved in dichloromethane and filtered through a
small celite plug. The filtrate was concentrated under vacuum to ca.
10 cm3 and hexane was added to precipitate the product as a pale
orange solid (0.109 g, 57%). Found (Calc. For C18H24O4P2S4Pt): C
31.67 (31.35), H 3.22 (3.51), S 23.33 (23.18)%.
Isomer (b): 31P NMR (CDCl3) : 114.7. 1H NMR (CDCl3) : 7.87
3
3
(dd, 2H, J(31P–1H) 14.1 Hz, J(1H–1H) 8.7 Hz, o-ArH), 6.88 (dd,
2H, J(31P–1H) 3.0 Hz, J(1H–1H) 9.0 Hz, m-ArH), 4.28 (dq, 2H,
4
3
3J(31P–1H) 3.0 Hz, J(1H–1H) 7.2 Hz, CH2), 3.78 (s, 3H, ArOMe),
3
1.35 (t, 3H, J(1H–1H) 6.9 Hz, CH3). 13C NMR (CDCl3) : 163.4
3
(s, p-ArC), 132.2 (d, J (31P–13C) 16.6 Hz, m-ArC), 129.0 (d, J
(31P–13C) 121.3 Hz, Ar C-1), 114.3 (d, 2J (31P–13C) 17.3 Hz, o-ArC),
63.3 (s, CH2), 55.9 (s, ArOCH3), 16.6 (s, CH3).
3
1
Isomer (a): 31P NMR (CDCl3) : 111.7 (s, 2J 31P–195Pt 377.8 Hz).
3
3
1H NMR (CDCl3) : 7.96 (dd, 2H, J(31P–1H) 15.0 Hz, J(1H–1H)
9.0 Hz, o-ArH), 6.92 (dd, 2H, 4J(31P–1H) 3.3 Hz, 3J(1H–1H) 7.5 Hz,
m-ArH), 4.40 (dq, 2H, 3J(31P–1H) 1.5 Hz, 3J(1H–1H) 7.2 Hz, CH2),
Selected IR data (KBr) /cm−1: 1181 (s), 1026 (m), 655 (m), 550
(m). Mass Spec (FAB): (M)+ 600.
3.80 (s, 3H, ArOMe), 1.39 (t, 3H, J(1H–1H) 7.2 Hz, CH3). 13C
3
NMR (CDCl3) : 163.4 (s, p-ArC), 132.1 (d, 3J (31P–13C) 15.1 Hz,
Bis[(isopropoxy)-4-methoxyphenylphosphonodithioato]Pd
(5p). A mixture of PdCl2(PhCN)2 (0.101 g, 0.264 mmol) and 1
(0.150 g, 0.528 mmol) in propan-2-ol (15 cm3) was refluxed for
2 h. The solvent was removed under reduced pressure, the result-
ing brown solid was redissolved in dichloromethane and filtered
through a small celite plug. The filtrate was concentrated under vac-
uum to ca. 10 cm3 and hexane was added to precipitate the product
m-ArC), 129.4 (d, J (31P–13C) 113.9 Hz, Ar C-1), 114.4 (d, J
(31P–13C) 16.6 Hz, o-ArC), 63.8 (s, CH2), 55.9 (s, ArOCH3), 16.7
(d, 3J(31P–13C) 7.5 Hz, CH3).
1
2
Isomer (b): 31P NMR (CDCl3) : 108.9 (s, 2J 31P–195Pt 377.9 Hz).
3
3
1H NMR (CDCl3) : 7.96 (dd, 2H, J(31P–1H) 15.0 Hz, J(1H–1H)
9.0 Hz, o-ArH), 6.89 (dd, 2H, 4J(31P–1H) 3.3 Hz, 3J(1H–1H) 7.5 Hz,
2 4 8 2
D a l t o n T r a n s . , 2 0 0 4 , 2 4 7 7 – 2 4 8 6

View Online
m-ArH), 4.36 (dq, 2H, 3J(31P–1H) 1.5 Hz, 3J(1H–1H) 7.2 Hz, CH2),
3J(31P–1H) 2.4 Hz, 3J(1H–1H) 6.9 Hz, CH2), 3.76 (s, 3H, ArOMe),
3
3
3.79 (s, 3H, ArOMe), 1.38 (t, 3H, J(1H–1H) 7.2 Hz, CH3). 13C
1.28 (t, 3H, J(1H–1H) 7.0 Hz, CH3). 13C NMR (CDCl3) : 163.0
NMR (CDCl3) : 163.4 (s, p-ArC), 132.1 (d, 3J (31P–13C) 15.1 Hz,
(d, J (31P–13C) 3.0 Hz, p-ArC), 132.8 (d, J (31P–13C) 14.3 Hz,
4
3
1
2
m-ArC), 129.3 (d, J (31P–13C) 113.9 Hz, Ar C-1), 114.3 (d, J
(31P–13C) 17.3 Hz, o-ArC), 63.8 (s, CH2), 55.9 (s, ArOCH3), 16.7
(d, 3J(31P–13C) 7.5 Hz, CH3).
m-ArC), 129.0 (d, 1J (31P–13C) 120.7 Hz, Ar C-1), 114.1 (d,
2J (31P–13C) 15.8 Hz, o-ArC), 63.1 (d, J (31P–13C) 6.8 Hz, CH2),
2
55.9 (s, ArOCH3), 16.5 (d, J(31P–13C) 9.1 Hz, CH3). Selected IR
3
Selected IR data (KBr) /cm−1: 1180 (s), 1026 (s), 661 (m), 549
(m). Mass Spec (FAB): (M)+ 689.
data (KBr) /cm−1: 1179 (s), 1026 (m), 652 (m), 551 (m). Mass
Spec (FAB): (1/2M)+ 607, (M − PS2O2C9H12)+ 967.
Bis[(isopropoxy)-4-methoxyphenylphosphonodithioato]Pt
(6p). A mixture of K2PtCl4 (0.219 g, 0.528 mmol) and 1 (0.300 g,
1.055 mmol) in propan-2-ol (15 cm3) was refluxed for 2 h. H2O
(15 cm3) was added and the reaction mixture was refluxed for a
further 1 h. An obvious orange precipitate was observed and col-
lected by suction filtration, washed firstly with H2O (2 × 10 cm3)
then propan-2-ol (2 × 10 cm3) and dried in vacuo to give an orange
solid (0.273 g, 72%).
Bis[(isopropoxy)-4-methoxyphenylphosphonodithioato]Cd
(7p). A mixture of Cd(CH3COO)2·2H2O (0.141 g, 0.528 mmol) and
2 (0.300 g, 1.06 mmol) in propan-2-ol (15 cm3) was refluxed for
2 h. The solvent was removed under reduced pressure, the resulting
white solid was redissolved in dichloromethane and filtered through
a small celite plug. The filtrate was concentrated under vacuum to
ca. 10 cm3 and hexane was added to precipitate the product as a
white solid (0.249 g, 74%). Colourless crystals suitable for X-ray
analysis were grown by vapour diffusion of hexane into a chloro-
form solution. Found (Calc. For C40H56O8P4S8Cd2): C 37.80 (37.74),
Found (Calc. For C20H28O4P2S4Pt): C 33.33 (33.47), H 3.86
(3.94), S 18.31 (17.84)%.
Isomer (a): 31P NMR (CDCl3) : 107.7 (s, 2J 31P–195Pt 377.8 Hz).
1
H 4.47 (4.44), S 20.35 (20.11)%. 31P NMR (CDCl3) : 104.0. H
3
3
1H NMR (CDCl3) : 7.96 (dd, 2H, J(31P–1H) 14.1 Hz, J(1H–1H)
3
3
NMR (CDCl3) : 7.93 (dd, 2H, J(31P–1H) 14.6 Hz, J(1H–1H)
9.9 Hz, o-ArH), 6.91 (dd, 2H, 4J(31P–1H) 3.0 Hz, 3J(1H–1H) 8.9 Hz,
9.0 Hz, o-ArH), 6.85 (dd, 2H, 4J(31P–1H) 3.3 Hz, 3J(1H–1H) 9.0 Hz,
m-ArH), 5.16 (dsept, 1H, J(31P–1H) 2.4 Hz, J(1H–1H) 6.0 Hz,
3
3
m-ArH), 5.00 (dsept, 1H, J(31P–1H) 2.4 Hz, J(1H–1H) 6.3 Hz,
3
3
CH), 3.80 (s, 3H, ArOMe), 1.38 (d, 6H, J(1H–1H) 6.0 Hz. 13C
3
CH), 3.76 (s, 3H, ArOMe), 1.29 (d, 6H, J(1H–1H) 6.3 Hz. 13C
3
NMR (CDCl3) : 162.7 (s, p-ArC), 133.3 (d, 3J (31P–13C) 11.4 Hz,
NMR (CDCl3) : 163.4 (d, 4J (31P–13C) 3.0 Hz, p-ArC), 133.1 (d, 3J
(31P–13C) 14.3 Hz, m-ArC), 129.6 (d, 1J (31P–13C) 122.2 Hz, Ar C-1),
114.3 (d, 2J (31P–13C) 15.8 Hz, o-ArC), 73.1 (d, 2J (31P–13C) 7.6 Hz,
CH), 56.3 (s, ArOCH3), 24.5 (d, 3J (31P–13C) 3.8 Hz, CH3). Selected
IR data (KBr) /cm−1: 1182 (m), 1029 (m), 663 (m), 539 (s). Mass
Spec (FAB): (M − PS2O2C9H12)+ 1009, (M)+ 1270.
m-ArC), 120.4 (d, J (31P–13C) 123.7 Hz, Ar C-1), 114.0 (d, J
(31P–13C) 16.6 Hz, o-ArC), 71.0 (d, 2J (31P–13C) 6.8 Hz, CH), 55.9
(s, ArOCH3), 24.8 (s, CH3).
1
2
Isomer (b): 31P NMR (CDCl3) : 104.8 (s, 2J 31P–195Pt 377.3 Hz).
3
3
1H NMR (CDCl3) : 7.96 (dd, 2H, J(31P–1H) 14.1 Hz, J(1H–1H)
9.9 Hz, o-ArH), 6.89 (dd, 2H, 4J(31P–1H) 3.0 Hz, 3J(1H–1H) 9.0 Hz,
m-ArH), 5.14 (dsept, 1H, J(31P–1H) 1.8 Hz, J(1H–1H) 6.6 Hz,
3
3
Bis[(methoxy)-4-methoxyphenylphosphonodithioato]Hg
(8m). A mixture of HgCl2 (0.159 g, 0.585 mmol) and 1 (0.300 g,
1.71 mmol) in methanol (15 cm3) was refluxed for 2 h. The sol-
vent was removed under reduced pressure, the resulting white
solid was redissolved in dichloromethane and filtered through a
small celite plug. The filtrate was concentrated under vacuum to
ca. 10 cm3 and hexane was added to precipitate the product as a
white solid (0.306 g, 78%). Found (Calc. For C32H40O8P4S8Hg2): C
28.81 (28.74), H 2.78 (3.02), S 19.42 (19.23)%. 31P NMR (CDCl3)
CH), 3.79 (s, 3H, ArOMe), 1.37 (d, 6H, J(1H–1H) 6.2 Hz. 13C
3
NMR (CDCl3) : 162.7 (s, p-ArC), 131.8 (d, 3J (31P–13C) 14.5 Hz,
m-ArC), 120.4 (d, J (31P–13C) 123.7 Hz, Ar C-1), 113.8 (d, J
(31P–13C) 16.6 Hz, o-ArC), 71.0 (d, 2J (31P–13C) 6.8 Hz, CH), 55.7
(s, ArOCH3), 24.3 (s, CH3).
1
2
Selected IR data (KBr) /cm−1: 1181 (s), 1025 (m), 661 (m), 546
(m). Mass Spec (FAB): (M)+ 717.
1
3
: 108.8. H NMR (CDCl3) : 7.98 (dd, 2H, J(31P–1H) 14.2 Hz,
3J(1H–1H) 8.7 Hz, o-ArH), 6.96 (dd, 2H, 4J(31P–1H) 3.6 Hz, 3J(1H–
1H) 8.7 Hz, m-ArH), 3.95 (d, 3H, 2J(1H–1H) 15.6 Hz, CH3), 3.85 (s,
3H, ArOMe). 13C NMR (CDCl3) : 163.2 (d, 4J (31P–13C) 3.8 Hz, p-
ArC), 132.7 (d, 3J (31P–13C) 14.3 Hz, m-ArC), 128.6 (d, 1J (31P–13C)
123.8 Hz, Ar C-1), 114.1 (d, 2J (31P–13C) 16.6 Hz, o-ArC), 55.9 (s,
ArOCH3), 53.1 (d, 2J (31P–13C) 6.8 Hz, CH3). Selected IR data (KBr)
/cm−1: 1182 (s), 1023 (s), 660 (s), 535 (s). Mass Spec (FAB): (1/
2M)+ 667, (M − PS2O2C8H10)+ 1101, (M)+ 1333.
Bis[(methoxy)-4-methoxyphenylphosphonodithioato]Cd
(7m). A mixture of Cd(CH3COO)2·2H2O (0.156 g, 0.585 mmol)
and 1 (0.300 g, 1.71 mmol) in methanol (15 cm3) was refluxed for
2 h. The solvent was removed under reduced pressure, the resulting
white solid was redissolved in dichloromethane and filtered through
a small celite plug. The filtrate was concentrated under vacuum to
ca. 10 cm3 and hexane was added to precipitate the product as a
white solid (0.254 g, 75%). Found (Calc. For C32H40O8P4S8Cd2): C
33.02 (33.11), H 3.75 (3.48), S 22.18 (22.05)%. 31P NMR (CDCl3)
1
3
: 109.8. H NMR (CDCl3) : 8.00 (dd, 2H, J(31P–1H) 14.7 Hz,
3J(1H–1H) 9.0 Hz, o-ArH), 6.95 (dd, 2H, 4J(31P–1H) 3.6 Hz, 3J(1H–
1H) 9.0 Hz, m-ArH), 3.85 (d, 3H, 2J(1H–1H) 15.3 Hz, CH3), 3.84 (s,
3H, ArOMe). 13C NMR (CDCl3) : 163.1 (d, 4J (31P–13C) 3.0 Hz, p-
ArC), 132.8 (d, 3J (31P–13C) 14.3 Hz, m-ArC), 128.3 (d, 1J (31P–13C)
120.7 Hz, Ar C-1), 114.1 (d, 2J (31P–13C) 15.8 Hz, o-ArC), 55.9 (s,
ArOCH3), 53.1 (d, 2J (31P–13C) 7.5 Hz, CH3). Selected IR data (KBr)
/cm−1: 1179 (m), 1019 (vs), 661 (m), 536 (s). Mass Spec (FAB):
(1/2M)+ 580, (M–PS2O2C8H10)+ 925, (M)+ 1158.
Bis[(ethoxy)-4-methoxyphenylphosphonodithioato]Hg
(8e). A mixture of HgCl2 (0.151 g, 0.550 mmol) and 2 (0.300 g,
1.11 mmol) in ethanol (15 cm3) was refluxed for 2 h. The solvent
was removed under reduced pressure, the resulting white solid was
redissolved in dichloromethane and filtered through a small celite
plug. The filtrate was concentrated under vacuum to ca. 10 cm3
and hexane was added to precipitate the product as a white solid
(0.308 g, 80%). Colourless crystals suitable for X-ray analysis were
grown by vapour diffusion of hexane into a chloroform solution.
Found (Calc. For C36H48O8P4S8Hg2): C 30.95 (31.04), H 3.52 (3.48),
Bis[(ethoxy)-4-methoxyphenylphosphonodithioato]Cd
(7e). A mixture of Cd(CH3COO)2·2H2O (0.148 g, 0.555 mmol)
and 2 (0.300 g, 1.11 mmol) in ethanol (15 cm3) was refluxed
for 2 h. The solvent was removed under reduced pressure, the
resulting white solid was redissolved in dichloromethane and
filtered through a small celite plug. The filtrate was concentrated
under vacuum to ca. 10 cm3 and hexane was added to precipi-
tate the product as a white solid (0.311 g, 92%). Found (Calc.
For C36H48O8P4S8Cd2): C 35.91 (35.53), H 4.18 (3.98), S 20.87
1
S 18.67 (18.38)%. 31P NMR (CDCl3) : 105.2. H NMR (CDCl3)
3
3
: 7.91 (dd, 2H, J(31P–1H) 14.6 Hz, J(1H–1H) 9.0 Hz, o-ArH),
6.89 (dd, 2H, J(31P–1H) 3.3 Hz, J(1H–1H) 9.0 Hz, m-ArH), 4.30
4
3
(dq, 2H, J(31P–1H) 2.7 Hz, J(1H–1H) 6.9 Hz, CH2), 3.77 (s, 3H,
3
3
ArOMe), 1.34 (t, 3H, J(1H–1H) 6.9 Hz, CH3). 13C NMR (CDCl3)
3
: 163.1 (d, J (31P–13C) 3.0 Hz, p-ArC), 132.6 (d, J (31P–13C)
4
3
14.3 Hz, m-ArC), 129.1 (d, J (31P–13C) 123.0 Hz, Ar C-1), 114.2
1
(d, 2J (31P–13C) 15.8 Hz, o-ArC), 63.2 (d, 2J (31P–13C) 6.8 Hz, CH2),
1
3
(21.04)%. 31P NMR (CDCl3) : 106.5. H NMR (CDCl3) : 7.93
55.9 (s, ArOCH3), 16.5 (d, J(31P–13C) 9.1 Hz, CH3). Selected IR
(dd, 2H, 3J(31P–1H) 14.4 Hz, 3J(1H–1H) 9.0 Hz, o-ArH), 6.87 (dd,
data (KBr) /cm−1: 1177 (s), 1029 (s), 646 (m), 551 (w). Mass Spec
4
3
2H, J(31P–1H) 3.0 Hz, J(1H–1H) 9.0 Hz, m-ArH), 4.17 (dq, 2H,
(FAB): (1/2M)+ 685, (M − PS2O2C9H12)+ 1143.
D a l t o n T r a n s . , 2 0 0 4 , 2 4 7 7 – 2 4 8 6
2 4 8 3

View Online
Bis[(isopropoxy)-4-methoxyphenylphosphonodithioato]Hg
(8p). A mixture of HgCl2 (0.143 g, 0.528 mmol) and 2 (0.300 g,
1.06 mmol) in propan-2-ol (15 cm3) was refluxed for 2 h. The
solvent was removed under reduced pressure, the resulting white
solid was redissolved in dichloromethane and filtered through a
small celite plug. The filtrate was concentrated under vacuum to ca.
10 cm3 and hexane was added to precipitate the product as a white
solid (0.218 g, 57%). Colourless crystals suitable for X-ray analysis
were grown by vapour diffusion of hexane into a chloroform solu-
tion. Found (Calc. For C40H56O8P4S8Hg2): C 32.90 (33.15), H 3.66
solid (0.216 g, 70%) Colourless crystals suitable for X-ray analy-
sis were grown by vapour diffusion of hexane into a chloroform
solution. Found (Calc. For C40H56O8P4S8Zn2): C 40.98 (40.96), H
4.77 (4.82), S 21.53 (21.81)%. 31P NMR (CDCl3) : 98.5. 1H NMR
(CDCl3) : 7.88 (dd, 2H, 3J(31P–1H) 14.9 Hz, 3J(1H–1H) 8.7 Hz, o-
ArH), 6.88 (dd, 2H, 4J(31P–1H) 3.3 Hz, 3J(1H–1H) 8.7 Hz, m-ArH),
5.05 (dsept, 1H, 3J(31P–1H) 2.7 Hz, 3J(1H–1H) 6.3 Hz, CH), 3.77 (s,
3H, ArOMe), 1.34 (d, 6H, 3J(1H–1H) 6.3 Hz. 13C NMR (CDCl3) :
162.9 (s, p-ArC), 132.4 (d, 3J (31P–13C) 15.1 Hz, m-ArC), 129.4 (d,
2
1J (31P–13C) 121.0 Hz, Ar C-1), 114.1 (d, J (31P–13C) 15.9 Hz, o-
1
(3.90), S 18.01 (17.66)%. 31P NMR (CDCl3) : 102.7. H NMR
ArC), 72.6 (d, 2J (31P–13C) 6.8 Hz, CH), 55.9 (s, ArOCH3), 24.4 (d,
3J (31P–13C) 3.8 Hz, CH3). Selected IR data (KBr) /cm−1: 1181 (s),
1029 (m), 658 (w), 543 (m). Mass Spec (FAB): (M − PS2O2C9H12)+
915, (M − O2C10H13)+ 1011.
(CDCl3) : 7.91 (dd, 2H, 3J(31P–1H) 14.4 Hz, 3J(1H–1H) 9.0 Hz, o-
ArH), 6.88 (dd, 2H, 4J(31P–1H) 3.6 Hz, 3J(1H–1H) 9.0 Hz, m-ArH),
3
3
5.13 (dsept, 1H, J(31P–1H) 1.8 Hz, J(1H–1H) 6.6 Hz, CH), 3.78
(s, 3H, ArOMe), 1.35 (d, 6H, 3J(1H–1H) 6.6 Hz. 13C NMR (CDCl3)
: 163.1 (d, J (31P–13C) 3.0 Hz, p-ArC), 132.7 (d, J (31P–13C)
4
3
Bis[(methoxy)-4-methoxyphenylphosphonodithioato]Sn
(10m). A mixture of SnCl2 (0.111 g, 0.585 mmol) and 1 (0.300 g,
1.71 mmol) in methanol (15 cm3) was refluxed for 2 h. The solvent
was removed under reduced pressure, the resulting pale yellow
solid was redissolved in dichloromethane and filtered through a
small celite plug. The filtrate was concentrated under vacuum to ca.
10 cm3 and hexane was added to precipitate the product as a pale
yellow solid (0.277 g, 81%). Found (Calc. For C32H40O8P4S8Sn2): C
33.09 (32.77), H 3.48 (3.44), S 21.66 (21.83)%. 31P NMR (CDCl3)
14.3 Hz, m-ArC), 129.5 (d, J (31P–13C) 123.8 Hz, Ar C-1), 114.2
1
(d, 2J (31P–13C) 15.9 Hz, o-ArC), 73.3 (d, 2J (31P–13C) 7.6 Hz, CH),
55.9 (s, ArOCH3), 24.5 (d, J (31P–13C) 4.5 Hz, CH3). Selected IR
3
data (KBr) /cm−1: 1179 (m), 1025 (m), 663 (m), 539 (s). Mass Spec
(FAB): (1/2M)+ 723, (M − PS2O2C9H12)+ 1185, (M − C2H5)+ 1417,
(M)+ 1446.
Bis[(methoxy)-4-methoxyphenylphosphonodithioato]Zn
(9m). A mixture of ZnCl2 (0.080 g, 0.585 mmol) and 1 (0.300 g,
1.71 mmol) in methanol (15 cm3) was refluxed for 2 h. The sol-
vent was removed under reduced pressure, the resulting white
solid was redissolved in dichloromethane and filtered through a
small celite plug. The filtrate was concentrated under vacuum to
ca. 10 cm3 and hexane was added to precipitate the product as a
white solid (0.188 g, 61%). Found (Calc. For C32H40O8P4S8Zn2): C
36.33 (36.23), H 4.01 (3.80), S 24.54 (24.13)%. 31P NMR (CDCl3)
1
3
: 95.1. H NMR (CDCl3) : 7.91 (dd, 2H, J(31P–1H) 15.0 Hz,
3J(1H–1H) 9.0 Hz, o-ArH), 6.95 (dd, 2H, 4J(31P–1H) 3.3 Hz, 3J(1H–
1H) 9.0 Hz, m-ArH), 3.86 (d, 3H, 2J(1H–1H) 15.6 Hz, CH3), 3.84 (s,
3H, ArOMe). 13C NMR (CDCl3) : 163.0 (d, 4J (31P–13C) 3.8 Hz, p-
ArC), 132.1 (d, 3J (31P–13C) 14.3 Hz, m-ArC), 130.7 (d, 1J (31P–13C)
127.5 Hz,Ar C-1), 114.1 (d, 2J (31P–13C) 15.8 Hz, o-ArC), 56.0 (d, 2J
(31P–13C) 11.3 Hz, CH3), 52.4 (s, ArOCH3). Selected IR data (KBr)
/cm−1: 1180 (m), 1024 (vs), 663 (m), 539 (s). Mass Spec (FAB):
(1/2M)+ 586, (M − PS2O2C8H10)+ 939, (M)+ 1172.
1
3
: 105.1. H NMR (CDCl3) : 7.96 (dd, 2H, J(31P–1H) 14.9 Hz,
3J(1H–1H) 9.0 Hz, o-ArH), 6.97 (dd, 2H, 4J(31P–1H) 3.3 Hz, 3J(1H–
1H) 9.0 Hz, m-ArH), 3.90 (d, 3H, 2J(1H–1H) 15.6 Hz, CH3), 3.85 (s,
3H, ArOMe). 13C NMR (CDCl3) : 163.2 (d, 4J (31P–13C) 3.8 Hz, p-
ArC), 132.6 (d, 3J (31P–13C) 15.1 Hz, m-ArC), 128.4 (d, 1J (31P–13C)
122.1 Hz, Ar C-1), 114.2 (d, 2J (31P–13C) 15.8 Hz, o-ArC), 55.9 (s,
ArOCH3), 52.9 (d, 2J (31P–13C) 6.8 Hz, CH3). Selected IR data (KBr)
/cm−1: 1181 (m), 1026 (s), 663 (m), 542 (s). Mass Spec (FAB):
(1/2M)+ 531, (M − PS2O2C8H10)+ 831.
Bis[(ethoxy)-4-methoxyphenylphosphonodithioato]Sn
(10e). A mixture of SnCl2 (0.076 g, 0.550 mmol) and 2 (0.300 g,
1.11 mmol) in ethanol (15 cm3) was refluxed for 2 h. The solvent
was removed under reduced pressure, the resulting white solid
was redissolved in dichloromethane and filtered through a small
celite plug. The filtrate was concentrated under vacuum to ca.
10 cm3 and hexane was added to precipitate the product as a white
solid (0.235 g, 69%). Found (Calc. For C36H48O8P4S8Sn2): C 35.27
(35.18), H 4.12 (3.94), S 20.34 (20.83)%. 31P NMR (CDCl3) : 89.1.
Bis[(ethoxy)-4-methoxyphenylphosphonodithioato]Zn
(9e). A mixture of ZnCl2 (0.076 g, 0.550 mmol) and 2 (0.300 g,
1.11 mmol) in ethanol (15 cm3) was refluxed for 2 h. The solvent
was removed under reduced pressure, the resulting white solid was
redissolved in dichloromethane and filtered through a small celite
plug. The filtrate was concentrated under vacuum to ca. 10 cm3
and hexane was added to precipitate the product as a white solid
(0.193 g, 62%). Colourless crystals suitable for X-ray analysis were
grown by vapour diffusion of hexane into a chloroform solution.
Found (Calc. For C36H48O8P4S8Zn2): C 38.67 (38.71), H 4.02 (4.34),
3
3
1H NMR (CDCl3) : 7.83 (dd, 2H, J(31P–1H) 14.9 Hz, J(1H–1H)
9.0 Hz, o-ArH), 6.87 (dd, 2H, 4J(31P–1H) 3.3 Hz, 3J(1H–1H) 9.0 Hz,
m-ArH), 4.69 (dq, 2H, 3J(31P–1H) 3.0 Hz, 3J(1H–1H) 7.2 Hz, CH2),
3.78 (s, 3H, ArOMe), 1.29 (t, 3H, J(1H–1H) 6.9 Hz, CH3). 13C
3
NMR (CDCl3) : 163.2 (d, 4J (31P–13C) 3.0 Hz, p-ArC), 132.1 (d, 3J
(31P–13C) 15.3 Hz, m-ArC), 129.0 (d, 1J (31P–13C) 123.1 Hz,Ar C-1),
114.4 (d, 2J (31P–13C) 16.6 Hz, o-ArC), 63.0 (d, 2J (31P–13C) 6.9 Hz,
CH2), 55.9 (s, ArOCH3), 16.5 (d, 3J(31P–13C) 8.0 Hz, CH3). Selected
IR data (KBr) /cm−1: 1182 (s), 1024 (s), 655 (m), 545 (m). Mass
Spec (FAB): (1/2M)+ 614, (M − PS2O2C9H12)+ 982.
1
S 22.84 (22.92)%. 31P NMR (CDCl3) : 101.3. H NMR (CDCl3)
3
3
: 7.89 (dd, 2H, J(31P–1H) 14.6 Hz, J(1H–1H) 9.0 Hz, o-ArH),
6.88 (dd, 2H, J(31P–1H) 3.3 Hz, J(1H–1H) 9.0 Hz, m-ArH), 4.24
4
3
Bis[(isopropoxy)-4-methoxyphenylphosphonodithioato]Sn
(10p). A mixture of SnCl2 (0.100 g, 0.528 mmol) and 2 (0.300 g,
1.06 mmol) in propan-2-ol (15 cm3) was refluxed for 2 h. The
solvent was removed under reduced pressure, the resulting pale
yellow solid was redissolved in dichloromethane and filtered
through a small celite plug. The filtrate was concentrated under
vacuum to ca. 10 cm3 and hexane was added to precipitate the
product as a pale yellow solid (0.219 g, 65%). Found (Calc.
For C40H56O8P4S8Sn2): C 37.62 (37.39), H 3.97 (4.40), S 20.40
(dq, 2H, J(31P–1H) 2.7 Hz, J(1H–1H) 6.9 Hz, CH2), 3.77 (s, 3H,
3
3
ArOMe), 1.31 (t, 3H, J(1H–1H) 6.9 Hz, CH3). 13C NMR (CDCl3)
3
: 163.0 (d, J(31P–13C) 3.0 Hz, p-ArC), 132.5 (d, J (31P–13C)
4
3
14.3 Hz, m-ArC), 128.7 (d, J (31P–13C) 122.6 Hz, Ar C-1), 114.1
1
(d, 2J (31P–13C) 16.6 Hz, o-ArC), 62.9 (d, 2J (31P–13C) 6.8 Hz, CH2),
55.9 (s, ArOCH3), 16.4 (d, J(31P–13C) 8.3 Hz, CH3). Selected IR
3
data (KBr) /cm−1: 1182 (s), 1026 (s), 654 (m), 543 (s). Mass Spec
(FAB): (1/2M)+ 559, (M − PS2O2C9H12)+ 873.
1
(19.92)%. 31P NMR (CDCl3) : 98.5. H NMR (CDCl3) : 7.88
Bis[(isopropoxy)-4-methoxyphenylphosphonodithioato]Zn
(9p). A mixture of ZnCl2 (0.072 g, 0.528 mmol) and 2 (0.300 g,
1.06 mmol) in propan-2-ol (15 cm3) was refluxed for 2 h. The
solvent was removed under reduced pressure, the resulting white
solid was redissolved in dichloromethane and filtered through a
small celite plug. The filtrate was concentrated under vacuum to ca.
10 cm3 and hexane was added to precipitate the product as a white
(dd, 2H, 3J(31P–1H) 14.1 Hz, 3J(1H–1H) 9.0 Hz, o-ArH), 6.89 (dd,
4
3
2H, J(31P–1H) 3.0 Hz, J(1H–1H) 9.0 Hz, m-ArH), 5.09 (dsept,
1H, 3J(31P–1H) 2.4 Hz, 3J(1H–1H) 6.2 Hz, CH), 3.77 (s, 3H,
ArOMe), 1.34 (d, 6H, J(1H–1H) 6.2 Hz. 13C NMR (CDCl3) :
3
162.7 (s, p-ArC), 132.0 (d, J (31P–13C) 15.0 Hz, m-ArC), 129.1
3
(d, 1J (31P–13C) 125.6 Hz, Ar C-1), 114.1 (d, 2J (31P–13C) 16.4 Hz,
o-ArC), 71.8 (d, 2J (31P–13C) 6.8 Hz, CH), 55.9 (s, ArOCH3), 24.3
2 4 8 4
D a l t o n T r a n s . , 2 0 0 4 , 2 4 7 7 – 2 4 8 6

View Online
Table 4 Details of the X-ray data collections and refinements
Compound
4m
4p
7p
8e
Empirical formula
Crystal colour, habit
Crystal dimensions/mm
Crystal system
C16H20NiO4P2S4
Purple, prism
0.2 × 0.05 × 0.05
Monoclinic
P2(1)/c
C20H28NiO4P2S4
Purple, prism
0.18 × 0.1 × 0.1
Triclinic
C40H56Cd2O8P4S8
Colourless, block
0.1 × 0.1 × 0.1
Triclinic
P1
C36H48Hg2O8P4S8
Colourless, block
0.1 × 0.1 × 0.1
Monoclinic
P2(1)/c
Space group
P1
a/Å
b/Å
c/Å
/°
11.823(3)
6.5091(15)
14.414(4)
90
110.464(7)
90
7.8059(13)
8.7446(15)
10.8461(18)
99.405(3)
96.962(3)
112.419(3)
661.38(19)
1
11.308(2)
11.604(3)
12.339(3)
83.965(4)
65.562(3)
68.987(3)
1378.5(5)
1
15.301(3)
14.741(2)
10.5504(17)
90
94.994(3)
90
/°
/°
U/Å3
1039.2(4)
2
2370.7(7)
2
Z
M
525.21
1.678
1.510
581.31
1.460
1.194
1270.01
1.530
1.234
1390.28
1.948
7.002
Dc/g cm−3
/mm−1
F(000)
540
302
644
1352
Measured reflections
Independent reflections (Rint)
Final R1, R2 [I > 2(I)]
6428
2001(0.0285)
0.0240, 0.0567
3771
2369(0.0087)
0.0300, 0.0776
8814
4936(0.0147)
0.0216, 0.0470
13693
4241(0.0655)
0.0338, 0.0621
Table 5 Details of the X-ray data collections and refinements
Compound
8p
9e
9p
11e
11p
Empirical formula
Crystal colour, habit
Crystal dimensions/mm
Crystal system
C40H56Hg2O8P4S8
Colourless, block
0.1 × 0.1 × 0.1
Triclinic
C36H48Zn2O8P4S8
Colourless, prism
0.1 × 0.05 × 0.04
Triclinic
C40H56Zn2O8P4S8
C18H24PbO4P2S4
C40H56Pb2O8P4S8
Colourless, prism
0.17 × 0.1 × 0.1
Triclinic
P1
Colourless, block
0.2 × 0.04 × 0.01
Monoclinic
C2/c
Colourless, block
0.14 × 0.1 × 0.02
Triclinic
P1
Space group
P1
P1
a/Å
b/Å
c/Å
/°
10.417(3)
10.925(3)
12.287(3)
94.419(7)
96.945(5)
106.225(7)
1323.7(7)
1
10.796(2)
11.222(2)
12.495(2)
65.482(18)
77.56(2)
79.46(2)
1337.4(4)
1
11.240(2)
11.580(2)
12.307(3)
85.470(4)
64.877(3)
68.546(3)
1344.4(5)
1
22.504(6)
11.582(3)
9.857(2)
90
114.824(6)
90
11.2492(16)
12.1942(17)
12.4142(17)
90
93.228(2)
90
/°
/°
U/Å3
2331.8(10)
4
1499.3(4)
1
Z
M
1446.39
1.814
6.274
1206.02
1.497
1.376
1175.95
1.452
1.366
701.74
1.999
7.754
1545.76
1.712
6.038
Dc/g cm−3
/mm−1
F(000)
708
626
608
1360
762
Measured reflections
Independent reflections (Rint)
Final R1, R2 [I > 2(I)]
7772
4459(0.0564)
0.0410, 0.0761
7767
4501(0.0288)
0.0419, 0.0996
7926
4755(0.0393)
0.0733, 0.2143
6948
2102(0.0284)
0.0237, 0.0474
8988
5390(0.0265)
0.0276, 0.0643
(d, 3J (31P–13C) 3.3 Hz, CH3). Selected IR data (KBr) /cm−1: 1180
(s), 1027 (s), 674 (w), 534 (m). Mass Spec (FAB): (1/2M)+ 642,
(M − PS2O2C10H14)+ 1021.
The solvent was removed under reduced pressure, the resulting
pale brown solid was redissolved in dichloromethane and filtered
through a small celite plug. The filtrate was concentrated under
vacuum to ca. 10 cm3 and hexane was added to precipitate the prod-
uct as a white solid (0.261 g, 67%). Colourless crystals suitable for
X-ray analysis were grown by vapour diffusion of hexane into a
chloroform solution. Found (Calc. For C36H48O8P4S8Pb2): C 30.72
(30.77), H 3.36 (3.45), S 17.79 (18.22)%. 31P NMR (CDCl3) : 97.7.
Bis[(methoxy)-4-methoxyphenylphosphonodithioato]Pb
(11m). A mixture of Pb(CH3COO)2·3H2O (0.222 g, 0.585 mmol)
and 1 (0.300 g, 1.71 mmol) in methanol (15 cm3) was refluxed for
2 h. The solvent was removed under reduced pressure, the resulting
sticky white solid was redissolved in dichloromethane and filtered
through a small celite plug. The filtrate was concentrated under vac-
uum to ca. 10 cm3 and hexane was added to precipitate the product
as a white solid (0.245 g, 62%). Found (Calc. For C32H40O8P4S8Pb2):
C 28.33 (28.49), H 2.91 (2.99), S 19.22 (18.99)%. 31PNMR (CDCl3)
3
3
1H NMR (CDCl3) : 7.86 (dd, 2H, J(31P–1H) 14.6 Hz, J(1H–1H)
9.0 Hz, o-ArH), 6.87 (dd, 2H, 4J(31P–1H) 3.3 Hz, 3J(1H–1H) 9.0 Hz,
m-ArH), 4.16 (dq, 2H, 3J(31P–1H) 3.0 Hz, 3J(1H–1H) 6.9 Hz, CH2),
3
3.78 (s, 3H, ArOMe), 1.29 (t, 3H, J(1H–1H) 7.0 Hz, CH3). 13C
NMR (CDCl3) : 162.5 (d, 4J (31P–13C) 3.1 Hz, p-ArC), 132.3 (d, 1J
(31P–13C) 124.6 Hz, Ar C-1), 131.5 (d, 3J (31P–13C) 14.5 Hz, m-ArC),
113.7 (d, 2J (31P–13C) 16.6 Hz, o-ArC), 61.7 (d, 2J (31P–13C) 7.3 Hz,
CH2), 55.5 (s, ArOCH3), 16.3 (d, 3J(31P–13C) 8.3 Hz, CH3). Selected
IR data (KBr) /cm−1: 1181 (s), 1027 (m), 654 (m), 551 (m). Mass
Spec (FAB): (1/2M)+ 703, (M − PS2O2C9H12)+ 1157.
1
3
: 100.9. H NMR (CDCl3) : 7.86 (dd, 2H, J(31P–1H) 14.7 Hz,
3J(1H–1H) 9.0 Hz, o-ArH), 6.88 (dd, 2H, 4J(31P–1H) 3.3 Hz, 3J(1H–
1H) 9.0 Hz, m-ArH), 3.78 (s, 3H, ArOMe), 3.76 (d, 3H, 2J(1H–1H)
15.3 Hz, CH3). 13C NMR (CDCl3) : 163.0 (d, 4J (31P–13C) 3.2 Hz, p-
ArC), 131.8 (d, 3J (31P–13C) 15.1 Hz, m-ArC), 129.7 (d, 1J (31P–13C)
125.5 Hz, Ar C-1), 114.1 (d, 2J (31P–13C) 15.8 Hz, o-ArC), 55.9 (s,
ArOCH3), 52.2 (d, 2J (31P–13C) 8.3 Hz, CH3). Selected IR data (KBr)
/cm−1: 1177 (s), 1020 (vs), 666 (m), 552 (m). Mass Spec (FAB):
(M − PS2O2C8H10)+ 1115.
Bis[(isopropoxy)-4-methoxyphenylphosphonodithioato]Pb
(11p). A mixture of Pb(CH3COO)2·3H2O (0.200 g, 0.528 mmol)
and 2 (0.300 g, 1.06 mmol) in propan-2-ol (15 cm3) was refluxed
for 2 h. The solvent was removed under reduced pressure, the result-
ing brown solid was redissolved in dichloromethane and filtered
through a small celite plug. The filtrate was concentrated under
vacuum to ca. 10 cm3 and hexane was added to precipitate the prod-
Bis[(ethoxy)-4-methoxyphenylphosphonodithioato]Pb (11e).
A mixture of Pb(CH3COO)2·3H2O (0.211 g, 0.550 mmol) and 2
(0.300 g, 1.11 mmol) in ethanol (15 cm3) was refluxed for 2 h.
D a l t o n T r a n s . , 2 0 0 4 , 2 4 7 7 – 2 4 8 6
2 4 8 5

View Online
Chem. Forsch., 1973, 35, 65; (c) G. Svensson and J. Albertsson,
uct as a white solid (0.223 g, 58%). Colourless crystals suitable for
X-ray analysis were grown by vapour diffusion of hexane into a
chloroform solution. Found (Calc. For C40H56O8P4S8Pb2): C 32.96
(32.88), H 3.93 (3.87), S 17.99 (17.52)%. 31P NMR (CDCl3) : 95.4.
Acta Chem. Scand., 1991, 45, 820; (d) I. Haiduc, D. B. Sowerby and
S. F. Lu, Polyhedron, 1995, 14, 3389; (e) I. Haiduc, D. B. Sowerby
and S. F. Lu, Polyhedron, 1996, 15, 2469; (f) J. S. Casas, M. S.
Garcia-Tasende, A. Sanchez, J. Sordo, E. M. Vazquez-Lopez, E. E.
Castellano and J. Zukerman-Schpector, Inorg. Chim. Acta, 1994,
219, 115; (g) K. H. Ebert, H. J. Breunig, C. Silvestru, I. Stefan and
I. Haiduc, Inorg. Chem., 1994, 33, 1695; (h) C. Silvestru, I. Haiduc,
R. Cea-Olivares and S. Hernandez-Ortega, Inorg. Chem. Acta, 1995,
233, 151; (i) M. C. Aragoni, M. Arca, F. Demartin, F. A. Devillanova,
C. Graiff, F. Isaia, V. Lippolis, A. Tiripicchio and G. Verani, J. Chem.
Soc., Dalton Trans., 2000, 2671.
9 (a) L. Malatesta and R. Pizzotti, Chim. Ind., 1945, 27, 6; (b) Malatesta
and R. Pizzotti, Chim. Ind., 1946, 76, 167; (c) P. S. Shetty, P. Jose and
Q. Fernando, J. Chem. Soc., Chem. Commun., 1968, 788; (d) H. Hartung,
Z. Chem., 1967, 7, 241; (e) J. P. Fackler, Jr. and L. D. Thompson, Jr.,
Inorg. Chim. Acta, 1981, 48, 45.
3
3
1H NMR (CDCl3) : 7.85 (dd, 2H, J(31P–1H) 14.6 Hz, J(1H–1H)
9.0 Hz, o-ArH), 6.86 (dd, 2H, 4J(31P–1H) 3.3 Hz, 3J(1H–1H) 9.0 Hz,
3
3
m-ArH), 4.97 (dsept, 1H, J(31P–1H) 3.0 Hz, J(1H–1H) 6.0 Hz,
CH), 2.01 (s, 3H, ArOMe), 1.27 (d, 6H, J(1H–1H) 6.3 Hz. 13C
3
NMR (CDCl3) : 162.7 (d, 4J (31P–13C) 3.8 Hz, p-ArC), 133.1 (d, 1J
(31P–13C) 126.0 Hz, Ar C-1), 132.1 (d, 3J (31P–13C) 14.3 Hz, m-ArC),
114.0 (d, 2J (31P–13C) 16.6 Hz, o-ArC), 71.5 (d, 2J (31P–13C) 6.8 Hz,
CH), 55.8 (s, ArOCH3), 24.8 (d, 3J (31P–13C) 3.8 Hz, CH3). Selected
IR data (KBr) /cm−1: 1179 (s), 1029 (s), 656 (w), 542 (m). Mass
Spec (FAB): (1/2M)+ 731, (M − PS2O2C10H14)+ 1199.
10 (a) M. C. Aragoni, M. Arca, F. Demartin, F. A. Devillanova, C. Graiff,
F. Isaia, V. Lippolis, A. Tiripicchio and G. Verani, Eur. J. Inorg. Chem.,
2000, 2239; (b) M. Arca, F. Demartin, F. A. Devillanova, A. Garau,
F. Isaia, F. Lelj, V. Lippolis, A. Tiripicchio and G. Verani, J. Chem. Soc.,
Dalton Trans., 1998, 3731; (c) M. C. Aragoni, M. Arca, F. Demartin,
F. A. Devillanova, A. Garau, F. Isaia, F. Lelj, V. Lippolis, A. Tiripicchio
and G. Verani, J. Am. Chem. Soc., 1999, 121, 7098; (d) M. Arca,
A. Cornia, F. A. Devillanova, A. C. Fabretti, F. Isaia, V. Lippolis and
G. Verani, Inorg. Chim. Acta, 1997, 262, 81.
11 (a) M. P. Cava and M. I. Levinson, Tetrahedron, 1985, 41(22), 5061;
(b) R. A. Cherkasov, G. A. Kutyrev and A. N. Pudovik, Tetrahedron,
1981, 37, 1019; (c) T. Ozturk, Tett. Lett., 1996, 37(16), 2821; R. Jones,
D. J. Williams, P. T. Wood and J. D. Woollins, Polyhedron, 1987, 6, 539.
12 Y. Özcan, S. Ide, M. Karakus and H. Yilmaz, Acta Crystallogr., Sect. C:
Cryst. Struct. Commun., 2002, 58, 388.
X-ray crystallography. Tables 1–3 contain slected bond lengths
and angles. Tables 4 and 5 list details of data collections and refine-
ments. For, 4m, 8p, 9e and 11e, data were collected at 93 K using
Mo-K radiation [MM007 Rotating Anode source with confocal
optics] and a Rigaku Mercury system; for 4m, 7p, 8e, 9p and 11p at
125 K using a Bruker SMART [sealed tube] system. Intensities were
corrected for Lorentz-polarisation and for absorption. The structures
were solved by the heavy atom method or by direct methods. The
positions of the hydrogen atoms were idealised. Refinements were
by full-matrix least squares based on F2 using SHELXTL.27
CCDC reference numbers 237196–237204.
See http://www.rsc.org/suppdata/dt/b4/b406411a/ for crystallo-
graphic data in CIF or other electronic format.
13 I. P. Gray, H. L. Milton, A. M. Z. Slawin and J. D. Woollins, Dalton
Trans., 2003, 3450.
14 M. R. St.J. Foreman,A. M. Z. Slawin and J. D. Woollins, J. Chem. Soc.,
Dalton Trans., 1996, 3653.
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2 4 8 6
D a l t o n T r a n s . , 2 0 0 4 , 2 4 7 7 – 2 4 8 6