Metal thiophosphonates and related compounds: An emerging area of supramolecular coordination chemistry

Article abstract of DOI:10.1039/b603764j

Nine new compounds containing PS ligands of the types [P(O ^tBu)S₃]^2-, [ArP(S^tBu)S ₂]^- and [ArP(O^tBu)S₂]^- are reported (Ar = 4-anisyl). It is demonstrated that the topology of alkali metal ion and ligand composition influence the structure of supramolecular arrangements. The Royal Society of Chemistry 2006.

Full text of DOI:10.1039/b603764j

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PAPER
www.rsc.org/dalton | Dalton Transactions
Metal thiophosphonates and related compounds: an emerging area
of supramolecular coordination chemistry†
Weifeng Shi,a Maryam Shafaei-Fallah,a Christopher E. Ansona and Alexander Rothenberger*a,b
Received 14th March 2006, Accepted 13th April 2006
First published as an Advance Article on the web 24th April 2006
DOI: 10.1039/b603764j
Nine new compounds containing PS ligands of the types [P(OtBu)S3]2−, [ArP(StBu)S2]− and
[ArP(OtBu)S2]− are reported (Ar = 4-anisyl). It is demonstrated that the topology of alkali metal
ion and ligand composition influence the structure of supramolecular arrangements.
Introduction
The interest in novel materials brought coordination chemistry
of P/S-containing precursors into focus and it is widely known
that phosphorus- and sulfur- or selenium-containing compounds
such as R3PE, RP(E)(ESiMe3)2, [RP(E)(l-E)]2 (E = S, Se) (R =
organic group) are useful starting materials for metal chalcogenide
nanoparticles, molecular complexes with P-chalcogenide ligands
and chalcogen transfer reactions.1–7
Scheme 1 Stepwise synthesis of phosphonodithioate and diselenolate
metal salts (R = 4-anisyl, Ph, E = S, Se; Rꢀ = Me, Et, iPr, M = metal).
Coordination chemistry in this field concentrates on a variety
of ligands designed by formally replacing O atoms in phosphate
ions with OR, SR, S,. . . and combinations thereof and so far the
most compounds reported in this area contain dithiophosphonato
[(RO)2PS2]− ligands.8–12 Lawesson’s reagent (LR) [RP(S)(l-S)]2
(R = 4-anisyl) widely known as a powerful thionation reagent in
organic synthesis,13 and the Se analogous compound Woollins’
reagent [PhP(Se)(l-Se)]2 (W. R.)14,15 offer an alternative route
to complexes containing P/S- or P/Se-based anionic ligands
(Scheme 1). Initially sodium phosphonodithioate or-selenolate
alkali metal salts are formed in situ and subsequently reacted
with transition metal salts. The generated [RP(ORꢀ)E2]− ligands
are bidentate and chelate metal atoms via chalcogen atoms whilst
the introduced alkoxide group is not involved in coordination
(Scheme 1).6,7 As part of a wider study of the reactivity of late
transition metal alkoxides with P/S-precursors it was recently
shown that reactions of CuOtBu with LR in aprotic solvents
produce Cu(I) complexes containing the dianionic ligand [(RS2P–
Scheme 2 Preparation of [Cu2(l2-ArS2P–O–PS2Ar)(PPh3)4] (Ar = 4-ani-
syl, M = Cu).
structures and less common reactivities of metal complexes with
P-chalcogenide ligands which might offer a new route to ternary
P–chalcogen–metal-based materials.
Results and discussion
The section is subdivided into three parts summarizing recent
investigations on the reactivity of Cu(I) alkoxides and thiolates
with LR and P2S3, followed by the synthesis and first crystal
structures of molecular and supramolecular assemblies of alkali
metal phosphonodithioate salts. Finally under miscellaneous the
thermal properties of a phosphonodithioate salt and an unusual
polymeric potassium trithiophosphonate demonstrate potential
future developments.
t
O–PS2R]2− (R = 4-anisyl) and Bu2O in high yield (Scheme 2).16
Addition reactions of Cu salts with PS precursors
The surprising discovery prompted investigations of the broader
applicability of the synthetic route (Scheme 2) by slightly modify-
ing Woollins’ approach (scheme 1) and reacting metal alkoxides
or thiolates with P2S5, P2S3 and LR in ethereal solvents.
An initial result of these efforts represented the synthesis
of [Cu3{PS2(OPS2OtBu)2}(PPh3)4] which was obtained by the
reaction of CuOtBu with P2S5 and where ether elimination has
also been observed.17 Here we report recent progress from these
and related investigations focusing on so far unknown solid-state
When CuOtBu and P2S3 are dissolved in a mixture of THF
and toluene, crystals of [Cu4{l3-P(OtBu)S3}2(PPh3)4] (1, 1a) were
obtained after addition of the auxiliary ligand PPh3 (Fig. 1).
From amorphous precipitate crystals of 1 and 1a were seperated
manually and characterised. In the unit cell of 1 there are two
independent molecules lying about inversion centres, and in the
polymorph 1a there is one molecule in the unit cell, also lying about
an inversion centre (bond lengths in both compounds are similar).
1 consists of a centrosymmetric distorted hexagonal prismatic ar-
rangement of two [P(OtBu)S3]2− anions and four [Cu(PPh3)]+ units
(Fig. 1). Each of the S-donor atoms bridges two Cu atoms resulting
in tetrahedral coordination environments for Cu atoms with Cu–S
and Cu–P bond distances in commonly observed ranges. The
most striking feature of 1 is the formation of [tBuOPS3]2− ligands
which is mechanistically difficult to rationalize. The moderate yield
aInstitut fu¨r Anorganische Chemie der Universita¨t Karlsruhe, Geb. 30.45,
Engesserstr. 15a, 76131, Karlsruhe, Germany. E-mail: ar252@chemie.uni-
karlsruhe.de
bInstitut fu¨r Nanotechnologie, Forschungszentrum Karlsruhe GmbH, Post-
fach 3640, 76021, Karlsruhe, Germany
† This paper is dedicated to Professor Hansgeorg Schno¨ckel on the
occasion of his 65th birthday.
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Fig. 2 Molecular structure of 2 in the solid state. Selected bond
◦
˚
lengths (A) and angles ( ): Cu(1)–P(3) 2.2659(5), Cu(1)–P(2) 2.2698(5),
Cu(1)–S(1) 2.4538(5), Cu(1)–S(2) 2.4675(6), P(1)–S(1) 1.9903(7),
P(1)–S(2) 1.9978(7), P(1)–S(3) 2.1033(7); P(3)–Cu(1)–P(2) 122.69(2),
P–Cu–S 102.08(2)–120.83(2), S(1)–Cu(1)–S(2) 84.288(18), S(1)–P(1)–S(2)
111.79(3), S(1)–P(1)–S(3) 117.09(3), S(2)–P(1)–S(3) 100.89(3).
Fig. 1 Molecular structure of one of the two crystallographically
independent molecules of 1 in the solid state. Selected bond lengths (A)
˚
and angles (◦): Cu–P 2.2264(9)–2.2467(10), Cu–S 2.2739(9)–2.7390(12),
P(3)–O(1) 1.601(2), P(3)–S(1) 2.0302(12), P(3)–S(2) 2.0304(13), P(3)–S(3)
2.0416(11); P–Cu–S 99.75(4)–121.99(3), S–Cu–S 81.62(3)–125.52(3),
O(1)–P(3)–S(2) 113.32(10), S(1)–P(3)–S(2) 109.47(5), O(1)–P(3)–S(3)
97.72(10), S(1)–P(3)–S(3) 117.19(5), S(2)–P(3)–S(3) 108.73(5).
Synthesis and structures of alkali metal phosphonodithioate salts
A different approach overcoming the solubility problems of
coinage metal complexes related to 2 was the use of alkali
metal alkoxides or thiolates in reactions with LR. For alkoxides,
alkali metal phosphonodithioate salts are generated, which are
commonly prepared in situ and used in subsequent metathesis
reactions.6 Up until now, however, no structural evidence for alkali
metal phosphonodithioate salts exists. In that sense the synthesis
and characterisation of 3–6 form the basis of a potentially emerg-
ing supramolecular chemistry of alkali metal phosphonodithioate
salts (Scheme 4).
in which 1 is formed indicates the complexity of the reaction.
Attempts to gain a mechanistic insight by NMR experiments
in a variety of solvents failed and at this stage it is clear that
further attempts are required in order to gain synthetic access to
compounds related to 1 on larger scale. So far reactions of CuOtBu
with P2S3 and P2S5 are of limited practical value despite the fact
that the novel compounds [Cu3{PS2(OPS2OtBu)2}(PPh3)4] and 1
were obtained.17
For this reason it seemed more fruitful to concentrate on
P/S precursors containing solubilizing organic functional groups.
For the first time reactions of Cu(I) thiolates and LR were
investigated and it turned out that they just work as well as the
reactions between alkoxides and LR. This is here demonstrated
by the first structurally characterised example of a metal complex
containing ligands of the type [RP(SRꢀ)S2]− (R, Rꢀ = organic
group). These were previously described by Nizamov et al. but
no crystal structures are reported.18 [Cu(ArP(StBu)S2)(PPh3)2] (2)
was obtained in moderate yield (Scheme 3).
Scheme 4 Synthesis of 3–6 (Ar = 4-anisyl, M = Na, K; DME =
1,2-dimethoxyethane) and indicated coordination mode of the generated
anion in 5 and 6; O atoms of methoxy groups are not involved in bonding
to Na atoms in 3 and 4.
The generated dithiophosphonato anion in these reactions
contains four donor centres which could all be involved in
metal bonding (Scheme 4). In previously reported examples of
metal complexes with similar PS anions, S atoms are commonly
chelating metal ions, whereas coordination of OtBu or methoxy
groups to metal atoms has not been detected. A reason for
these previous observations might be the rotation of the alkoxy-
substituents in solution, their involvement in hydrogen bonding
to solvent molecules or a preference of the metal ion for softer
Scheme 3 Preparation of [Cu(ArP(StBu)S2)(PPh3)2] (2).
In the solid state 2 exhibits a simple arrangement of one
[ArP(StBu)S2]− ligand chelating Cu(1) via S atoms (Fig. 2). Tetra-
hedrally surrounded Cu(1) is in addition coordinated by two
P atoms of PPh3 groups. In this case the formation of larger
aggregates is hinderedbythe steric requirements ofPPh3. Attempts
to modify organic groups of phosphines and thiols are ongoing.
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donor atoms.19 Reported examples of polymeric or oligomeric
complexes are held together by additional donor molecules or
secondary bonding interactions.6,20,21 In the solid state 3 exists as a
polymer of [ArP(OtBu)S2]− ions held together by Na atoms (Fig. 3,
top). The anion and [Na(thf)]+ cation are topologically different
(e.g., [ArP(donor-centre)3]− and [(thf)Na(empty coordination-
site)4]+). In the extended solid-state structure they are arranged
in alternating cis/trans orientation of neighbouring aromatic and
thf rings along the polymer. In contrast to the Cu complexes 1
and 2 a change in the topology of the metal atom Na atom is
easily achieved. 4 was obtained from a hexane–DME solution
(Scheme 4) and the structural consequence of the increase of Na
coordination numbers from five in 3 to six in 4 is displayed in Fig. 3.
In the solid state 4 consists of a centrosymmetric arrangement of
two [{ArP(OtBu)S2}Na(dme)] units with bond lengths similar to
those listed for 3 (Fig. 3).
The observation of deaggregation by change of solvents seems
trivial at first sight. It is assumed, however, that the use of
topologically different ions represents a potentially useful con-
cept for the design of alkali metal containing polymers. As a
consequence alkali metal ions of different size should result in
a variety of alkali metal dithiophosphonate arrangements in the
solid state. In the case of the Li+ ion only oily residues were
obtained despite various attempts in a range of solvents. Larger
K+ ions, however, turned out to have a significant influence on the
design of polymeric alkali metal phosphonodithioates. Akin to 4
(Fig. 3, bottom) the coordination number of the alkali metal ion
in 5 (Fig. 4) is six hence a similar centrosymmetric arrangement
now of two [{ArP(OtBu)S2}K(thf)] units is formed. The main
difference between 4 and 5, however are increased bond distances
of potassium ions to neighboring atoms in comparison to sodium
ions in 3 and 4. As a consequence a higher ordered structure held
together by more and weaker electrostatic interactions is found
in 5 and the DME solvate 6 (Fig. 4, 5). A striking feature of
5 and 6 is the fact that coordination of [ArP(OtBu)S2]− ions to
the alkali metal involves all donor centres (Scheme 4) resulting
in [K2{ArP(OtBu)(l-S)S}2(thf)2] constitutional units linked into a
polymetallacyclophane by coordination of O atoms of 4-anisyl
substituents to potassium ions. The use of DME during the
synthesis of 6 imposed no major structural changes and bond
lengths are similar to those reported for 5.
Fig. 4 Solid-state structure of a building block in polymeric 5. Final label
letter A denotes the symmetry operation 1 − x, 1 − y, 1 − z. Selected bond
◦
˚
lengths (A) and angles ( ): K(1)–O(3) 2.635(2), K(1)–O(1a) 2.8715(15),
O(2)–K 2.7934(16), K(1)–S(1) 3.2164(8), K(1)–S(2A) 3.1632(13), K(1)–
S(2) 3.2015(8), P(1)–O(1) 1.6226(17), P(1)–C(1) 1.816(2), P(1)–S(1)
1.9742(8), P(1)–S(2) 1.9830(10); O(1)–P(1)–S(1) 113.00(7), O(1)–P(1)–S(2)
103.07(7), S(1)–P(1)–S(2) 117.64(3), S–K–S 63.67(2)–106.24(3), O–K–O
69.03–108.86(4), O(3)–K(1)–S(2A) 160.81(5), O–K–S 55.72(4)–155.23(4).
Fig. 3 Top: Solid-state structure of a building block in polymeric 3.
Connections to adjacent units are indicated by dashed open bonds. Final
label letter A denotes the symmetry operation 1/2 − x, y − 1/2, 1/2 − z.
◦
˚
Selected bond lengths (A) and angles ( ): Na(1)–O(3) 2.345(5), Na(1)–
O(1A) 2.445(3), Na–S 2.772(2)–2.874(2), P(1)–O(1) 1.609(3), P(1)–C(1)
1.799(4), P(1)–S(2) 1.9688(16), P(1)–S(1) 1.9973(14); O(3)–Na(1)–O(1A)
102.59(13), O–Na–S 65.12(9)–151.04(12), S(1A)–Na(1)–S(1) 139.26(9),
S(1A)–Na(1)–S(2) 97.31(7), S(1)–Na(1)–S(2) 72.85(5), O(1)–P(1)–S(2)
113.98(13), O(1)–P(1)–S(1) 102.39(11), S(2)–P(1)–S(1) 116.01(7). Bottom:
Molecular structure of 4 in the solid state. Only one orientation of
two-fold-disordered DME molecules (50% occupancy each) is displayed.
The synthetic and first structural models from alkali metal
phosphonodithioates showed that supramolecular coordination
chemistry of these ions and the crystal packing can be influenced
if topologically different cations and anions are used. In contrast
to tetrahedrally coordinated Cu(I) the use of multivalent alkali
metal cations in a variety of ethereal solvents offers potential for
investigations with related anions.
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ingredients necessary for unusual supramolecular architectures,
e.g., a heavier alkali metal and weak electrostatic interactions to
S-donor centres in [ArP(StBu)S2]− anions (Scheme 6, Fig. 7).
Scheme 6 Synthesis of 8.
Fig. 5 Structure of a section of polymeric 6.
Miscellaneous
Little is known about thermal properties of metal phospho-
nodithioates. In a pilot study following up the previously described
ether elimination during the preparation of [Cu2(l2-ArS2P–O–
PS2Ar)(PPh3)4] (Scheme 2) a metathesis reaction of 5 with CdCl2
was used to study the thermolysis of [Cd2{ArP(OtBu)(l-S)S}4] (7)
(Scheme 5, Fig. 6).17
Scheme 5 Synthesis of 7.
Fig. 7 Solid-state structure of a tetrameric building block of 8 (left) and
arrangement of units in the polymer (right; only a-C atoms of StBu groups
˚
and O atoms of THF are displayed). Selected bond lengths (A) and angles
(◦): P(1)–C(1) 1.814(5), P(1)–S(1) 1.982(2), P(1)–S(2) 1.985(2), P(1)–S(3)
2.123(2), K(1)–O 2.758(6), 2.896(4), K(1)–S(1) 3.238(2), other short K(1)–
S 3.333(2), 3.370(2), 3.437(2), K(1)–S(2) 3.679(2), K(1)–S(3) 3.785(2),
S(3)–C(8) 1.877(8); C(1)–P(1)–S(1) 109.13(19), C(1)–P(1)–S(2) 111.4(2),
S(1)–P(1)–S(2) 115.07(9), C(1)–P(1)–S(3) 105.7(2), S(1)–P(1)–S(3)
115.60(10), S(2)–P(1)–S(3) 99.26(9).
Fig. 6 Molecu◦lar structure of 7 in the solid-state. Selected bond lengths
In the solid state 8 consists of a tetrameric arrangement of
[ArP(StBu)S2K] units in which K(1), S(1) and symmetry equivalent
atoms form a distorted cubic arrangement (Fig. 7, left) with
imposed 4 symmetry held together by coordination of O atoms
of methoxy groups to K atoms.
˚
(A) and angles ( ): Cd–S 2.5160(7)–2.9877(7), P(1)–O(1) 1.5804(19), P(2)–
O(3) 1.5860(19), P–S 1.9973(9)–2.0424(8); S(4)–Cd(1)–S(1) 134.00(2),
S(4)–Cd(1)–S(3) 79.16(2), S(1)–Cd(1)–S(3) 106.97(2), S(2)–P(1)–S(1)
111.75(4), S(3)–P(2)–S(4) 111.38(4).
¯
Potassium atoms in 8 are seven-coordinated by S and O atoms
with rather large distances to O and S atoms (Fig. 7). The
[ArP(StBu)S2K]4 building block in 8 represents a repeating unit
with electron donor/acceptor properties to be explored in future
investigations.
In the solid state 7 exists as a centrosymmetric dimer, a structural
motif commonly found in similar Cd complexes.6,22 A differential
thermal analysis of 7 showed that from 126 ◦C on a weight loss of
18.2% occurs which is in fairly good agreement for the expected
weight loss of 19.6% for 7 − 2tBu2O. Similar observations were
made for 3–6 but investigations of their thermal behaviour and the
characterisation of thermolysis products are ongoing.
Another aspect of current interest is to develop coordination
polymers of trithiophosphonates containing [ArP(StBu)S2]− or
related anions. The application of synthetic concepts developed
from the first structurally characterised alkali metal phospho-
nodithioates 3–6 prompted the investigations of solid-state struc-
tures of alkali metal trithiophosphonates. It was hoped to achieve
the preparation of this new class of compounds with all the
Conclusions
The results reported in this paper show that phosphorus- and
sulfur-containing reagents can be easily transformed by direct
reactions with metal alkoxides and thiolates. In the case of 1 an
unusual break-up of P2S3 is reported and 2 represents the first
crystallographically characterised complex containing ligands of
the type [RP(SR)S2]−. The Cu-complexes are either difficult to
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obtain in high yield or result in simple arrangements due to the
topological similarity of tetrahedral P environments of PS anions
and Cu+ cations. Subsequently, reactions of alkali metal alkoxides
with LR were investigated and it was found that the topology of
alkali metal cations, which can more easily be influenced than that
of Cu+ gives rise to supramolecular arrangements found in 3, 5 and
6. By the metathesis reaction of 5 (prepared in situ) with CdCl2
7 was prepared, which can be thermally decomposed possibly
(decomp.). Found: C, 48.40; H, 6.31. C15H24NaO3PS2 requires C,
48.63; H, 6.53%; mmax/cm−1 (KBr) 2973s, 2873s (OCH3), 1592s,
=
1496s (P–C), 1237s, 1102s, 683s br (P S); dH (400 MHz; CDCl3;
25 ◦C) 1.53 (9H, s, OC(CH3)3), 1.80 (4H, m, 2 × OCH2CH2), 3.63
(4H, m, 2 × OCH2CH2), 3.78 (3H, s, OCH3), 6.78 (2H, m, ArH),
8.08 (2H, m, ArH); dP (162 MHz; CDCl3; 25 ◦C; 65% H3PO4)
96.7.
4: A mixture of Lawesson’s reagent 606 mg (1.5 mmol) and
NaOtBu 288 mg (3.0 mmol) was dissolved in 10 mL DME. The
light yellow (almost colorless) solution was stirred overnight
at room temperature and then the solution was layered with
80 mL hexane. Storage of the solution at room temperature for
2 weeks produced colorless crystals of 4; 0.4 g, yield 34%, mp
127 ◦C. Found: C, 46.20; H, 6.69. C30H52Na2O8P2S4 requires C,
46.38; H, 6.75%; mmax/cm−1 (KBr) 2924s br, 2822s (OCH3), 1590s,
t
releasing Bu2O. Further work on the differential thermolysis of
complexes with crystallographic characterisation of products is
planned. Finally it was demonstrated by the characterisation of 8
that further exciting results in the emerging area of supramolecular
coordination chemistry with P-chalcogenide ligands and alkali
metals are to be expected when parameters, e.g., topology of alkali
metal ion and ligand composition are modified.
=
1492s (P–C), 1231s, 1090s, 683s br (P S).
5: A mixture of Lawesson’s reagent 606 mg (1.5 mmol) and
KOtBu 336 mg (3.0 mmol) was dissolved in 10 mL THF. The
light yellow (almost colorless) solution was stirred overnight at
room temperature and then the solution was layered with 50 mL
hexane. Storage of the solution at room temperature for 4 days
Experimental
All operations were carried out in an atmosphere of purified
dinitrogen. All solvents were dried over the appropriate drying
agent and freshly distilled prior to use. CuOtBu and CuStBu were
prepared according to published procedures.23,24 Other starting
materials were purchased from Aldrich and used without further
purification. Crystals were dried under reduced pressure prior to
analysis.
1: A mixture of CuOtBu 137 mg (1.0 mmol), P2S3 79 mg
(0.5 mmol) and PPh3 524 mg (2.0 mmol) was dissolved in 15 mL
toluene. The mixture was stirred for 7 h. Solvent concentration
within a double-Schlenk tube produced very light yellow (almost
colorless) crystals of 1a after 4 days together with a colourless
◦
produced colorless crystals of 5; 0.84 g, yield 72%, mp ∼120 C
(decomp.). Found: C, 46.35; H, 6.02. C15H24KO3PS2 requires C,
46.61; H, 6.26%; mmax/cm−1 (KBr) 2970s, 2840s (OCH3), 1591s,
=
1493s (P–C), 1230s, 1096s, 678s br (P S); dH (400 MHz; CDCl3;
25 ◦C) 1.49 (9H, s, OC(CH3)3), 1.79 (4H, m, 2 × OCH2CH2), 3.64
(4H, m, 2 × OCH2CH2), 3.77 (3H, s, OCH3), 6.76 (2H, m, ArH),
8.13 (2H, m, ArH); dP (162 MHz; CDCl3; 25 ◦C; 65% H3PO4)
96.6.
6: A mixture of Lawesson’s reagent 606 mg (1.5 mmol) and
KOtBu 336 mg (3.0 mmol) was dissolved in 10 mL DME. The
light yellow (almost colorless) solution was stirred overnight at
room temperature and then the solution was layered with 60 mL
hexane. Storage of the solution at room temperature for 5 days
◦
amorphous precipitate. 0.08 g, yield 19%, mp 175 C (decomp.,
brown solid). Found: C, 55.52; H, 4.52. C80H78Cu4O2P6S6 requires
C, 56.39; H, 4.61% (despite repeated attempts a more accurate
analysis could not be obtained, indicating that solid samples of 1a
are contaminated by amorphous byproducts); mmax/cm−1 (KBr)
3049m, 2971m, 1434s (P–C), 1241s, 1092s, 692s (P S). 1 was
synthesized by using 15 mL THF instead of 15 mL toluene; 0.2 g,
yield 47%
◦
produced colorless crystals of 6; 0.93 g, yield 77%, mp ∼115 C
=
(decomp.). Found: C, 44.14; H, 6.22. C15H26KO4PS2 requires C,
44.53; H, 6.48%; mmax/cm−1 (KBr) 2970s, 2840m (OCH3), 1592s,
=
1496s (P–C), 1235s, 1101s, 677s (P S).
2: A mixture of Lawesson’s reagent 202 mg (0.5 mmol) and
CuStBu 306 mg (2.0 mmol) was dissolved in 8 mL THF. The
yellow solution was stirred for about 3 h at room temperature.
The solvent was removed under reduced pressure, and the residue
was redissolved by addition of a solution of PPh3 (0.57 M in
THF, 4 mL). The solution was layered with 50 mL hexane and
stored at room temperature for 3 weeks produced colorless crystals
of 2; 0.25 g, yield 29%, mp 185–187 ◦C. Found: C, 64.00; H,
5.11. C47H46CuOP3S3 requires C, 64.18; H, 5.27%; mmax/cm−1 (KBr)
3053m, 2957m, 2835w (CH3O), 1592s, 1495s (P–C), 1249s, 692s
7: To a mixture of KOtBu 224 mg (2.0 mmol) and CdCl2
184 mg (1.0 mmol) was added 10 mL DME. After the yellow
cloudy solution was heated at 50 ◦C for 3 h Lawesson’s reagent
202 mg (0.50 mmol) was added. The precipitate was filtered off
and the colorless solution layered with 25 mL hexane. Storage
of mixture at room temperature for 2 weeks produced colorless
crystals of 7. 0.21 g, yield 63%, mp 126 ◦C (decomp., mass
change (differential thermal analysis) found −18.2%; mass change
expected for C44H64Cd2O8P4S8 − 2tBu2O: −19.6%); Found: C,
40.57; H, 4.57. C44H64Cd2O8P4S8 requires C, 39.85; H, 4.86%;
mmax/cm−1 (KBr) 2976s, 2834m (OCH3), 1591s, 1497s (P–C), 1249s,
(P S). dH (400 MHz; CDCl3; 25 ◦C) 1.28 (9H, s, OC(CH3)3),
=
=
3.90 (3H, s, OCH3), 6.86 (2H, m, ArH), 7.30 (30H, m, PPh3),
8.08 (2H, m, ArH); dC (100 MHz; CDCl3; 25 ◦C) 32.0, 52.4, 55.3,
128.2, 128.3, 129.2, 132.4, 132.6, 133.8, 133.9, 134.1; dP (162 MHz;
CDCl3; 25 ◦C; 65% H3PO4) 74.9, −4.8 (br, s, PPh3).
1106s, 672s (P S).
8: A mixture of Lawesson’s reagent 202 mg (0.5 mmol) and
KStBu 128 mg (1.0 mmol) was dissolved in 8 mL THF. The
colorless solution was stirred overnight at room temperature and
then the solution was layered with 70 mL hexane. Storage of
the solution at room temperature for 2 weeks produced colorless
crystals of 8; 0.32 g, yield 80%, mp 115 ◦C (decomp.). Found:
C, 44.33; H, 5.78. C60H96K4O8P4S12 requires C, 44.75; H, 6.01%;
mmax/cm−1 (KBr) 2955s, 2836m (OCH3), 1590s, 1494s (P–C), 1238s,
3: A mixture of Lawesson’s reagent 606 mg (1.5 mmol) and
NaOtBu 288 mg (3.0 mmol) was dissolved in 10 mL THF. The
light yellow (almost colorless) solution was stirred overnight at
room temperature and then the solution was layered with 50 mL
hexane. Storage of the solution at room temperature for 5 days
◦
=
produced colorless crystals of 3; 0.79 g, yield 71%, mp ∼120 C
1095s, 664s br (P S).
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The Royal Society of Chemistry 2006
Dalton Trans., 2006, 3257–3262 | 3261
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Crystallography
Data were measured on a STOE IPDS II and a STOE STADI
IV (Kuma CCD detector) diffractometer, using Mo-Ka radi-
ation. The structures were solved by direct methods, and re-
fined by full-matrix least-squares against F2 using all data (see
Table 1 for details).25 Hydrogen atoms were placed in idealized
positions.
CCDC reference numbers 292989, 292991–292993 and 601692–
601700.
For crystallographic data in CIF or other electronic format see
DOI: 10.1039/b603764j
Acknowledgements
We thank the DFG Center for Functional Nanostructures (W. S.)
and the Forschungszentrum Karlsruhe (A. R.) for financial
support. A. R. thanks Prof. D. Fenske for his support.
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