Synthesis and characterization of bimetallic single-source precursors (Ph3P)2M(μ-SEt)2e(SEt)2 for MES2 chalcopyrite materials (M = Cu, Ag and E = In, Ga, Al)

Article abstract of DOI:10.1002/ejic.201700115

We report the synthesis and characterization of I-III bimetallic complexes (Ph₃P)₂M(μ-SEt)₂E(SEt)₂ (M = Cu, Ag and E = In, Ga, Al), as well as (Ph₃P)₂M(μ-Cl)₂ECl₂ comp

Full text of DOI:10.1002/ejic.201700115

A Journal of
Accepted Article
Title: Synthesis and Characterization of Bimetallic Single Source
Precursors (Ph3P)2M(µ-SEt)2E(SEt)2 for MES2 Chalcopyrite
Materials (M = Cu, Ag and E = In, Ga, Al)
Authors: Kelsey R. Margulieux, Chivin Sun, Matthew T. Kihara, Adam
C. Colson, Lev N. Zakharov, Kenton H. Whitmire, Andrew W.
Holland, and Joshua Pak
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To be cited as: Eur. J. Inorg. Chem. 10.1002/ejic.201700115
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10.1002/ejic.201700115
European Journal of Inorganic Chemistry
FULL PAPER
Synthesis and Characterization of Bimetallic Single Source
Precursors (Ph3P)2M(µ-SEt)2E(SEt)2 for MES2 Chalcopyrite
Materials (M = Cu, Ag and E = In, Ga, Al)
Kelsey R. Margulieux,[a] Chivin Sun,[a] Matthew T. Kihara,[a] Adam C. Colson,[b] Lev N. Zakharov,[c]
Kenton H. Whitmire,*[d] Andrew W. Holland*[a] and Joshua J. Pak*[a]
complexes employing similar synthetic strategies, and we have
reported on an alternative preparation of the original complex.7
Traditionally, these species have been studied for the purpose of
preparing CuIn(S,Se)2 thin films, nanorods or nanoparticles for
photovoltaic and other optoelectric applications. In addition to
Cu-In containing SSPs, there have been sporadic reports on
preparation and use of SSPs containing Ag-In8 and Cu-Ga.9 To
the best of our knowledge this series remains incomplete, and
no systematic series of I-III bimetallic complexes has been
pursued. Such a series would not only offer fundamental
comparisons of various organometallic species in terms of their
structures and reactivities, but also provide new tools for
preparing and studying more complex I-III chalcogenide
materials, such as quaternary CuInxGa1-xS2 nanoparticles.10
Herein, we report the preparation and characterization
of a series of I-III bimetallic SSPs of the form (Ph3P)2M(µ-
SEt)2E(SEt)2 for nanomaterials of MES2 (M = Cu, Ag and E = In,
Ga, Al). Minor variations to a common synthetic strategy
afforded all these SSPs, which include several new complexes
and the first reported Ag-Al SSP. These SSPs provide new
opportunities to explore the relationships of structure and
reactivity to the identities of the metals present without the
complications introduced through differing phosphine or thiolate
ligands.
Abstract: We report the synthesis and characterization of I-III
bimetallic complexes (Ph3P)2M(µ-SEt)2E(SEt)2 (M=Cu, Ag and E = In,
Ga, Al), as well as (Ph3P)2M(µ-Cl)2ECl2 complexes isolated during
their syntheses. The thiolate complexes can be used as single source
precursors (SSPs) to prepare various I-III chalcogenide
semiconductor materials. Some SSPs of the series required minor
variation in reaction conditions to be prepared. The organometallic
complexes were structurally characterized by X-ray diffraction. The
SSPs are compared in terms of their solid-state structures, basic
reactivity and potential suitability as precursors for chalcopyrite
materials.
Introduction
The use of molecular single source precursors (SSPs)
has been established as a powerful strategy to prepare
materials including binary and ternary metal chalcogenides and
oxides.1 Via solvothermal reactions to make particles2 and
chemical vapor deposition to prepare thin films, among other
techniques,3 a well-designed molecular single source precursor
can afford outstanding control of stoichiometry, phase, shape,
and size, and thus enable fine-tuning of the physical properties
of a target material.
Several I-III chalcogenide semiconductors have drawn
recent interest for their unique optical and catalytic properties,
particularly given theirpotential applications in photovoltaics,
bioimaging, and electronic devices.4 Although the multisource
precursor strategies most often employed in the syntheses of
these materials can be direct and economical, they offer limited
flexibility to modify reaction conditions without jeopardizing the
success of the synthesis. The use of I-III bimetallic
Results and Discussion
1. Syntheses
The syntheses of (Ph3P)2M(µ-SEt)2E(SEt)2 compounds
(1-6) are achieved through variations on a procedure already
reported for Cu-In analog 1, which involves initial formation of a
chloride substituted bimetallic phosphine complex, followed by
ligand substitution with thiolate groups (Scheme 1).7e The
addition of ECl3 to (Ph3P)2MCl in C6H6, followed by heating for 1
hour at 60-80 °C, provides benzene-soluble chloro-bridged
intermediates. These complexes are treated with 4 equivalents
of NaSEt and stirred at 60-80 °C, and subsequent filtration to
remove NaCl and evaporation of volatiles produces the desired
SSPs in high yields (eq 1). The primary differences among the
conditions required for the syntheses of 1-6 are in the times and
temperatures required (vida infra).
chalcogenide SSPs to prepare I-III chalcogenide thin films and
nanoparticles thus offers the potential for more precise and
detailed variations on these materials.5 Since the initial report of
(Ph3P)2Cu(µ-SEt)2In(SEt)2 (1), by Hirpo et al.,6 several groups
have reported syntheses of Cu-In and Ag-In bimetallic
[a]
Department of Chemistry, Idaho State University, Pocatello, Idaho
83209, USA
E-mail: hollandr@isu.edu
Et
1. ECl3
2. 4 NaSEt
Ph3P
Ph3P
Cl
Cl
Cl
Cl
Ph3P
Ph3P
S
SEt
SEt
(Ph3P)2MCl
M
E
M
E
www2.isu.edu/chem/people/faculty/hollandr
E-mail: pakjosh@isu.edu
S
60-80 oC, C6H6
60-80 oC, C6H6
Et
www2.isu.edu/chem/people/faculty/pakjosh
Department of Chemistry and Biochemistry, Boise State University,
Boise, Idaho, 83725, USA
M = Cu, Ag
E = In, Ga, Al
ME = CuIn 1, CuGa 2, CuAl 3
AgIn 4, AgGa 5, AgAl 6
[b]
E-mail: adamcolson@boisestate.edu
CAMCOR Microanalytical Facility, 1253 University of Oregon,
Eugene, Oregon 97403, USA
Department of Chemistry, Rice University, Houston, Texas 77251,
USA
Scheme 1. Preparation of bimetallic complexes 1-6.
[c]
[d]
Previous exploration of the Cu-In system revealed that
(Ph3P)2Cu(µ-SEt)2In(SEt)2 (1) is formed through a series of
intermediates including a bimetallic chloride complex isolated as
E-mail: whitmire@rice.edu
wrg.rice.edu/Whitmire_Research_Group/Home.html
Supporting information for this article is available on the WWW
under http:…
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10.1002/ejic.201700115
European Journal of Inorganic Chemistry
FULL PAPER
the dimeric 8-membered ring {(Ph3P)2Cu(µ-Cl)2InCl2}2 (7). This
species ultimately cleaves to the 4-membered ring structure
upon introduction of thiolate ligands, which sequentially replace
first at the bridging positions and then at the terminal positions.
This sequence of substitution has been determined by X-ray
characterization of the partially substituted species. The
progress of the substitution is also readily assessed by 1H NMR
spectroscopy, as both integration ratios and chemical shifts
respond to increasing thiolate substitution. Although exchange
on the NMR timescale renders all thiolate groups as a single set
of ethyl resonances at room temperature, the methylene signal
shifts steadily from δ 2.62 ppm in the monothiolate to δ 2.96
ppm in final tetrathiolate SSP 1. Heating the reaction mixture to
80 °C for 12 hours achieved full conversion to 1, and as
previously reported this method has been successfully employed
to prepare 400 g of the complex in a yield of 94%.7e The
amenability of this one-pot approach to efficient, monitored
scale-up is its primary advantage over the original synthesis.
This method has now been adapted for related SSPs,
equilibrium toward products by removing the volatile PMe3 under
vacuum. This approach allowed for isolation of 4 in 78% yield
following recrystallization, and its 1H NMR spectrum is provided
in Figure 1).
1. InCl3
Et
3. 2 PPh3
2. 4 NaSEt
Ph3P
Ph3P
S
SEt
SEt
(Me3P)2MCl
(Me3P)2AgIn(SEt)4
Ag
In
S
60 oC, C6H6
60 oC, C6H6
Et
4
Scheme 2. Preparation of bimetallic complex 4 using PMe3-containing
synthon.
beginning with the analogous Cu-Ga system (Ph3P)2Cu(µ-
SEt)2Ga(SEt)2 (2). Low initial yields of complex 2 were attributed
to the sensitivity of GaCl3 toward moisture, and subsequent
application of more rigorous inert atmosphere techniques
yielded 2 in 88% yield after 12 hours of heating at 80 °C. Best
results are achieved with freshly sublimed GaCl3. Aluminum
analogue (Ph3P)2Cu(µ-SEt)2Al(SEt)2 (3) was prepared by similar
means, and like 2 required significant precautions against
moisture throughout. In this case a somewhat longer reaction
time of 3 days at 80 °C was required to achieve full substitution
of the chlorides with thiolate groups, which again was
Figure 1. 1H NMR Spectrum of complex 4 in CD2Cl2.
Fortunately, the retardation of the substitution step at
60 °C was less severe for target complexes other than 4, and
both (Ph3P)2Ag(µ-SEt)2Ga(SEt)2 (5) and (Ph3P)2Ag(µ-
SEt)2Al(SEt)2 (6) were prepared in reasonable times and good
yields without resorting to PMe3-containing synthons.
Preparation of complex 5 was achieved in 72% yield after 5
days. Unlike the simple spectra of gallium and indium syntheses,
reaction mixtures produced NMR spectra including intermediate
species during the formation of Ag-Al complex 6, which required
heating at 3 days at 60 °C to achieve 67% yield. All silver
containing complexes 4-6 were prepared most effectively with
protection from ambient light, and remained moderately
sensitive following crystallization. To the best of our knowledge,
complex 6 is the first reported SSP combining Ag and Al with
thiolate ligands.
accompanied by a shift in the methylene 1H NMR signal from δ
2.64 to 2.96 ppm (in C6D6) during the progress of the
substitution. Application of higher reaction temperatures
produced intractable mixtures including colored solid impurities
consistent with the formation of CuAlS2. The typical yield for the
preparation of this complex at 80 °C was 82%.
The preparation of SSPs containing silver, complexes
4-6, posed greater challenges. In the attempted synthesis of
(Ph3P)2Ag(µ-SEt)2In(SEt)2 (4) by the same method used for
copper analogue 1, combination of AgCl, PPh3, and InCl3
yielded the desired bimetallic chloride complex, but black
precipitates and significantly lower yields were observed upon
heating this complex with NaSEt at 80 °C. These precipitates
likely resulted from undesired Ag-S redox interactions, and
although these were not prevented simply by exclusion of
ambient light, they were avoided by dark reactions at the lower
temperature of 60 °C. Unfortunately, at this temperature reaction
times in excess of three weeks were required for complete
thiolate substitution to form the desired complex 4.
Close analogues of precursor 4 have previously been prepared
efficiently by other means, but to explore the limits of this
synthetic sequence another variation of the method was
explored.7g More rapid preparation of 4 was accomplished by the
in situ formation of the sterically less hindered (PMe3)Ag(µ-
SEt)2In(SEt)2 analogue (13) followed by phosphine exchange
(Scheme 2). The initial hypothesis underlying this approach was
that the incorporation of the smaller PMe3 ligand might allow
more facile substitution of the thiolate groups, and the thiolate
complex was indeed produced in less than 2 days of heating at
60 °C. Unexpectedly, the PMe3 complex 13 included only one of
the more basic phosphine ligands, perhaps indicating a structure
related to those of known oligomeric silver thiolate complexes,11
and this larger structural change may also contribute to the
acceleration of this metathesis. The PMe3 complex 13 was
easily converted to complex 4 by introducing 2 equivalents of
PPh3 to the reaction mixture and driving the exchange
All the syntheses of complexes 1-6 are believed to
proceed through intermediate chloride complexes 7-12 of the
general form (Ph3P)2M(µ-Cl)2ECl2, and the synthesis and
isolation of the chloride intermediate in the Cu-In system, a
dimer of the form {(Ph3P)2M(µ-Cl)2ECl2}2, 7, has been previously
reported.7e Application of the same synthetic approach used to
isolate 7, addition of ECl3 to (PPh3)2MCl complex followed by
heating at 60 °C for 1-3 hours, affords Cu-Ga (8), Cu-Al (9), Ag-
In (10), Ag-Ga (11) and Ag-Al (12) analogues (eq 1). These
species proved kinetically competent as intermediates in the
overall syntheses, but their isolation was not required for the
efficient preparation of 2-6. The Cu-Ga complex 8 adopts a
dimeric structure featuring an 8-membered ring analogous to
that of 7, while silver complexes (PPh3)2Ag(µ-Cl)2ECl2 (10-12)
were all isolated as monomeric species. Efforts to isolate a
corresponding Cu-Al complex resulted in crystallization of the
disproportionation product [(Ph3P)3Cu][AlCl4], 9, Figure 5.
1. ECl3
(Ph3P)2MCl
M = Cu, Ag
{(Ph3P)2Cu(µ-Cl)2ECl2}2 or (Ph3P)2Ag(µ-Cl)2ECl2
(1)
60-80 oC, C6H6
E = In (7), Ga (8)
E = In (10), Ga (11), Al (12)
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10.1002/ejic.201700115
European Journal of Inorganic Chemistry
FULL PAPER
Among all six SSPs, complex 1 appears to be the least
sensitive to moisture, whereas complexes 2-6 slowly hydrolyze
in ambient atmosphere. The chlorine-containing synthetic
intermediates 7-12 were uniformly more sensitive to atmospheric
exposure than the thiolate-bearing complexes. For this reason,
care should be used in the NaSEt source employed in synthesis;
significantly superior results were achieved when NaSEt was
freshly prepared before use and stored in an anhydrous
environment.
2. X-ray Crystal Structures
The crystal structure of (Ph3P)2Cu(µ-SEt)2In(SEt)2 (1)
was reported by Hirpo et al.,6 and herein we report X-ray crystal
structures of 2-6 (Figures 2 and 3). These include a structure of
the Ag-In complex 4 closely related to that of the
methanethiolate analog previously reported by Hepp and
coworkers.7g. As complexes in this series vary only in identities
of M and E, they offer the opportunity to observe trends in bond
lengths (Table 1) and angles (Table 2) that result strictly from
differences in the metal and metalloid, rather than variations
introduced through steric or electronic properties of the ligands.
Like complex 1, the Al analog 3 exhibits a nearly
planar MS2E core, and an anti disposition of bridging thiolate
substituents about this ring. The central ring of the Cu-Ga
complex 2 is puckered by about 10°, and those of the silver
analogues 4-6 all feature an angle of 22-23° between the two
Ag–S–E planes. In all four of these butterfly structures the ethyl
groups of the bridging thiolate ligands adopt a syn geometry to
point away from the center of the molecule. Surprisingly, the
previously reported solvent-free structure of 4 exhibits similar
bond lengths but an anti orientation of bridging thiolate
substituents, suggesting that this structural detail is most likely
attributable to crystal packing optimization. Each of the four
structures features additional bond length differences
attributable to such considerations: M–P bonds in the direction
of the bridging thiolate substituents are significantly shorter (by
0.05 Å in the silver complexes) than those pointed away from
these groups, and the two Ag–(µ-S) bonds also differ by at least
0.06 Å in all four cases. None of these dissymmetrical elements
is reflected in NMR spectroscopy of these compounds in the
solution state; all exhibit a single set of triphenylphosphine
signals and only one set of ethyl thiolate resonances. Further
investigation of the evident solution-state fluxionality of these
complexes is underway.
Figure 3. X-ray crystal structures of (Ph3P)2Ag(µ-SEt)2In(SEt)2 (4), and
(Ph3P)2Ag(µ-SEt)2Ga(SEt)2 (5), with 50% probability thermal ellipsoids
depicted. Compounds 4 and 5 co-crystallized with C6H6, which is omitted for
clarity and does not exhibit any contacts within van der Waals sums. H atoms
are omitted for clarity.
The two metals in all these crystal structures behave almost
independently – that is, bond angles and distances at M depend little
on the identity of E, and vice versa. Both copper and silver exhibit
P1–M–P2 angles ranging from 112-120°, which appear to be
constricted by nearby thiolates relative to the ≥135° angles observed
in the corresponding chloride complexes (vida infra). Cu–(µ-S)
bonds, at 2.38-2.45 Å, are longer than many reported for other
bridging copper thiolate systems, although the most relevant points
of comparisons are more complex oligomeric structures.12 The
corresponding bonds in silver complexes are also atypically long,
averaging 2.65 Å in each of the three complexes.13 Bond angles (µ-
S1)–Cu–(µ-S2) are roughly 10° wider than their S–Ag–S analogues,
which may be required to accommodate shorter Cu–(µ-S) bond
lengths within the 4-membered ring. Cross-ring contacts between
the two sulfurs and between the two metals are roughly in the range
of their summed van der Waals radii, and not sufficiently below these
values to suggest specific attractive interactions.
Table 1. Selected bond lengths and contacts (Å) in SSPs of the form
(Ph3P)2M(µ-SEt)2E(SEt)2, 1-6. (µ-S) designates a bridging sulfur atom, (t-S)
designate a terminal sulfur atom, and where applicable the shorter bond in
each class is reported.
1a
2
3
4
5
6
M / E
Cu / In
Cu / Ga
Cu / Al
Ag / In
Ag / Ga
Ag / Al
E–(µ-S)
E–(t-S)
M–S1
2.494(2)
2.419(3)
2.418(2)
2.3159(8)
2.2423(8)
2.3800(8)
2.4527(9)
2.3010(8)
2.2693(8)
3.5040(10)
3.1655(5)
2.2716(11)
2.2185(11)
2.4013(6)
2.4172(8)
2.2894(7)
2.2782(7)
3.5112(9)
3.1063(9)
2.4959(6)
2.4272(7)
2.6247(6)
2.6847(6)
2.5017(6)
2.4523(5)
3.6577(8)
3.5526(4)
2.3192(8)
2.2429(9)
2.6159(8)
2.6829(8)
2.4497(7)
2.5025(8)
3.465(1)
2.2892(7)
2.2273(8)
2.6185(6)
2.6824(5)
2.5030(6)
2.4508(5)
3.4513(8)
3.4539(7)
M–S2
M–P1
2.278(2)
M–P2
(µ-S1)···(µ-S2)
M···E
3.603(3)
3.337
3.4711(5)
Figure 2. X-ray crystal structures of (Ph3P)2Cu(µ-SEt)2Ga(SEt)2, (2), and
(Ph3P)2Cu(µ-SEt)2Al(SEt)2 (3), with 30% probability thermal ellipsoids
depicted. Compound 2 co-crystallized with C6H6, which is omitted for clarity. H
atoms are omitted for clarity.
[a] As previously reported by Hirpo et al.6
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10.1002/ejic.201700115
European Journal of Inorganic Chemistry
FULL PAPER
Bonds to bridging thiolates sulfur atoms are lengthened by
approximately 0.07 Å relative to those involving the terminal thiolates
bound to the same main group metal E, and E–S bond lengths
involving terminal thiolates agree closely within 0.02 Å of those of
free tetrathiolatometallate anions.14 This represents a relatively weak
lengthening, compared to 0.016 Å difference in Al and Ga {E(SR)3}2
dimers.15 The (µ-S)–E–(µ-S) angle within the ring is constricted by
geometric constraints to a range of 92-101°, and the angle between
the terminal thiolate substituents correspondingly expands slightly
from the tetrahedral ideal to 111-114°. Overall, the indifference of M
and E to each other, the long Cu–S and Ag−S bond lengths, and the
weakly impacted bridging E–S bond lengths, suggest that these
complexes might exhibit characteristics of [(PPh3)2M]+ cations
weakly coordinated to [E(SEt)4]− anions, and this perspective would
be consistent with the observation of rapid solution phase exchange
processes currently under further investigation.
Figure 4. X-ray crystal structure of {(Ph3P)2Cu(µ-Cl)2Ga(Cl)2}2, 8, with 50%
probability thermal ellipsoids depicted. H atoms are omitted for clarity.
We previously reported that the chloride Cu-In species,
{(Ph3P)2Cu(µ-Cl)2In(Cl)2}2, 7, exists as a dimer in the solid state.7e
The analogous Cu-Ga species, {(Ph3P)2Cu(µ-Cl)2Ga(Cl)2}2, 8, was
also isolated as a dimer with minimal differences apart from those
corresponding to gallium’s smaller atomic radius (Figure 4, Tables 3
and 4). The isolated (Ph3P)2Ag(µ-Cl)2ECl2 species 10-12 are
isostructural monomers (Figure 6). All chloride complexes 7-12
appear to feature weak interactions between constituent
phosphinometal and tetrachlorometallate components, with long
Cu−(µ-Cl) distances of 2.49-2.54 Å in the 8-membered rings 7 and 8,
and exceptionally long Ag−(µ-Cl) bond distances in 10-12 of 2.88-
2.91 Å.16 The latter contrast with a distance of only 2.63 Å in
[(PPh3)2AgCl]2,17 and comparable values in related complexes.18 The
long Ag–(µ-Cl) distances are accompanied by tight (µ-Cl1)−Ag−(µ-
Cl2) angles of 71-77°, and corresponding opening of the P1−Ag−P2
angle to 137°. In each case, bridging E−(µ-Cl) bonds are lengthened
by only 0.03-0.05 Å relative to the terminal E−Cl bonds, which in turn
match closely to those of the corresponding uncoordinated [ECl4]−
anions.19 The expanded rings in 7 and 8 are not atypical of copper’s
widely varied coordination geometries, and the outer sphere salt
crystallized as 9 likely reflects the weak coordination seen in this
series of complexes, and other related compounds.
Figure 5. X-ray crystal structure of [(Ph3P)3Cu][AlCl4], 9, with 50% probability
thermal ellipsoids depicted. H atoms are omitted for clarity.
Table 2. Selected bond angles (deg) in SSPs of the form (Ph3P)2M(µ-
SEt)2E(SEt)2, 1-6. Terminal sulfur atoms are labeled (t-S1) and (t-S2),
bridging sulfur atoms are labeled (µ-S1) and (µ-S2), and where applicable
the smaller angle in each class is reported.
1a
2
3
4
5
6
Figure 6. X-ray crystal structures of (Ph3P)2Ag(µ-Cl)2InCl2 10, and (Ph3P)2Ag(µ-
Cl)2GaCl2, 11, with 50% probability thermal ellipsoids depicted. H atoms are
omitted for clarity.
M / E
Cu / In
Cu / Ga
Cu / Al
Ag / In
Ag / Ga
Ag / Al
(µ-S1)–M–(µ-S2)
P1–M–P2
96.33(8)
120.7(1)
112.73(8)
92.50(7)
85.59(7)
92.95(3)
111.96(3)
114.35(3)
98.26(3)
83.13(3)
93.56(3)
117.10(3)
113.56(4)
100.65(4)
82.92(3)
87.08(2)
119.06(2)
114.05(2)
94.19(2)
86.52(2)
81.66(2)
119.33(3)
112.06(4)
96.83(3)
87.69(3)
81.23(2)
119.28(2)
111.08(3)
97.57(3)
89.00(2)
Table 3. Selected bond lengths (Å) for the (Ph3P)2M(µ-Cl)2E(Cl)2 dimers 7
and 8, and monomers 10-12. Terminal chlorines atoms are labeled (t-Cl),
bridging chlorines are labeled as (µ-Cl), and where applicable the shorter
bond length of each class is listed.
(t-S1)–E–(t-S2)
(µ-S1)–E–(µ-S2)
M–(µ-S1)–E
7*
8
10
11
12
M / E
Cu / In
Cu / Ga
Ag / In
Ag / Ga
Ag / Al
[a] As previously reported by Hirpo et al.6
E–(µ-Cl)
E–(t-Cl)
M–(µ-Cl)
M–P
2.3752(7)
2.3231(9)
2.4944(5)
2.2478(6)
2.1970(4)
2.1490(5)
2.5174(4)
2.2492(4)
2.3601(8)
2.3216(9)
2.8750(9)
2.4281(7)
2.1832(6)
2.1440(8)
2.8887(7)
2.4294(5)
2.1416(9)
2.1066(9)
2.8998(7)
2.4289(6)
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10.1002/ejic.201700115
European Journal of Inorganic Chemistry
FULL PAPER
Table 4. Selected bond angles (deg) for the series of the (Ph3P)2M(µ-
Cl)2E(Cl)2 dimers 7 and 8, and monomers 10-12. Terminal chlorines are
labeled (t-Cl1) and (t-Cl2), bridging chlorines are labeled (µ-Cl1) and (µ-Cl2),
and where applicable the smaller angle of each class is listed.
To make an initial assessment of the suitability of these
complexes as precursors for solid-state materials, differential
scanning calorimetry and thermogravimetric analysis (DSC-TGA)
were used to explore the thermal behaviors of the complexes. In
a typical decomposition experiment, a small quantity (about 20
mg) of I-III complex was heated from ambient temperature to
450 °C under nitrogen at a heating rate of 10 °C/min (Figure 7).
Melting points (associated with endotherms at constant weights),
decomposition temperatures (corresponding to exotherms and
7*
8
10
11
12
M / E
Cu / In
113.95(3)
107.22(2)
Cu / Ga
112.80(3)
Ag / In
111.60(4)
Ag / Ga
111.35(4)
Ag / Al
111.14(4)
(t-Cl1)–E–(t-Cl2)
(t-Cl1)–E–(µ-
Cl1)
107.46 (2)
114.72(3)
112.43(3)
112.04(4)
(µ-Cl1)–E–(µ-
Cl2)
M–(µ-Cl1)–E
(µ-Cl1)–M–(µ-
Cl2)
104.75(2)
105.20(2)
131.80(2)
95.42 (1)
133.80(2)
98.95(3)
91.73(2)
77.44(2)
137.03(2)
102.76(2)
92.31(2)
72.56(2)
136.74(2)
103.61(3)
92.48(3)
71.22(2)
137.03(2)
130.33(2)
94.67(2)
P1–M–P2
133.50(2)
Table 5. Crystallographic Data for Bimetallic Thiolate Complexes 2-6
2·½C6H6
C47H53CuGaP2
S4
3
4·½C6H6
C47H53AgInP2
S4
5·½C6H6
C47H53AgGaP2
S4
6·½C6H6
C47H53AgAlP2
S4
significant weight loss), and % weight loss values were
empirical
formula
formula
weight
crystal
size [mm]
crystal
descriptio
n
C44H50AlCuP2
S4
determined from these experiments (Table 7). The melting
transition temperatures of complexes ranged from 111 °C for Ag-
Ga complex (5) to 136 °C for Cu-Ga complex (2), and
decomposition temperatures from 275 °C (5) to 300 °C (2). There
appear to be no clear trends in the melting or decomposition
temperatures based on composition of the complexes, as all the
values measured fall within a narrow window close to that of
established Cu-In SSP 1. In all cases, significant weight loss
begins about 20 °C after the melting transition. The substances
remaining after decomposition are expected to be MES2 materials,
and comparisons between the predicted and observed % weight
loss values are consistent with this supposition. Observed %
weight losses were consistently less than theoretical values for
MES2 formation, with differences ranging from 2% to 9% of total
mass. The slight retention of weight upon decomposition is
attributed to the fact that some byproducts may be physically
embedded in the products, or chemically bound to the surface of
the resulting material such that they could not be volatilized.
985.66
941.38
0.28 x 0.23 x
0.20
859.59
0.35 x 0.30 x
0.25
1030.8
0.27 x 0.21 x
0.11
942.96
0.36 x 0.32 x
0.18
0.45 x 0.25 x
0.17
colorless
prism
colorless
prism
colorless
block
colorless
block
colorless
block
crystal
system
space
group
V [Å3]
Dcalc
monoclinic
monoclinic
triclinic
triclinic
triclinic
P21/c
4593.63(18)
P21/n
4324.66(16)
P-1
2343.2(4)
P-1
2316.8(5)
P-1
2322.0(5)
g/cm3
a [Å]
1.361
1.32
1.461
1.413
1.349
18.5906(5)
12.1690(2)
20.9709(5)
90
104.4749(9)
90
12.2975(3)
21.6762(3)
16.4418(4)
90
99.3410(9)
90
12.879(1)
13.609(1)
14.262(1)
76.799(2)
85.887(2)
74.340(2)
2
12.873(2)
13.487(2)
14.201(2)
76.678(2)
85.701(2)
74.966(2)
2
12.867(2)
13.479(2)
14.239(2)
76.678(2)
85.882(2)
75.081(2)
2
b [Å]
c [Å]
α [deg]
β [deg]
γ [deg]
Z
4
4
absorptio
n
coefficien
t [mm-1
F (000)
T [K]
]
1.332
1956
150
0.823
1800
150
1.187
1050
173
1.285
1014
273
0.733
978
173
total no.
reflection
s
10520
9892
10150
29619
10075
unique
reflection
s (I >
2σ(I))
R-factor
(%)
7505
4.48
7242
4.39
9429
2.52
11111
3.87
9128
2.74
goodnes
s of fit
1.032
1.012
1.038
1.004
1.049
Table 6. Crystallographic Data for Bimetallic Chloride Complexes 8
and 10-12
8
10
11
12
empirical
formula
formula
weight
C72H60Cl8Cu2Ga2P4
C36H30Cl4AgInP2
C36H30Cl4AgGaP2
C36H30Cl4AgAlP2
1598.2
889.03
843.93
801.19
crystal size
[mm]
crystal
0.34 x 0.22 x
0.14
0.28 x 0.22 x
0.14
0.28 x 0.19 x 0.12
0.38 x 0.27 x 0.10
colorless blocks
description
colorless blocks
colorless blocks
colorless blocks
crystal
system
space group
V (Å3)
triclinic
P-1
1749.8(2)
1.518
12.2520(8)
12.9578(9)
13.1746(9)
89.534(1)
70.404(1)
64.162(1)
2
monoclinic
P21/n
3679.5(2)
1.605
12.859(3)
21.790(6)
13.201(4)
90
95.876(4)
90
monoclinic
P21/n
3621.9(6)
1.548
12.800(1)
21.761(2)
13.089(1)
90
96.536(2)
90
monoclinic
P21/n
3615.2(1)
1.472
12.805(2)
21.769(4)
13.054(2)
90
96.538(3)
90
Dcalc g/cm3
a [Å]
Figure 7. Example DSC-TGA curves of complex 4.
b [Å]
c [Å]
α [deg]
β [deg]
γ [deg]
Z
Table 7. DSC and TGA of complexes 1-6.
SSP
Actual % Weight
Loss
Theoretical %
Weight Loss
Melting Point
DSC (°C)
End Decomp.
DSC-TGA (°C)
4
4
4
absorption
coefficient
1 Cu-In
2 Cu-Ga
3 Cu-Al
4 Ag-In
5 Ag-Ga
6 Ag-Al
71
71
75
69
66
69
74
78
82
71
74
78
120
136
123
128
111
126
290
300
300
295
275
290
[mm-1
]
1.8
808
173
1.561
1760
173
1.692
1688
173
0.991
1616
173
F (000)
T [K]
total no.
reflections
unique
reflections (I
> 2σ(I))
R-factor (%)
goodness of
fit
7576
8039
7907
7888
7107
2.24
7108
2.35
7061
2.9
6870
2.75
1.054
1.042
1.031
1.022
3. Thermal Analysis
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10.1002/ejic.201700115
European Journal of Inorganic Chemistry
FULL PAPER
during which the solution went clear. NaSEt (81.2 g, 0.914 mol)
was then added and stirred for 12 h at 80 °C, filtered through
celite and volatiles removed in vacuo to collect 2 as a white solid
(190.5 g, 88.0 % yield). White crystals for X-ray analysis were
grown by vapor diffusion of pentane into benzene to yield
Conclusions
This report demonstrates that methods used for the
synthesis of bimetallic Cu-In chloride and thiolate complexes
may be readily extended to other metals within these groups,
usually with minimal modifications. Thiolate complexes 1-6
exhibit similar solid state structures, differing primarily in the
degree of puckering observed in the central MS2E ring, and
undergo thermal decomposition processes comparable to those
of proven CuInS2 chalcopyrite precursor 1. This bodes well for
the utility of these complexes as precursors for semiconductors,
and previous work in the Cu-In system suggests that these
SSPs may be further modified by ligand exchange reactions to
fine-tune their utility in material synthesis. Continuing work
focuses on the use of these precursors in the preparation of
pure and alloyed nanomaterials, and investigation of their
solution phase behavior as it pertains to both materials
applications and fundamental structural features.
2 C6H6. Analysis calculated for C44H50CuGaP2S4: C, 58.6; H,
×
5.58; S, 14.2. Found: C, 59.91; H, 5.56; S, 14.07. 1H NMR (300
MHz, CD2Cl2): d 7.39-7.23 (m, 30H, Ar), 2.61 (q, 8H, SCH2, J =
7.6 Hz), 1.20 (t, 12H, CH3, J = 7.2 Hz). 13C NMR (76 MHz,
CD2Cl2): d 134.17 (d, Ar, J = 10.8 Hz), 129.96 (s, Ar), 128.90
(bs, Ar), 128.63 (s, Ar), 23.64 (s, Et), 19.65 (s, Et). 31P NMR (121
MHz, CD2Cl2): d -0.84. The DSC spectrum of 2 registered a
sharp endothermic peak centered at 136 °C with energy of 24.96
J/g, taken to be the melting point, and another sharp
endothermic peak centered at 298 °C with energy of 272.2 J/g,
taken to be the decomposition point. The TGA trace of 2
registered a weight loss of 71.26% between the temperatures of
80-400 °C.
Bis(triphenylphosphine) copper(I) aluminum(III)
tetraethylthiolate, (Ph3P)2Cu(µ-SEt)2Al(SEt)2 (3). In ca. 40 mL
of C6H6, PPh3 (3.12 g, 11.9 mmol) was dissolved and CuCl (.595
g, 6.0 mmol, anhydrous) was added. Suspension was stirred for
4 h with periodic sonication to generate a uniform white
suspension. Anhydrous AlCl3 (1.56 g, 6.32 mmol, 1.0 equiv) was
then added and the vessel was sonicated for 5 min, then heated
to 60 °C for 3 h, after which the suspension was fully dissolved.
NaSEt (2.10 g, 25.0 mmol) was delivered and the suspension
was then heated to 60 °C for an additional 3 d. Volatiles
removed in vacuo to yield light yellow solid (4.17 g, 81.5 %
yield). Clear yellow crystals for X-ray analysis were grown by
vapor diffusion of pentane into benzene. Analysis calculated for
C44H50CuAlP2S4: C, 61.48; H, 5.86; S, 14.92. Found: C, 61.98;
H, 5.65; S, 9.71.21 1H NMR (300 MHz, C6D6): d 7.49 (m, 12H,
Ar), 7.10-6.96 (m, 18H, Ar), 2.61 (bq, 8H, SCH2, J = 6.9 Hz),
1.24 (bt, 12H, CH3, J = 6.9 Hz). 1H NMR (300 MHz, CD2Cl2): d
7.40-7.24 (m, 30H, Ar), 2.61 (q, 8H, SCH2, J = 8.6 Hz), 1.24 (t,
12H, CH3, J = 7.2 Hz). 13C NMR (76 MHz, CD2Cl2): d 134.19 (d,
Ar, J = 13.7 Hz), 129.96 (s, Ar), 128.88 (d, Ar), 128.64 (s, Ar),
22.75 (s, Et), 19.92 (s, Et). 31P NMR (121 MHz, CD2Cl2): d 1.41.
The DSC spectrum of 3 registered a sharp endothermic peak
centered at 124 °C with energy of 60.61 J/g, taken to be the
melting point, and another sharp endothermic peak centered at
301 °C with energy of 402.4 J/g, taken to be the decomposition
point. The TGA trace of 3 registered a weight loss of 74.96%
between the temperatures of 80-400 °C.
Experimental Section
All operations were conducted under nitrogen
atmosphere using standard Schlenk techniques. Glassware was
dried a minimum of 12 h at 150 °C prior to use. Aluminum (III)
chloride, (AlCl3, anhydrous, 99.985%, metals basis), gallium (III)
chloride (GaCl3, ultra dry, 99.999 %, metals basis), indium (III)
chloride (InCl3, anhydrous, 99.99%, metals basis), silver (I)
chloride (AgCl, ultra dry, 99.997%, metals basis), and
triphenylphosphine (Ph3P, 99+%) were purchased from Alfa
Aesar. GaCl3 was used immediately on opening ampoule or
sublimed prior to use. Copper (I) chloride (CuCl, 99.999%, extra
pure, purified) and ethanethiol (CH3CH2SH, 99+%) were
purchased from Acros Organics. Commercial reagents were
stored under inert atmosphere but otherwise used as received.
Solvents (benzene, tetrahydrofuran, diethyl ether, and pentane)
were dried using an Innovative Technology Inc. solvent
purification system (activated alumina, copper catalyst,
molecular sieves columns), degassed, and tested with
sodium/benzophenone ketyl prior to use.
Elemental analyses were carried out by Atlantic
Microlab, Inc. or Columbia Analytical Services. The 1H, 13C, and
31P NMR data were obtained on a JEOL ECX 300 instrument.
Chemical shits are reported in d units relative to the residual
solvent peaks of the respective NMR solvent. DSC and TGA
measurements were collected on a TA Instruments SDT Q600
calibrated using the melting points of Zn and In.
Bis(triphenylphosphine) silver(I) indium(III)
Sodium ethanethiolate was prepared by refluxing ethyl
thiol over sodium metal in a suspension of diethyl ether. Solvent
was then decanted from the solid NaSEt and evacuated to
dryness. (Ph3P)2CuCl was generated by the addition of 2
equivalents PPh3 to CuCl in C6H6, stirred for 4 h at room
temperature, then evacuated to dryness. (Ph3P)2AgCl was
prepared by the addition of 2 equivalents PPh3 to AgCl in CHCl3,
stirred for 4 h at room temperature and evacuated to dryness.
GaCl3 was sublimed prior to use. All other reagents were
obtained anhydrous from commercial sources and used without
further purification.
tetraethylthiolate, (Ph3P)2Ag(µ-SEt)2In(SEt)2 (4). AgCl (1.446
g, 10.09 mmol) was suspended in 500 mL solvent (1:4 ratio,
THF:C6H6) and PMe3 (1.80 mL, 20.2 mmol) was then added and
stirred for 4 h. InCl3 (2.232 g, 10.09 mol) was then added and
stirred for 1 h at 60 °C, during which the solution went clear.
NaSEt (3.395 g, 40.36 mmol) was then added and stirred for 2
days at 60 °C in the dark, and the solution was filtered through
celite and volatiles removed in vacuo. The resulting solid was
then redissolved in 500 mL of toluene and PPh3 (5.293 g, 20.09
mol) was then added and stirred under reduced pressure to
dryness to yield 4 as a white solid (7.81 g, 78.0 % yield). Clear
colorless crystals for X-ray analysis were grown by vapor
diffusion of pentane into benzene. Analysis calculated for
C44H50AgInP2S4: C, 53.3; H, 5.08; S, 12.9. Found: C, 54.93; H,
5.22; S, 11.99.21 1H NMR (300 MHz, CD2Cl2): d 7.40-7.30 (m,
30H, Ar), 2.66 (q, 8H, SCH2, J = 7.2 Hz), 1.17 (t, 12H, CH3, J =
7.2 Hz). 13C NMR (76 MHz, CD2Cl2): d 134.09 (d, Ar, J = 16.6
Bis(triphenylphosphine) copper(I) gallium(III)
tetraethylthiolate, (Ph3P)2Cu(µ-SEt)2Ga(SEt)2 (2). In a 5 L
round bottom, PPh3 (126.3 g, 0.480 mol) was dissolved in 1.5 L
solvent (1:1 ratio, THF:C6H6) and CuCl (23.9 g, 0.241 mol) was
then added and stirred for 4 h at room temperature, then GaCl3
(42.4 g, 0.241 mol) was added and stirred for 1 h at 80 °C,
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10.1002/ejic.201700115
European Journal of Inorganic Chemistry
FULL PAPER
CD2Cl2): 7.80-7.22 (m, 30H, Ar). 13C NMR (76 MHz, CD2Cl2): d
134.04 (s, Ar), 131.06 (s, Ar), 130.37 (bs, Ar), 129.41 (s, Ar). 31
NMR (121 MHz, CD2Cl2): d 0.19. DSC of 8 registered a sharp
peak centered at 173.0 °C, taken to be the melting point, with
decomposition observed above 249.6 °C.
Hz), 133.75, 130.20, 129.17 (d, Ar, J = 8.7 Hz), 128.63, 23.14,
21.02. 31P NMR (121 MHz, C6D6): d 5.92, br. The DSC spectrum
of 4 registered a sharp endothermic peak centered at 128 °C
with energy of 39.76 J/g, taken to be the melting point, and
another sharp endothermic peak centered at 294 °C with energy
of 174.4 J/g, taken to be the decomposition point. The TGA
trace of 4 registered a weight loss of 69.4% between the
temperatures of 80-400 °C.
P
Bis(triphenylphosphine) silver(I) indium(III) tetrachloride,
(Ph3P)2Ag(µ-Cl)2In(Cl)2 (10). In the glovebox, (Ph3P)2AgCl (789
mg, 1.18 mmol) and InCl3 (267 mg, 1.21 mmol, 1.0 equiv) were
suspended in C6H6 and heated to 60 °C for 1 h. The solution
was cooled slowly to isolate clear, colorless crystals for X-ray
analysis (734 mg, 70% yield). Analysis calculated for
Bis(triphenylphosphine) silver(I) gallium(III)
tetraethylthiolate, (Ph3P)2Ag(µ-SEt)2Ga(SEt)2, (5).
(Ph3P)2AgCl (7.06 g, 10.57 mmol) and GaCl3 (1.86 g, 10.57
mmol) were suspended in C6H6 and heated to 60 °C for 2 h.
Once fully dissolved, NaSEt (3.56 g, 42.28 mmol) was delivered
and the suspension was returned to heating for 3 days in the
dark. Volatiles were then removed in vacuo to yield an off-white
solid (7.2 g, 72% yield). The colorless crystals for X-ray analysis
were grown by vapor diffusion of pentane into benzene. Analysis
calculated for C44H50AgGaP2S4: C, 55.8; H, 5.32; S, 13.6. Found:
C, 56.97; H, 5.09; S,10.62.21 1H NMR (300 MHz, C6D6): d 7.50-
7.42 (m, 12H, Ar), 7.10-6.97 (m, 18H, Ar), 2.65 (q, 8H, SCH2, J =
7.6 Hz), 1.21 (t, 12H, CH3, J = 7.2 Hz). 13C NMR (76 MHz,
CD2Cl2): d 134.11 (d, Ar, J = 17.3 Hz), 133.71 (d, Ar, J = 17.3
C36H30AgCl4InP2: C, 48.6; H, 3.40. Found: C, 45.31; H, 3.33. 1H
NMR (300 MHz, CD2Cl2): d 7.56-7.38 (m, 30H, Ar). 13C NMR (76
MHz, CD2Cl2): d 134.16 (s, Ar), 131.57 (s, Ar), 130.02 (bs, Ar),
129.72 (s, Ar). 31P NMR (121 MHz, CD2Cl2): d 13.16 (br d, JAg-P
500 Hz).20 DSC of 10 registered a sharp peak centered at
184.0 °C, taken to be the melting point, with decomposition
observed above 213.6 °C.
≈
Bis(triphenylphosphine) silver(I) gallium(III) tetrachloride,
(Ph3P)2Ag(µ-Cl)2Ga(Cl)2 (11). In the glovebox, (Ph3P)2AgCl (582
mg, 0.871 mmol) and GaCl3 (154 mg, 0.872 mmol, 1.0 equiv)
were suspended in C6H6 and heated to 60 °C for 1 h. The
solution was cooled slowly to isolate clear, colorless crystals for
X-ray analysis (566 mg, 77% yield). Analysis calculated for
C36H30AgCl4GaP2: C, 51.2; H, 3.58. Found: C, 51.46; H, 3.57. 1H
NMR (300 MHz, CD2Cl2): d 7.50-7.38 (m, 30H, Ar). 13C NMR (76
MHz, CD2Cl2): d 134.17 (s, Ar), 131.56 (s, Ar), 130.06 (bs, Ar),
Hz), 130.28, 129.16 (d, Ar, J = 9.3 Hz), 128.63, 23.53, 19.57. 31
NMR (121 MHz, C6D6): d 7.49, br. The DSC spectrum of 5
registered a sharp endothermic peak centered at 111 °C with
energy of 15.32 J/g, taken to be the melting point, and another
P
sharp endothermic peak centered at 273 °C with energy of 278.0
J/g, taken to be the decomposition point. The TGA trace of 5
registered a weight loss of 65.83% between the temperatures of
80-400 °C.
129.69 (s, Ar). 31P NMR (121 MHz, CD2Cl2): d 12.96 (br d, JAg-P
500 Hz). DSC of 11 registered a sharp peak centered at
192.0 °C, taken to be the melting point, with decomposition
observed at 211 °C.
≈
Bis(triphenylphosphine) silver(I) aluminum(III)
tetraethylthiolate, (Ph3P)2Ag(µ-SEt)2Al(SEt)2 (6). (Ph3P)2AgCl
(7.84 g, 11.74 mmol) and anhydrous AlCl3 (1.59 g, 11.89 mmol,
1.01 equiv) were suspended in ca. 50 mL of C6H6 and heated to
60 °C for 2 h, resulting in a yellow colored suspension. NaSEt
(3.98 g, 47.3 mmol, 4.03 equiv) was then added and heated at
60°C for 6 days in the dark. The clear yellow solution was
decanted, filtered through celite and evaporated to dryness to
yield 7.1 g of 6 as a yellow solid (7.12 g, 67.1% yield). The clear
yellow crystals for X-ray analysis were grown by vapor diffusion
of pentane into benzene. Analysis calculated for
C44H50AgAlP2S4: C, 58.5; H, 5.58; S, 14.2. Found: C, 59.7; H,
5.68; S, 12.0.21 1H NMR (300 MHz, C6D6): d 7.54-7.42 (m, 12H,
Ar), 7.10-6.97 (m, 18H, Ar), 2.61 (q, 8H, SCH2, J = 7.2 Hz), 1.18
(t, 12H, CH3, J = 7.2 Hz). 1H NMR (300 MHz, CD2Cl2): d 7.43-
7.25 (m, 30H), 2.61 (q, 8H, SCH2, J = 6.9 Hz), 1.18 (t, 12H, CH3,
J = 7.5 Hz). 13C NMR (76 MHz, CD2Cl2): d 134.18 (d, Ar, J =
16.6 Hz), 133.58 (d, Ar, J = 20.2 Hz), 130.27, 129.12 (d, Ar, J =
9.4 Hz), 128.63, 22.91, 20.48. 31P NMR (121 MHz, CD2Cl2): d
6.49, br. The DSC spectrum of 6 registered a sharp endothermic
peak centered at 126 °C with energy of 2.679 J/g, taken to be
the melting point, and another sharp endothermic peak centered
at 290 °C with energy of 255.8 J/g, taken to be the
Bis(triphenylphosphine) silver(I) aluminum(III) tetrachloride,
(Ph3P)2Ag(µ-Cl)2Al(Cl)2 (12). In the glovebox, (Ph3P)2AgCl (863
mg, 1.29 mmol) and AlCl3 (178 mg, 1.33 mmol, 1.0 equiv) were
suspended in C6H6 and heated to 60 °C for 1 h. The solution
was cooled slowly to isolate clear, colorless crystals for X-ray
analysis (641 mg, 62% yield). Analysis calculated for
C36H30AgAlCl4P2: C, 54.0; H, 3.77. Found: C, 53.72; H, 3.76. 1H
NMR (300 MHz, CD2Cl2): d 7.57-7.35 (m, 30H, Ar). 13C NMR (76
MHz, CD2Cl2): d 134.12 (s, Ar), 131.58 (s, Ar), 129.97 (bs, Ar),
129.69 (s, Ar). 31P NMR (121 MHz, CD2Cl2): d 13.20 (br d, JAg-P
500 Hz). DSC of 12 registered a sharp peak centered at
186.0 °C, taken to be the melting point, with decomposition
observed above 212 °C.
≈
X-ray Structure Determination
Diffraction intensities were collected on a Bruker Apex CCD or
Nonius Kappa CCD diffractometer using MoKα radiation λ=
0.71073 Å. For basic crystallographic parameters, see Tables 5
and 6. Space groups were determined based on systematic
absences and/or intensities statistics. Absorption corrections
were applied by SADABS.22a Structures were solved by direct
methods and Fourier techniques and refined on F2 using full
matrix least-squares procedures. Non-H atoms were refined with
anisotropic thermal parameters. H atoms were placed in
calculated positions and refined in a rigid group model. All
calculations have been performed by the Bruker SHELXTL97
package.22b
decomposition point. The TGA trace of 6 registered a weight
loss of 68.76% between the temperatures of 80-400 °C.
Bis[bis(triphenylphosphine)copper(I) gallium(III)
tetrachloride], {(Ph3P)2Cu(µ-Cl)2Ga(Cl)2}2 (8). (Ph3P)2CuCl
(327 mg, 0.52 mmol) and GaCl3 (94.5 mg, 0.54 mmol, 1.0 equiv)
were suspended in C6H6 and heated to 60 °C for 1 h. The
solution was cooled slowly to isolate clear, colorless crystals
(266 mg, 64% yield). Analysis calculated for C77H60Cl8Cu2Ga2P4:
C, 54.1; H, 3.78. Found: C, 52.15; H, 3.64. 1H NMR (300 MHz,
This article is protected by copyright. All rights reserved.

10.1002/ejic.201700115
European Journal of Inorganic Chemistry
FULL PAPER
CCDC 1537712 (for 2), 1537714 (for 3), 1537713 (for 4),
1537718 (for 5), 1537715 (for 6), 1537717 (for 8), 1537719 (for
10), 1537716 (for 11), and 1537720 (for 12), contain the
supplementary crystallographic data for this paper. These data
can be obtained free of charge from The Cambridge
Crystallographic Data Centre.
42, 7713-7715; h) O. Kluge, D. Friedrich, G. Wagner, H. Krautscheid,
Dalton. Trans. 2012, 41, 8635-8642.
[8]
[9]
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10.1002/ejic.201700115
European Journal of Inorganic Chemistry
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A single synthetic strategy affords several bimetallic thiolate complexes combining Cu or Ag with Al,
Ga, or In. These compounds, targeted as single source precursors for ternary chalcogenide materials,
adopt crystal structures with puckered MS2E rings and elongated M−S bonds, and as solids decompose
in the 250-300 °C range.
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