Synthesis and Structural Characterization of Copper(I) Phenylselenolate Complexes Stabilized by N,N′-Donor Ligands

Article abstract of DOI:10.1002/zaac.201400584

The reaction of sodium phenylselenolate and copper(I) chloride generates in situ a "CuSePh" species, which can be stabilized by N,N′-donor ligands such as bpy (2, 2′-bipyridine) or phen (1, 10-phenanthroline) in order to generate compounds with μ₂

Full text of DOI:10.1002/zaac.201400584

Journal of Inorganic and General Chemistry
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ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
DOI: 10.1002/zaac.201400584
Synthesis and Structural Characterization of Copper(I) Phenylselenolate
Complexes Stabilized by N,NЈ-Donor Ligands
Bruno N. Cabral,[a] Luana E. Zawatski,[a] Ulrich Abram,*[b] and Ernesto S. Lang*[a]
Keywords: Phenylselenolate; Copper(I) cluster; N,NЈ-Donor ligands, Copper, Selenium
Abstract. The reaction of sodium phenylselenolate and copper(I) coordination N,NЈ-donor ligands prevents from the rapid formation
chloride generates in situ a “CuSePh” species, which can be stabilized
of less soluble polymers and gives access to three new compounds,
[{Cu4(phen)3(μ2-SePh)(μ3-
by N,NЈ-donor ligands such as bpy (2,2Ј-bipyridine) or phen [{Cu2(bpy)2(μ3-SePh)}{CuCl2}2]2,
(1,10-phenanthroline) in order to generate compounds with μ2-SePh– SePh)}2(μ2-Cl)2] (CuCl2)2·2(PhSe)2, and [Cu6(bpy)2(μ2-SePh)2(μ3-
or μ3-SePh– groups connecting the copper atoms. The intermediate SePh)4]·(THF).
stabilization of mononuclear “CuSePh” building blocks by the
ring with μ2-coordinated phenylselenolato ligands. NMR spec-
1 Introduction
troscopic and cryoscopic measurements of this complex indi-
The investigation of molecular compounds of coinage
cate that the solid-state structure is maintained in solution.
metals, which are bridged by chalcogen atoms, represents an
Electrooxidation of a copper anode in a toluene/acetonitrile
area of ever increasing activity in recent chemical and material
solution of diphenyl diselenide and triphenylphosphine
science research.[1–3] This is mostly due to the high interest in
gives [(Ph3P)Cu(μ2-SePh)2Cu(PPh3)2]·CH3CN in excellent
controlling the size and shape of cluster compounds generated
yields,[13] but could not be extended to a general route for the
by binary and ternary coinage metal chalcogenides, which
synthesis of such compounds. That’s why in recent years one-
leads to properties being between the semiconducting and met-
pot reactions of silylated phenylchalcogenolate sources
allic phases.[4–6] Due to the multidisciplinary importance of
(mainly PhESiMe3, E = Se, Te) with copper(I) salts and ancilli-
metal chalcogenolates in fields like biological chemistry, sup-
ary phosphine ligands have been established as main routes for
ramolecular chemistry, and material research, they attract at-
the synthesis of copper selenolato complexes.[1–6] The method-
tention not only to chemists, but also to physicists, biochem-
ology developed for the preparation of such phosphine-coordi-
ists, and other researchers, who in some way work with chalco-
nated Cu2Se clusters can be tailored in order to incorporate
gen compounds.[7–9]
chemical functionality onto the surfaces of frameworks.[14]
As part of our interest in the synthesis of chalcogenolato
Fenske et al. described the synthesis of the polyanionic cluster
compounds of low-valent metal ions,[10,11] particularly cop-
[pyH]6[(CuCl)9(μ3-SePh)5(μ4-SePh)] by the treatment of tetra-
per(I), we started a study with in situ stabilized “PhSeCu” spe-
copper(I)phosphonitocavitand with PhSeSiMe3 in THF at low
cies for the synthesis of new cluster compounds. Stabilization
temperatures.[15] More recently, the same authors included
was performed by the addition of N,NЈ-donor ligands such as
4,4Ј-bipyridine in a similar synthetic route for the synthesis of
2,2Ј-bipyridine (bpy) or 1,10-phenanthroline (phen). To the
the dinuclear complex [Cu2(SeC6H4SMe)2(PPh3)2(4,4Ј-bpy)2]
best of our knowledge, the first compound of this class, the
and
three
one-dimensional
coordination
[Cu2(SePh)2(dppm)(4,4Ј-
polymers:
dinuclear complex [Cu{Se(2,4,6-iPr3C6H2)}2(2,2Ј-bpy)2], was
obtained by the reaction of the hexanuclear cluster
[Cu{Se(2,4,6-iPr3C6H2)}]6 with 2,2Ј-bipyridine.[12] The re-
sulting copper complex forms a folded four-membered Cu2Se2
[Cu6(SePh)6(PPh3)3(4,4Ј-bipy)],
bpy)], and [Cu2(SePh)2(dppe)(4,4Ј-bpy)]. The latter three com-
pounds contain polynuclear selenolato copper complexes,
which are linearly cross-linked by the bipyridine ligands.[16]
In continuation of our recent work in this field, herein we
present the synthesis and structural analysis of three novel CuI
phenylselenolato clusters with 2,2Ј-bipyridine co-ligands.
* Prof. Dr. E. S. Lang
Fax: +55-55-3220-8031
E-Mail: eslang@ufsm.br
* Prof. Dr. Ulrich Abram
Fax: +49-30-838-52676
E-Mail: ulrich.abram@fu-berlin.de
[a] Departamento de Química
Universidade Federal de Santa Maria
97105–900 Santa Maria, RS, Brazil
[b] Institute of Chemistry and Biochemistry
Freie Universität Berlin
2 Results and Discussion
2.1 Synthetic Considerations
The treatment of copper(I) chloride with one equivalent of
sodium phenylselenolate in an ethanol/tetrahydrofuran mixture
Fabeckstr. 34–36
14195 Berlin, Germany
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Scheme 1. Schematic description of the performed reactions.
yields a precipitate, which can be redissolved by the addition
of bpy/dmf, phen/dmf, or bpy/CH3CN solutions in one-pot re-
actions. Such procedures generate the three new compounds
shown in Scheme 1: [{Cu2(bpy)2(μ3-SePh)}{CuCl2}2]2 (1),
[{Cu4(phen)3(μ2-SePh)(μ3-SePh)}2(μ2-Cl)2](CuCl2)2·2(PhSe)2
(2), and [Cu6(bpy)2(μ2-SePh)2(μ3-SePh)4]·THF (3).
For the isolation of compounds 1–3 in crystalline form, it
was essential to optimize the reaction and crystallization condi-
tions since the ratio of the reactants as well as the amount and
the chemical nature of the solvent have an influence on the
crystallization of the products. One of the main factors to ob-
tain the new cluster compounds seems to be the time that the
mixture remains in solution before it crystallizes or precipi-
tates. The coordination of the N,NЈ-donor ligands and solvent Figure 1. Structure of compound 1, showing a planar Cu2Se2 ring in
the middle of the molecular structure. The dotted lines represent
Cu···Cu interactions. Hydrogen atoms are omitted for clarity. Sym-
metry operation to generate equivalent atoms: (‘) x, y, –z+1/2.
molecules allow intermediate products like “PhSeCu(N,NЈ-do-
nor)” or “PhSeCuCl(N,NЈ-donor)(solvent)” to remain in solu-
tion for longer periods before any precipitation occurs. That’s
why Scheme 1 also contains information about the reaction
time, which means the time before the crystallization of the
products from the corresponding solutions began. With in-
creasing reaction time, the nuclearity of the clusters and the
selenium/copper ratio increase.
Despite the low solubility of the clusters, we attempted some
NMR spectroscopic measurements. The obtained spectra indi-
cate that the solid-state structures of the clusters are not main-
tained in solution and dissociation into smaller fragments pro-
ceeds. The obtained “PhSeCu” species undergo rapid exchange
reactions. Grützmacher et al. reported similar decomposition
reactions for a number of copper chalcogenolato compounds,
although they could also identify a relatively large complex
subunit such as [{CuSe(2,4,6-iPr3C6H2)}2(bpy)2] by NMR
spectroscopy in solution.[12]
Figure 2. Structure of the cluster cation [{Cu4(phen)3(μ-SePh)(μ3-
SePh)}2(μ-Cl)2]2+ of compound 2. The [CuCl2]– anions and the co-
2.2 Structure Analysis
crystallized (PhSe)2 molecules do not present any interactions with
the dicationic units and therefore they were omitted. The dotted lines
represent Cu···Cu interactions. Hydrogen atoms are omitted for clarity.
Symmetry operations to generate equivalent atoms: (‘) = x,–y+3/2,
The molecular structures of compounds 1–3 together with
their atomic numbering schemes are shown in Figure 1, Fig-
ure 2, and Figure 3. Crystal data and structure refinement are –z+1.
Z. Anorg. Allg. Chem. 2015, 739–743
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Table 1. Crystal data and structure refinement for 1–3.
1
2
3
Empirical formula
C26H21Cl2Cu3N4Se
729.95
C120H88Cl6Cu10N12Se8
3177.80
C60H54Cu6N4OSe6
1702.07
Formula weight /g·mol–1
Temperature /K
296(2)
293(2)
296(2)
Radiation; λ /Å
Crystal system, space group
Mo-Kα; 0.71073
triclinic, P1
Mo-Kα; 0.71073
monoclinic, P21/c
Mo-Kα; 0.71073
monoclinic, P21/c
¯
Unit cell dimensions
a /Å
b /Å
c /Å
α /°
9.7723(6)
14.3984(5)
20.6458(8)
22.0179(8)
90
13.978(1)
15.211(1)
29.222(2)
90
10.6861(7)
13.5912(8)
77.032(4)
β /°
72.377(4)
75.542(4)
1292.7(1)
2; 1.875
4.084
720
119.062(2)
90
5721.1(4)
2; 1.845
4.559
101.457(5)
90
6089.4(8)
4; 1.857
5.687
γ /°
Volume /Å3
Z; density calculated /g·cm–3
Absorption coefficient /mm–1
F(000)
3112
3312
Crystal size /mm
Theta range for data collection θ /°
Index ranges
0.15ϫ0.03ϫ0.03
1.59 to 25.30
–11 Յ h Յ 11
–12 Յ k Յ 12
–16 Յ l Յ 16
15282
0.16ϫ0.13ϫ0.1
1.62 to 25.5
–17 Յ h Յ 17
–25 Յ k Յ 25
–26 Յ l Յ 26
131894
0.16ϫ0.13ϫ0.1
1.42 to 30.67
–20 Յ h Յ 20
–21 Յ k Յ 21
–41 Յ l Յ 41
105611
Reflections collected
Independent reflections [Rint
Completeness
]
4691 [0.0663]
99.7%
10654 [0.1488]
99.9%
18790 [0.0796]
99.7%
Absorption correction
Min. and max. transmission
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I Ͼ 2σ(I)]
Gaussian
Gaussian
Gaussian
0.5794 and 0.8873
4691 / 0 / 325
0.997
R1 = 0.0550
wR2 = 0.1254
R1 = 0.1092
wR2 = 0.1519
1.150 and –0.868
0.647 and 0.7459
10654 / 0 / 703
0.939
R1 = 0.0508
wR2 = 0.1016
R1 = 0.1405
wR2 = 0.1200
0.828 and –0.637
0.6940 and 1.0000
18790 / 0 / 520
1.093
R1 = 0.0786
wR2 = 0.1627
R1 = 0.1640
wR2 = 0.2019
1.763 and –0.789
a)
R indices (all data)
Largest diff. peak and hole /e–Å–3
a) R1 = Σ|Fo–Fc|/Σ|Fo|; wR2 = Σ[w(Fo –Fc ) /Σ(wFo )]–1/2
.
2
2 2
2
presented in Table 1 and selected bond lengths and angles are
listed in Table 2.
The copper atoms in 1 are bonded in three different coordi-
nation environments. The Cu1 atoms of the [CuCl2]– units are
located outside the main plane of the central dicationic unit.
They establish interactions with Cu3 and Se1 of 2.761(1) Å
and 2.690(2) Å, respectively.
The Cu2 atoms are coordinated to N3, N4, Se1, and Se1Ј in
a distorted tetrahedral environment. The Cu3 atom coordinates
to Se1, N1, and N2 in a trigonal environment. In the core of
this compound we can identify the Se atoms as the main con-
nectors, which maintain the structural motif. The μ3-SePh
groups connect all central four Cu atoms and reinforce the
Cu···Cu interactions, which appear with bond lengths in the
range of 2.643–2.761 Å.
The solid-state structure of compound 2 consists of a dicat-
ionic [Cu8(phen)6(SePh)4Cl2]2+ unit, two [CuCl2]– anions, and
two isolated (PhSe)2 molecules. Figure 2 shows the representa-
tion of the dimeric arrangement of the [Cu8(phen)6(μ2-
SePh)2(μ3-SePh)2(μ2-Cl)2]2+ cluster.
There are no interactions between the dicationic unit of 2
and the [CuCl2]– anions or the co-crystallized diphenyldiselen-
ide molecules.
Figure 3. Molecular structure of compound 3. Hydrogen atoms and
the THF solvate are omitted for clarity.
The structure of 1 can formally be described as a tetranu-
clear dicationic central unit of the composition [Cu4(bpy)4(μ3-
SePh)2]2+, which is stabilized by two peripheral [CuCl2]–
building blocks. Each of the central four copper atoms is
bonded to a 2,2Ј-bipyridine ligand and connected with the
others by (μ3-SePh)– anions. The resulting unit is with a crys-
tallographic center of inversion, which is located in the middle
of the Cu2Se2 ring.
The dicationic unit is
a centrosymmetric dimer of
[Cu4(phen)3(SePh)2Cl] with a center of inversion being in the
center of the eight-membered Cu6Cl2 ring. Each three of the
copper atoms in the ring are linked by a μ3-SePh group and
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Table 2. Selected bond lengths /Å and angles /° for 1–3.
copper atoms of the asymmetric units form zigzag chains by
Cu···Cu interactions (2.708–2.817 Å), which are reinforced by
the established μ3-SePh and μ2-SePh bridges.
1
Cu(1)–Se(1)
Cu(3)–Se(1)
Cu(2)–Se(1)
Cu(1)–Cu(3)
Cu(2)–Cu(3)
Cu(2)–Cu(2)i
Cu(1)–Cl(1)
Cu(1)–Cl(2)
2.690(2)
2.310(1)
2.414(1)
2.761(1)
2.867(1)
2.643(1)
2.157(3)
2.139(2)
Cu(1)–Cu(2)–Cu(3)
Cu(2)–Se(1)–Cu(3)
N(1)–Cu(2)–Cu(3)
Cu(2)–Se(1)–Cu(3)i
Cl(1)–Cu(1)–Cl(2)
104.08(4)
74.70(4)
99.4(2)
61.81(4)
148.8(1)
The structure of 3 consists of a neutral hexanuclear
[Cu6(bpy)2(μ2-SePh)2(μ3-SePh)4] cluster compound, which is
co-crystallized with one molecule of tetrahydrofuran. The cen-
tral copper atoms Cu2, Cu3, Cu4, and Cu5 construct a tetrahe-
dron through Cu···Cu interactions [2.453(1)–2.725(2) Å] and
Cu–Se–Cu bonds along the edges of the tetrahedron. Four of
these PhSe– ligands additionally connect the core of the cluster
with the terminal copper atoms Cu1 and Cu6, which finally
results in two μ2-PhSe– and four μ3-PhSe– ligands. Each ter-
minal copper atom possesses a tetrahedral coordination poly-
hedron resulting from the bonding of two μ3-PhSe– groups and
a 2,2Ј-bipyridine ligand.
2
Se(1)–Cu(2)
Se(1)–Cu(3)
Se(1)–Cu(1)
Se(2)–C(81)
Se(2)–Cu(4)
Se(2)–Cu(3)
Cu(1)–N(2)
Cu(1)–N(1)
Cu(1)–Cl(1)
Cu(1)–Cu(2)
Cu(2)–N(4)
Cu(2)–N(3)
Cu(2)–Cu(3)
Cu(3)–Cl(1)ii
Cu(3)–Cu(4)
Cu(4)–N(6)
Cu(4)–N(5)
2.285(1)
2.405(1)
2.435(1)
1.877(8)
2.305(1)
2.354(1)
2.056(5)
2.091(5)
2.332(2)
2.817(1)
2.016(5)
2.085(5)
2.708(1)
2.275(2)
2.747(1)
2.016(5)
2.077(5)
Se(1)–Cu(1)–Cu(2)
Se(1)–Cu(2)–Cu(3)
Cu(2)–Se(1)–Cu(3)
Cu(3)–Cu(2)–Cu(1)
Cu(2)–Se(1)–Cu(1)
Cu(3)–Se(1)–Cu(1)
Cl(1)–Cu(1)–Se(1)
Cl(1)–Cu(1)–Cu(2)
Se(1)–Cu(2)–Cu(1)
Se(2)–Cu(3)–Se(1)
Se(1)–Cu(3)–Cu(4)
Cu(2)–Cu(3)–Cu(4)
Cl(3)–Cu(5)–Cl(2)
50.96(3)
56.84(3)
70.47(4)
110.05(4)
73.19(4)
138.55(4)
103.33(6)
153.25(6)
55.85(3)
116.35(4)
111.08(4)
73.50(4)
178.1(1)
3 Conclusions
The subsequent formation of clusters of different sizes and
selenium contents during reactions of CuCl with PhSe– and
bidentate N,NЈ-donor ligands is another experimental proof of
the influence of experimental conditions on the structures of
the formed products in such reactions. Particularly the effect
that N,NЈ-donor ligands have on the solubility of the “CuSePh”
intermediates, as well as their contribution to the formation of
bridging μ2-PhSe– and μ3-PhSe– units seems to be essential.
The observed distances found for Cu···Cu interactions in the
compounds 1–3 are shorter than the sum of the van der Waals
radii (2.8 Å), suggesting that these interactions are reinforced
by the bonds to the bridging phenylselenolates.
The variety of products demonstrates how versatile the in-
fluence of N,NЈ-donor ligands can be in the synthesis of novel
“CuSePh” cluster compounds.
The time that the “CuSePh” intermediates remain in solution
can be considered as an important variable for the formation
of structural motifs in the target compounds. This is currently
subject of investigations in our laboratories with the aim to
understand the growing behavior of this class of cluster com-
pounds.
3
Cu(1)–Se(1)
Cu(1)–Se(3)
Cu(1)–Cu(2)
Cu(2)–Se(6)
Cu(2)–Se(3)
Cu(2)–Se(1)
Cu(2)–Cu(3)
Cu(2)–Cu(5)
Cu(2)–Cu(4)
Cu(3)–Se(6)
Cu(3)–Se(4)
Cu(3)–Cu(6)
Cu(3)–Se(2)
Cu(3)–Cu(5)
Cu(3)–Cu(4)
Cu(4)–Se(2)
Cu(4)–Se(1)
Cu(4)–Se(5)
Cu(4)–Cu(5)
Cu(5)–Se(3)
Cu(5)–Se(5)
Cu(5)–Se(4)
Cu(6)–Se(2)
Cu(6)–Se(4)
Cu(1)–Se(1)
Cu(1)–Se(3)
2.432(2)
2.442(1)
2.519(1)
2.353(1)
2.453(1)
2.544(1)
2.605(1)
2.723(1)
2.725(2)
2.339(1)
2.424(1)
2.488(1)
2.539(1)
2.671(1)
2.732(1)
2.348(1)
2.381(1)
2.403(2)
2.796(2)
2.378(1)
2.379(2)
2.382(1)
2.432(1)
2.493(1)
2.432(2)
2.442(1)
Se(1)–Cu(1)–Se(3)
Se(1)–Cu(1)–Cu(2)
Se(3)–Cu(1)–Cu(2)
Se(6)–Cu(2)–Se(3)
Se(6)–Cu(2)–Cu(1)
Se(6)–Cu(2)–Se(1)
Se(3)–Cu(2)–Se(1)
Se(6)–Cu(3)–Se(4)
Se(6)–Cu(3)–Cu(6)
Se(4)–Cu(3)–Cu(6)
Se(6)–Cu(3)–Se(2)
Se(2)–Cu(4)–Se(1)
Se(2)–Cu(4)–Se(5)
Se(1)–Cu(4)–Se(5)
Se(2)–Cu(4)–Cu(2)
Se(3)–Cu(5)–Se(5)
Se(3)–Cu(5)–Se(4)
Se(5)–Cu(5)–Se(4)
Se(2)–Cu(6)–Se(4)
Cu(1)–Se(1)–Cu(2)
Cu(4)–Se(1)–Cu(1)
Cu(4)–Se(2)–Cu(3)
Cu(6)–Se(2)–Cu(3)
Cu(5)–Se(3)–Cu(2)
Cu(1)–Se(3)–Cu(2)
Cu(5)–Se(5)–Cu(4)
103.14(5)
61.81(4)
59.23(4)
142.82(5)
143.01(5)
117.53(5)
99.64(5)
143.70(5)
137.69(5)
60.98(4)
115.69(5)
138.97(7)
113.57(6)
107.27(6)
112.33(5)
105.18(5)
141.38(6)
113.42(5)
101.60(4)
60.79(4)
114.86(6)
67.85(4)
60.03(4)
68.59(4)
61.95(4)
71.55(5)
4 Experimental Section
4.1 General
Solvents and standard reagents were obtained commercially (Aldrich
or Sigma) and purified by standard procedures.[17] Diphenyldiselenide
was prepared following literature procedure.[18] Elemental analyses
(CHN) were obtained with a VARIO EL analyzer (Elementar Analyse-
nsysteme GmbH) from São Paulo University, Brazil. Infrared spectra
were obtained with a Bruker Tensor 27 mid-IR spectrometer. The
analyses were obtained from pellets, with a sample of each compound
(5 mg) dispersed in KBr (50 mg). The absorption bands were regis-
tered using the following classifications of vibrations: ν(Caryl–H) for
stretching of Caryl–H; ν(C=C) for stretching of C=C; δop(C=C–H) for
out-of-plane deformation of C=C–H; and ν(C=N) for stretching of
C=N. Melting point analyses were done with a MicroQuímica
i
Symmetry transformations used to generate equivalent atoms:
–x+1, –y+1, –z; = –x, –y–1, –z–1.
=
ii
the resulting building blocks are connected by two μ2-Cl li-
gands. The copper atoms Cu4 and Cu4Ј are situated outside
the ring and connected to the central unit by μ2-SePh groups
and by Cu···Cu interactions with the Cu3 and Cu3Ј atoms,
respectively. With the exception of Cu3 and Cu3Ј all copper
atoms coordinate with 1,10-phenanthroline ligands. The four MQAPF-301 (0–360 °C).
Z. Anorg. Allg. Chem. 2015, 739–743
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option in SHELXL. Crystal data and more information about the deter-
minations of the structures are given in Table 1.
4.2 Synthesis of [{Cu2(bpy)2(μ3-SePh)}{CuCl2}2]2 (1)
NaBH4 (9.5 mg, 0.25 mmol, in a 0.5 m solution of DME) was added
to a solution of (PhSe)2 (39 mg, 0.125 mmol) in EtOH/THF (4 mL,
1:1). After the solution became transparent, CuCl (24.5 mg,
0.25 mmol) was added, which gave a yellow precipitate. 2,2Ј-Bipyr-
idine (40 mg, 0.25 mmol) dissolved in dimethylformamide (0.5 mL)
was added and the mixture was heated under reflux for 0.5 h. The
precipitate was re-dissolved and the mixture became dark red. During
the cooling period, dark red crystals were formed. Yield: 32 mg (53%)
based on CuCl. Melting point: 105–106 °C. C52H42Cl4Cu6N8Se2
(1459.9): calcd. C 42.78; H 2.90; N 7.68%; found: C 41.78; H 2.93;
N 7.46%. IR (KBr): ν˜ = 3050 [ν(Caryl–H)]; 1593 [ν(C=N)]; 1573,
1471, and 1439 [ν(C–C)]; 732 and 698 [δop(C=C–H)] cm–1.
Crystallographic data (excluding structure factors) for the structures in
this paper have been deposited with the Cambridge Crystallographic
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK. Copies
of the data can be obtained free of charge on quoting the depository
numbers CCDC-994524, CCDC-994525, and CCDC-994526 for
1–3 (Fax: +44-1223-336-033; E-Mail: deposit@ccdc.cam.ac.uk, http://
www.ccdc.cam.ac.uk)
Acknowledgments
This work was supported by funds from CNPq, CAPES and
FAPERGS.
4.3 Synthesis of [{Cu4(phen)3(μ2-SePh)(μ3-SePh)}2(μ2-
Cl)2](CuCl2)2·2(PhSe)2 (2)
References
NaBH4 (9.45 mg, 0.25 mmol, in a 0.5 m solution of DME) was added
to a solution of (PhSe)2 (39 mg, 0.125 mmol) in EtOH/THF (4 mL,
1:1). After the formation of a transparent solution, CuCl (24.5 mg,
0.25 mmol) was added, resulting in the formation of a yellow precipi-
tate. 1,10-Phenanthroline (45 mg, 0.25 mmol), dissolved in dimethyl-
formamide (5 mL), was added and the mixture was stirred at 85 °C for
0.5 h. The resulting clear red solution was kept in an atmosphere of
dry argon for 3 d. Red crystals precipitated during this time. Yield:
23 mg (29%) based on CuCl. Melting point: 112 °C.
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C120H88Cl6Cu10N12Se8 (3177.9): calcd. C 45.35; H 2.79; N 5.29%;
found: C 46.12; H 3.12; N 5.21%. IR (KBr): ν˜ = 3048 [ν(Caryl–H)];
1572 [ν(C=N)]; 1508, 1471, and 1432 [ν(C–C)]; 724 and 690
[δop(C=C–H)] cm–1.
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4.4 Synthesis of [Cu6(bpy)2(μ2-SePh)2(μ3-SePh)4]·(THF) (3)
NaBH4 (9.45 mg. 0.25 mmol in a 0.5 m solution of DME) was added
to a solution of (PhSe)2 (39 mg, 0.25 mmol) in EtOH/THF (4 mL, 1:1).
After the formation of
a transparent solution, CuCl (24.5 mg,
0.25 mmol) was added, resulting in the formation of a yellow precipi-
tate. 2,2Ј-Bipyridine (40 mg, 0.25 mmol) dissolved in THF (5 mL),
was added and the mixture was stirred at room temperature for
0.5 h. The resulting clear, dark red solution was stored in an atmo-
sphere of dry argon for one week, which gave dark red single
crystals. Yield: 21 mg (30%) based on CuCl. Melting point: 157 °C.
C60H54Cu6N4OSe6 (1702.1): calcd. C 42.34; H 3.20; N 3.29%; found:
C 40.35; H 3.05; N 3.38%. IR (KBr): ν˜ = 3047 [ν(Caryl–H)]; 1593
[ν(C=N)]; 1572, 1470, and 1436 [ν(C–C)]; 733 and 690 [δop(C=C–
H)] cm–1.
4.5 X-ray Structure Determinations
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A Bruker CCD X8 Kappa APEX II diffractometer equipped with a
graphite monochromator and Mo-Kα radiation (λ = 0.71073 Å) was
used for the X-ray structure analyses. The structures were solved by
direct methods with SHELXS and refined with SHELXL by using
anisotropic displacement parameters for all non-hydrogen atoms.[19]
The positions of the hydrogen atoms bonded to carbon atoms were
calculated for idealized positions and treated with the “riding model”
537.
[19] G. M. Sheldrick, Acta Crystallogr., Sect. A 2008, 64, 112–122.
Received: December 7, 2014
Published Online: January 22, 2015
Z. Anorg. Allg. Chem. 2015, 739–743
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