Group 11 complexes with imidazoline-2-thione or selone derivatives

Article abstract of DOI:10.1002/ejic.201100124

The reactions of the organodichalcogenone ligands Bbit[1,1′-(butane- 1,4-diyl)bis(3-methylimidazoline-2-thione)],Mbis [1,1′-methylenebis(3- methylimidazoline-2-selone)], Ebis [1,1′-(ethane-1,2-diyl)bis(3- methylimidazoline-2-selone)] and Pbis [1,1′-(pentane1,5-diyl)bis(3- methylimidazoline-2-selone)] with gold(I/III), silver(I) and copper(I) have been studied by elemental analysis, multinuclear (¹H, ¹³C, ¹⁹F, ³¹P and ⁷⁷Se) NMR spectroscopy and for several products obtained the molecular structures were also established by single-crystal X-ray diffraction analysis. In most cases the organodichalcogenone coordinates to two metallic fragments as a bidentate bridging ligand but the ligand Mbis coordinates to silver(I) in an unprecedented tetradentate bridging-chelate mode. Copyright

Full text of DOI:10.1002/ejic.201100124

FULL PAPER
DOI: 10.1002/ejic.201100124
Group 11 Complexes with Imidazoline-2-thione or Selone Derivatives
M. Teresa Aroz,[a] M. Concepción Gimeno,*[a] Monika Kulcsar,[a] Antonio Laguna,[a] and
Vito Lippolis[b]
Keywords: Gold / Silver / Copper / Selenium / N ligands / Supramolecular structures
The reactions of the organodichalcogenone ligands Bbit
[1,1Ј-(butane-1,4-diyl)bis(3-methylimidazoline-2-thione)],
19F, 31P and 77Se) NMR spectroscopy and for several products
obtained the molecular structures were also established by
single-crystal X-ray diffraction analysis. In most cases the or-
ganodichalcogenone coordinates to two metallic fragments
as a bidentate bridging ligand but the ligand Mbis coordi-
nates to silver(I) in an unprecedented tetradentate bridging-
chelate mode.
Mbis
Ebis
[1,1Ј-methylenebis(3-methylimidazoline-2-selone)],
[1,1Ј-(ethane-1,2-diyl)bis(3-methylimidazoline-2-se-
lone)] and Pbis [1,1Ј-(pentane1,5-diyl)bis(3-methylimid-
azoline-2-selone)] with gold(I/III), silver(I) and copper(I) have
been studied by elemental analysis, multinuclear (1H, 13C,
Furthermore, few complexes with any selone ligands have
been described for gold. In the complexes we describe, the
ligands predominantly coordinate as bidentate bridging two
metal centres; however, we also report a silver(I) complex
with Mbis in which the ligand acts as tetradentate bridging-
chelate organodichalcogenone system, which represents an
unprecedented mode of coordination for this type of ligand.
Introduction
The coordination chemistry of organochalcogenone
compounds featuring two or more 3-methylimidazole-2-
thione/selone groups has not been studied in depth in spite
of the potential that these species might have in biomedical
applications[1–3] as well as their interesting structural coor-
dination chemistry. A few complexes with these types of
ligands are described in the literature and most are charge
[5]
transfer or hypervalent T-shaped adducts with Br2,[4] I2
Results and Discussion
and IBr.[6] Recently new complexes with the chelating or-
ganodichalcogenone ligands Mbit/Mbis [1,1Ј-methyl-
enebis(3-methylimidazoline-2-thione/selone)] or Ebit/Ebis
[1,1Ј-(1,2-ethanediyl)bis(3-methylimidazoline-2-thione/sel-
one)] with nickel(II), cobalt(II),[7] rhodium(III) and iridi-
um(III)[8] have been reported. Complexes of Mbit with
Synthesis
The syntheses of Bbit,[13] Mbis and Ebis[5] are known in
the literature, and consist of two steps: the synthesis of the
appropriate 3-methylimidazolium bis-cation salt and its re-
action with elemental sulfur or selenium in methanol in the
presence of a slight excess of K2CO3. We have improved the
overall yield of this procedure by preparing quantitatively
the 3-methylimidazolium bis-cation salts from the reaction
of 1-methyl imidazole with an excess of the appropriate ter-
minal dihalide under solvent-free and reflux conditions.[14]
The use of solvent (AcOEt, THF) and stoichiometric quan-
tities of the reactants in this step generally causes a signifi-
cant decrease in yield of the 3-methylimidazolium bis-cation
salt intermediate. We have also applied this synthetic pro-
cedure to the preparation of the new ligand Pbis (see Exp.
Sect.).
other metals have also been studied: SbIII, BiIII [9] SnIV,[10]
,
PbII[11] and AgI.[12] The most intensely studied ligand is
Mbit and different coordination modes have been described
in its metal complexes. A bidentate chelate fashion is pre-
dominant in most of the complexes that have been structur-
ally characterised but other coordination modes such as bi-
dentate bridging two metal centres have been found in co-
balt(II)[7] and silver(I) polymeric complexes.[12]
Here we report the synthesis and characterization, both
in solution and solid state, of new complexes with Bbit,
Mbis, Ebis and Pbis with different metals: AuI, AuIII, AgI
and CuI. To the best of our knowledge no gold(I/III) or
copper(I) complexes have been reported with this type of
ligand and only one example is known with silver(I).
New gold(I/III) complexes were obtained by reacting the
organodichalcogenone ligands with [Au(C6F5)(tht)][15] (tht
=
tetrahydrothiophene), [Au(C6F5)3(tht)],[16] [Au(OTf)-
–
(PPh3)] (OTf = CF3SO3 ), or [Au(OTf)(PPh2py)] at room
temperature, in a 1:2 molar ratio in dry organic solvents,
i.e. THF (1, 2 and 4), CH2Cl2 (3, 5–13, 15 and 16) and
acetone (14) (Scheme 1). All of the complexes isolated have
a 1:2 ligand to metal stoichiometry and those structurally
characterised feature ligands bridging two metal fragments.
[a] Departamento de Química Inorgánica, Instituto de Ciencia de
Materiales de Aragón, Universidad de Zaragoza – CSIC,
50009 Zaragoza, Spain
[b] Dipartamento di Chimica Inorganica ed Analitica, Università
degli Studi di Cagliari,
S. S. 554 Bivio per Sestu, 09042 Monserrato (CA), Italy
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Group 11 Complexes with Imidazoline Derivatives
Scheme 1. i) 2 [Au(C6F5)(tht)], ii) 2 [Au(OTf)(PPh3)] or 2 [Au(OTf)(PPh2py)], iii) 2 [Au(C6F5)3(tht)].
Silver(I) complexes were obtained after using a similar ried out using [Cu(CH3CN)4]PF6 with the ligands in a mo-
procedure as described above. The reactions have been car- lar ratio of 1:1. On the basis of microanalytical data, for
ried out with [Ag(OTf)(PPh3)] or Ag(OTf) in a molar ratio the products we propose either a dinuclear structure with
of 1:2 (Scheme 2). We propose that 1:2 complexes similar two ligand units bridging two metal centres or a polymeric
to those of gold are obtained, containing ligands bridging structure (see Scheme 3); no coordinated acetonitrile mole-
two metal centres with the exception of 18 with Mbis. In cules have been detected in the NMR spectra of the prod-
this case we have obtained [Ag4(PPh3)4(Mbis)3] featuring a ucts.
unique adamantane-like Ag4Se6 central core. For this
All the isolated complexes form either stable white (1, 4,
reason the synthesis of complex 18 was repeated in 3:4 li- 5–7, 9–13, 17–26 and 27) or pale yellow (2, 3, 8, 9, 14–
gand/[Ag(OTf)(PPh3)] molar ratio obtaining the pure com- 16 and 28) crystalline solids, which were characterized by
pound in high yield. For copper(I) the reactions were car- elemental analysis, multinuclear NMR spectroscopy (1H,
Scheme 2. i) 2 [Ag(OTf)(PPh3)], ii) 4/3 [Ag(OTf)(PPh3)], iii) 2 Ag(OTf).
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following ranges: 3.56–3.78 for –CH3 and 6.54–6.80 ppm
1
for –CH2–. The H NMR spectrum of Ebis ligand exhibits
the following pattern in DMSO: 3.54 for –CH3 and
4.44 ppm for –(CH2)2–. The ranges of the values for the
corresponding complexes are: 3.40–3.81 for –CH3 and 4.51–
4.80 ppm for –CH2–. For the Pbis ligand in DMSO, 1H
NMR signals are observed at 1.23, 1.72 and 4.01 for –(CH2)
5– and at 3.55 ppm for –CH3; in the corresponding com-
plexes the range of variability of these resonances is 1.19–
1.36, 1.71–2.09, 4.07–4.42 and 3.64–3.99 ppm, respectively.
The –CH–CH– protons of the imidazole rings appear in the
range 7.12–7.76 ppm in the ligands and in the metal com-
plexes a downfield shift is observed.
For the gold(I) derivatives 1–4 the 19F NMR spectra
show one set of resonances corresponding to the pentafluo-
rophenyl group; two multiplets for the ortho and meta and
a triplet for the para fluorine. In contrast, in the gold(III)
derivitives 5–8 the 19F NMR spectra exhibit a typical
pattern for a square-planar geometry of the complex anion;
two sets of resonances in a 2:1 intensity ratio for the trans
and cis pentafluorophenyl groups, respectively. All the 19F
NMR spectra of the complexes containing the OTf group
show a single signal corresponding to the anion.
The room temperature 31P{1H} and 77Se NMR spectra
for all of the complexes exhibit a singlet resonance. This
behaviour is consistent with the equivalence, in solution and
on the NMR time scale, of the phosphorus and selenium
atoms, respectively, in the molecular unit of compounds
containing phosphane ligands.
Scheme 3. Proposed structures for the copper complexes.
19F, 31P{1H}, 77Se and 13C{1H} in some of the complexes)
in different deuterated solutions at room temperature. We
were able to grow single crystals suitable for X-ray diffrac-
tion studies of 2, 7, 13 and 18. The molecular structure of
Pbis was also determined.
In the 77Se NMR spectra a slight deshielding is observed
for the gold complexes of the same ligand, e.g. with Ebis
δSe = –23.4 in 3, 8.2 in 11 and 18.5 ppm in 15. This slight
deshielding is due to the different AuL fragments:
Au(C6F5), Au(PPh3)+, Au(PPh2py)+, respectively. The de-
NMR Studies of Complexes
The NMR spectra for the gold(I/III) complexes were re- shielding increases with the increasing donor character of
corded in different deuterated solvents {CDCl3 (2, 11–13), the AuL. A similar trend was observed for the silver com-
[D6]acetone (5, 7) and [D6]DMSO (1, 3, 4, 6, 8–10, 14– plexes, e.g. with Ebis δSe = –73.9 in 19 and –160.6 ppm in
16)}, at room temperature. Due to the low solubility of the 23 with Ag(PPh3)+ and Ag(OTf), respectively. The reso-
silver(I) and copper(I) complexes in organic solvents, their nances for the selenium in the copper complexes were not
NMR spectra were recorded in [D6]DMSO. The 77Se NMR observed after several hours because lack of solubility.
spectra were recorded in [D6]DMSO. The assignment of the
1H and 13C chemical shifts was made on the basis of 2D
(COSY, HMQC and HMBC) NMR experiments. The 13C
NMR spectra have not been recorded for all the complexes
Crystal Structures
because the low solubility, lack of information of the struc-
The crystal structure of the Pbis ligand and the com-
ture of many of them and, in the case of complexes with plexes 2, 7, 13 and 18 have been determined by single-crys-
pentafluorophenyl units, because these carbon atoms are tal X-ray diffraction studies and the crystallographic data
not usually observed in the 13C NMR spectra.
are given in Table 1.
1
The aliphatic region of the H NMR spectrum of the
The ORTEP diagram for Pbis is shown in Figure 1. The
ligand Bbit in DMSO presents the resonance signals 1.64, Pbis ligand crystallized with a water molecule. The molecu-
3.96 and 3.55 ppm for –(CH2)4– and –CH3. For the corre- lar structure shows that the imidazoline-2-selone rings are
sponding gold(I/III), silver(I) and copper(I) complexes the cis to each other and the bridging chain formed by the
ranges of the values of these resonances are: 1.73–1.83 and –(CH2)5– alkyl moiety assumes a zigzag conformation.
3.96–4.13 for –(CH2)4– and 3.42–3.62 ppm for –CH3. In the There are several secondary bonds that can be considered
1
case of the Mbis ligand the H NMR spectrum in DMSO as hydrogen bonds, the shortest are O1···H4# 2.353(2) Å
exhibits in the aliphatic region singlet resonances for –CH3 (# x – 1, y – 1, z) and Se2···H1# 2.680(45) Å with sub-
(3.56 ppm) and –CH2– (6.34 ppm) groups. For the corre- tended angles of 156.2 and 167.1°, respectively. These bonds
sponding metal complexes the resonances are found in the define a three dimensional supramolecular array (Figure 2).
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Group 11 Complexes with Imidazoline Derivatives
Table 1. Crystalllographic data for Pbis·H2O ligand and complexes 2, 7, 13 and 18.
Pbis·H2O
2
7
13·2CH2Cl2
18·2Me2CO·H2O
Empirical formula C13H22N4OSe2 C10.50H6AuF5N2Se C46H14Au2F30N4Se2 C52H50Au2Cl4F6N6O6P2S4 C112H118Ag4F12N12O17P4S4Se6
M
408.27
100(2)
orthorhombic
Pbca
11.513(2)
8.7040(17)
33.124(7)
90
531.10
100(2)
monoclinic
C2/c
10.897(2)
15.871(3)
14.972(3)
90
91.10(3)
90
2589.1(9)
8
1744.47
100(2)
monoclinic
P21/n
10.733(2)
13.859(3)
17.730(4)
90
106.23(3)
90
2532.2(9)
2
1694.89
100(2)
3289.54
100(2)
orthorhombic
Pbca
29.065(6)
29.208(6)
29.912(6)
90
90
90
25394(9)
8
2.528
T [K]
Crystal system
Space group
a [Å]
b [Å]
c [Å]
triclinic
¯
P1
11.530(2)
11.875(2)
12.164(2)
98.90(3)
95.97(3)°
116.05(3)
1450.2(5)
1
5.510
0.0499
0.1285
1.053
α [°]
β [°]
90
90
γ [°]
V [Å3]
Z
3319.3(11)
8
μ(Mo-Kα) [mm–1] 4.457
14.223
0.0165
0.0379
1.161
7.375
R1 [IϾ2σ(I)]
wR2
0.0288
0.0530
1.185
0.0201
0.0452
1.162
0.0408
0.0882
1.072
GOF on F2
2.562(2) Å, cf. sum of the respective van der Waals radii
∑rvdW(F,H) ≈ 2.70 Å].[17] Closer inspection of the crystal
structure revealed the presence of intermolecular F···Hmethyl
hydrogen bonding interactions [F5···H11b# 2.287(2) Å
(# –x, y, –z + 1/2)], which give rise to zigzag polymeric
chains in the crystal lattice (Figure 4).
Figure 1. ORTEP representation at 50% probability and atom
numbering scheme for Pbis in Pbis·H2O. Selected bond lengths [Å]
and angles (°): Se1–C2 1.854(3), Se2–C10 1.848(3), N2–C2–N1
105.6(2), N2–C2–Se1 127.27(18), N1–C2–Se1 127.09(19), N3–C10–
N4 105.6(2), N3–C10–Se2 127.23(18), N4–C10–Se2 127.16(18).
Figure 3. ORTEP representation at 50% probability and atom
numbering scheme for 2. Selected bond lengths [Å] and angles (°):
Au1–C1 2.035(3), Au1–Se1 2.4263(5), Se1–C7 1.894(4), C1–Au1–
Se1 177.49(10), C7–Se1–Au1 97.84(10), N1–C10–N1 109.6(4).
To date only one molecular structure containing the frag-
ment –C–Au–Se=, [Au(C6F5)(SePPh3)], has been re-
ported.[18] The compound has hydrogen bonding interac-
tions between two molecules forming dimers (F···H 2.51 Å).
In the crystal there are interdimer F···Hphenyl contacts
(F···H 2.56 Å), which result in a polymeric association of
the dimers.
The coordination geometry about the gold(I) atoms in 2
is linear [C1–Au1–Se1 177.49(10)°], whereas the bond con-
nection about the selenium atom is V-shaped [C7–Se1–Au1
Figure 2. A layer network based on intermolecular hydrogen bond-
ing in the crystal of Pbis·H2O.
Figure 3 presents the ORTEP diagram for complex 2 97.84(10)°]. These values are comparable to those found in
with the imidazoline-2-selone rings trans to each other. In [Au(C6F5)(SePPh3)]: C–Au–Se 177.1(1)° and P–Se–Au
the molecular structure weak intramolecular interactions 99.9(1)°. The Se1–Au1 bond length [2.4263(5) Å] in 2 is of
are formed between one fluorine atom of the C6F5 group the same magnitude as that found in [Au(C6F5)(SePPh3)]
and one hydrogen atom of the imidazoline ring [F1–H8 [Se–Au 2.416(1) Å].[18]
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Figure 4. View along the b axis of the chain polymer in 2.
A few structurally characterised metal complexes of contacts (F···H 2.48 Å and 2.52 Å) involving the methyl
Mbis have been reported: [NiBr2(Mbis)], [CoCl2(Mbis)]n, groups leads to a layered structure in which a monomeric
[Cp*Ir(Mbis)Cl]Cl and [Cp*Rh(Mbis)Cl][Cp*RhCl3].[7,8] complex unit is connected to four neighboring molecules
The complex [CoCl2(Mbis)]n is different from the others in (Figure 6).
that polymeric chains are formed through the coordinative
interactions established between the cobalt centres and the
selenium atoms of Mbis which behaves as a bridging-che-
late ligand. Also in this molecular structure, weak interac-
tions are present between the hydrogen atoms of the CH2
group and the imidazoline ring. The imidazoline-2-selone
rings are trans to each other, as in 2, and the coordination
geometry around the selenium atoms in [CoCl2(Mbis)]n is
V-shaped, with a C–Se–Co angle of 93.6°. In the other three
complexes of Mbis the ligand does not bridge two metal
centres but behaves as a chelating bidentate ligand forming
an eight-membered metallacycle with the metal centres.
Single crystals suitable for X-ray diffraction studies were
obtained for 7 and the molecular structure is presented in
the Figure 5. The molecular structures of 2 and 7 are very
similar. In 7, as in 2, the imidazoline-2-selone rings are trans
to each other and the ligand bridges two metal centres. Also
similar to 2, in 7 there are intramolecular F1···H4b contacts
between one fluorine atom of the C6F5 group and one hy-
drogen atom from the alkyl chain bridging the imidazoline
Figure 6. A layer network based on intermolecular hydrogen bond-
rings (Figure 5). Furthermore, the intermolecular F···H ing in 7.
Figure 5. ORTEP representation at 50% probability and atom numbering scheme for 7. Selected bond lengths [Å] and angles (°): Au1–
C21 2.043(3), Au1–C11 2.052(3), Au1–C31 2.061(3), Au1–Se1 2.4607(6), Se1–C1 1.884(3), C21–Au1–Se1 173.43(9), C11–Au1–Se1
97.69(8), C31–Au1–Se1 85.09(8), C21–Au1–C11 88.83(12), C21–Au1–C31 88.40(12), C1–Se1–Au1 103.58(9).
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Group 11 Complexes with Imidazoline Derivatives
The coordination geometry around the gold(III) atoms
Furthermore, the values of the sulfur–gold distances are
in 7 is square planar [C31–Au1–Se1 85.09(8)°, C11–Au1– similar in all four complexes: 2.313(2) in 13, 2.3335(17) in
Se1 97.69(8)°, C21–Au1–C31 88.40(12)°, C21–Au1–C11 [Au(PhTmMe)(PEt3)], 2.3511(12) in Au(BmMe)(PPh3) and
88.83(12)°] and distorted V-shaped around the selenium 2.3488(11) Å in [Au(TmtBu)(PPh3)].
atoms [C1–Se1–Au1 103.58(9)°]. The main reason for the
In 13, several secondary hydrogen bonds between the flu-
distortion from ideal square planar and V-shaped geome- orine atoms from the OTf groups and hydrogen atoms from
tries around the gold and selenium atoms could be due to the phenyl and pyridyl groups are also present to form a
the sterically demanding C6F5 groups. The selenium–gold polymeric chain in the crystal lattice: [F···Hpyridyl
distance [2.4607(6) Å] is comparable with those found in 2 {F2···H24# 2.617(7) Å, # –x + 1, –y, –z}] and F···Hphenyl
[2.4263(5) Å] and [Au(C6F5)(SePPh3)] [2.416(1) Å].[18]
[F1···H12 2.46(1) Å] (Figure 8).
The structure of 13 was also confirmed by X-ray diffrac-
Figure 9 presents the molecular structure of 18, which
tion studies and is shown in Figure 7. The gold(I) atoms crystallized with an acetone molecule. In the literature, the
have linear coordination geometry [P1–Au1–S1 molecular structure of only one complex featuring the frag-
a
173.77(7)°] and the sulfur atoms have a distorted V-shaped ment Ag–Se=C, [{μ-SeC(NH2)2}Ag{SeC(NH2)2}2]2Cl2·
geometry [C1–S1–Au1 106.5(3)°]. These values are similar 4DMF, has been established by single-crystal X-ray diffrac-
to those found in the other three complexes that contain an tion studies.[22]
imidazoline thione group: [Au(PhTmMe)(PEt3)][19] [TmMe
tris(2-mercapto-1-methylimidazolyl)borate] [P1–Au1–S1
=
171.55(7)° and C1–S1–Au1 101.0(2)°], [Au(TmtBu)(PPh3)][20]
[TmtBu = tris(2-mercapto-1-tert-butylimidazolyl)borate] [P–
Au–S1 97.21(4) and P–Au–S2 159.75(4)°] and [Au(BmMe)-
(PPh3)][21] [BmMe = bis(2-mercapto-1-methylimidazolyl)-
borate] [P–Au–S1 98.78(4)° and P–Au–S2 159.74(4)°], in
which both sulfur atoms are coordinated to the gold centre.
Figure 9. Molecular structure of the complex cation [Ag4(PPh3)4-
(Mbis)3]4+ in 18, all hydrogen atoms, phenyl gropus from PPh3 and
counter anions are omitted for clarity. Selected bond lengths [Å]
and angles (°): Ag1–Se1 2.6603(7), Ag1–Se3 2.6693(7), Ag1–Se6
2.7251(7), Ag2–Se5 2.6818(7), Ag2–Se1 2.6885(7), Ag2–Se2
2.6937(7), Ag3–Se6 2.6440(7), Ag3–Se4 2.6819(7), Ag3–Se5
2.7151(7), Ag4–Se3 2.6377(7), Ag4–Se2 2.6747(7), Ag4–Se4
2.6815(7), Se1–Ag1–Se3 108.18(2), Se1–Ag1–Se6 111.637(19), Se3–
Ag1–Se6 104.69(2), Se5–Ag2–Se1 104.29(2), Se5–Ag2–Se2
Figure 7. ORTEP representation at 50% probability and atom
numbering scheme for the complex cation [Au2(PPh2py)2(Bbit)]2+
in 13. All hydrogen atoms, counter anions and solvents (CH2Cl2)
are omitted for clarity. Selected bond lengths [Å] and angles (°):
Au1–S1 2.313(2), S1–C1 1.726(9), Au1–P1 2.264(2), P1–Au1–S1 102.40(2), Se1–Ag2–Se2 106.40(2), Se6–Ag3–Se4 109.66(2), Se6–
173.77(7), C1–S1–Au1 106.5(3), N1–C1–S1 124.4(8), N2–C1–S1 Ag3–Se5 108.58(2), Se4–Ag3–Se5 97.019(19), Se3–Ag4–Se2
128.1(8).
108.23(2), Se3–Ag4–Se4 109.41(2), Se2–Ag4–Se4 101.75(2).
Figure 8. View along the a axis of the chain polymer in 13.
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In complex 18, the tetracation [Ag4(PPh3)4(Mbis)3]4+ fea-
tures a rare adamantane-like Ag4Se6 central core with four
AgPPh3+ fragments bridged by three Mbis units (Figure 9).
In order to satisfy this topological disposition, each ligand
acts as a tetradentate bridging-chelate system, which is an
unprecedented coordination structural feature for organod-
iselone ligands. Each ligand is connected to three different
metal centres, each Se donor in each ligand bridges two
Experimental Section
General Procedures: Elemental (C, H, N and S) analyses were car-
ried out with a Perkin–Elmer 2400 microanalyzer. Room-tempera-
ture NMR spectra were recorded with a Bruker ARX 400 spec-
trometer (1H, 400 MHz, 13C{1H} 100.61 MHz, 19F, 376.5 MHz and
31P{1H} NMR, 161.9 MHz). The chemical shifts are reported in
ppm relative to the residual solvent peak [1H (CD3)2CO: 2.05,
CHCl3: 7.26 and DMSO 2.50 ppm], SiMe4, CFCl3 and H3PO4
85%, respectively. 77Se spectra were obtained at 76.4 MHz in
CDCl3 with a BRUKER ARX 400 spectrometer using dimethyl
selenide as an external standard. Cyclic voltammetric experiments
were performed by with an EG&G PARC Model 273 potentiostat.
A three-electrode system was used, which consisted of a platinum
disk working electrode, a platinum wire auxiliary electrode and a
saturated calomel reference electrode. The measurements were car-
ried out in CH2Cl2 with 0.1 m Bu4NPF6 as a supporting electrolyte.
Under the present experimental conditions, the ferrocenium/ferro-
cene couple was located at 0.47 V vs. SCE.
+
AgPPh3 units and, at the same time, the two Se donor
+
atoms from each ligand are bridged by one AgPPh3 unit
following the sequence Ag–Se–Ag–Se–Ag (the Se donors
belong to the same ligand). Consequently, the coordination
geometry around each silver centre is tetrahedral with each
silver(I) atom bonded to three selenium atoms and one
phosphorus atom. Interestingly, only one silver centre
[Ag(1) in Figure 9] is bound to three selenium atoms each
from a different ligand unit. The Ag–Se distances lie in the
range 2.6603(7) to 2.7251(7) Å, and are, therefore, similar
to those found in [{μ-SeC(NH2)2}Ag{SeC(NH2)2}2]2Cl2·
4DMF for the bridging selenourea units [2.706(2) and
2.750(2) Å]. In the Ag4Se6 core there are no interactions
between the silver atoms. Adamantane-like Ag4Se6 discrete
cluster arrangements have also been described in the com-
plex ions [Ag4(SePh)6]2–,[23] [Ag4(Se4)3]2–,[24] [Ag4{(Se-
Starting Materials: Solvents were dried and distilled prior to use.
1-methylimidazole, Ag(O3SCF3) and terminal alkyl dihalides are
commercially available. Other starting materials were prepared ac-
cording to literature methods: Bbit,[13] Mbis,[5] Ebis,[5]
[Au(C6F5)(tht)],[15] [Au(C6F5)3(tht)],[16] [AuCl(PPh3)],[27] [AuCl-
(PPh2py)],[28] [Ag(OTf)(PPh3)][29] and [Cu(NCMe)4]PF6.[30]
Pbis: A mixture of 1,5-bis(3-methyl-imidazolium)pentane diiodide
(obtained quantitatively by refluxing 1-methylimidazole in 1,5-di-
iodopentane for 2 h, followed by filtration and washing of the solid
with diethyl ether) (9.70 g, 0.02 mol), K2CO3 (4.5 g, 0.03 mol), ele-
2–
PPh2)2N}3]+,[25] and [Ag4(fcSe2)3]2– (fcSe2 = ferrocenyldi-
selenolate).[26] However, in all of these complex ions the ad-
amantane-like Ag4Se6 arrangement is distorted so as to
bring each silver(I) centre to assume a trigonal planar coor- mental Se (3.2 g, 0.04 mol) and ethanol (300 mL) was stirred under
reflux for 24 h and filtered hot through a pad of celite. The solution
was evaporated to dryness and the compound was obtained as an
orange powder by crystallization from CH2Cl2/ethanol; yield 70%,
5.46 g. C13H20N4Se (312.085): calcd. C 40.01, H 5.17, N 14.36;
dination of selenium atoms, and to establish Ag···Ag inter-
actions of about 3.0 Å with the other three metal centres
within a tetrahedral Ag4 disposition. The tetrahedral geom-
etry around each silver(I) centre in [Ag4(PPh3)4(Mbis)3]4+ is
determined by the presence of the coordinated PPh3, which
prevents the four metal centres from establishing ar-
gentophilic interactions with each other for steric reasons,
thus preserving a regular adamantane-like arrangement for
the Ag4Se6 cluster.
1
found C 39.98, H 5.14, N 14.30. H NMR (DMSO, 400 MHz): δ
3
3
= 1.23 [q, JHH = 7.7 Hz, 2 H, –(CH2)5–], 1.72 [q, JHH = 7.4 Hz,
3
4 H, –(CH2)5–], 3.55 (s, 6 H, –CH3), 4.01 [t, JHH = 7.3 Hz, 4 H,
–(CH2)5–], 7.33 (d, 3JHH = 2.3 Hz, 4 H, –CH=CH–), 7.34 (m, 3JHH
= 2.3 Hz, 4 H, –CH=CH–) ppm. 13C NMR (DMSO, 100.6 MHz):
δ = 22.57 and 27.93 [s, –(CH2)5–], 36.20 (s, –CH3), 48.33 [s,
The cyclic voltamomgram of 18 in dichloromethane –(CH2)5–], 119.34 and 120.42 (s, –CH=CH–), 154.15 (s, –C=Se),
77Se NMR (DMSO, 76.4 MHz): δ 11.13 (s, 2 Se) ppm. Crystals
suitable for X-ray diffraction analysis were grown from acetone/
diethyl ether.
shows features very similar to those observed for the free
ligand.[4]
[Au2(C6F5)2(Bbit)] (1): [Au(C6F5)(tht)] (0.13 g, 0.28 mmol) and Bbit
(0.042 g, 0.14 mmol) were stirred in THF (50 mL) for 1 h at room
temperature. The white solution was concentrated under reduced
pressure and solid was precipitated with hexane. The product was
Conclusions
collected by filtration and recrystallized from acetone/n-hexane
(1:5, v/v); yield 80%, 0.12 g. C24H18Au2F10N4S2·C3H6O (1068.056):
New gold(I/III), silver(I) and copper(I) complexes with
organodichalcogenone compounds featuring two 3-methyl-
imidazoline-2-thione/selone groups have been prepared and
characterized. These complexes are scarcely represented for
these types of ligands. In the complexes reported we have
found that coordination predominantly takes place with the
ligands bridging two metal centres, but we have found one
example for silver(I) with Mbis in which the ligand acts
as tetradentate bridging-chelate ligand, which represents an
unprecedented mode of coordination for this type of ligand.
This coordination mode gives rise to a rare example of an
Ag4Se6 cluster having a slightly distorted adamantane-like
structure.
calcd. C 30.34, H 2.26, N 5.24, S 5.99; found C 30.70, H 2.42, N
5.38, S 6.35. 1H NMR (DMSO, 400 MHz): δ = 1.85 [br. s, 4 H,
–(CH2)4–], 3.78 (s, 6 H, –CH3), 4.31 [br. s, 4 H, –(CH2)4–], 7.53 (br.
s, 4 H, –CH=CH–) ppm. 19F NMR (DMSO, 376.48 MHz): δ =
3
–162.4 (m, 4 F, –C6F5-meta), –160.3 (t, JFF = 21.2 Hz, 2 F, –C6F5-
para), –115.3 (m, 4 F, –C6F5-ortho) ppm.
[Au2(C6F5)2(Mbis)] (2): Compound 2 was synthesised by the same
procedure described for
1
using [Au(C6F5)(tht)] (0.127 g,
0.28 mmol) and Mbis (0.047 g, 0.14 mmol); yield 80%, 0.12 g.
C21H12Au2F10N4Se2 (1063.856): calcd. C 23.69, H 1.14, N 5.26;
1
found C 23.47, H 1.28, N 4.86. H NMR (CDCl3, 400 MHz): δ =
3
3.79 (s, 6 H, –CH3), 6.70 (s, 2 H, –CH2–), 6.89 (d, JHH = 2.1 Hz,
2890
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© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2011, 2884–2894

Group 11 Complexes with Imidazoline Derivatives
2 H, –CH=CH–), 8.14 (s, 2 H,br, –CH=CH–) ppm. 19F NMR para), –124.2 (m, 4 F, –C6F5-ortho), –121.8 (m, 8 F, –C6F5-para)
(CDCl3, 376.48 MHz): δ = –162.4 (m, 4 F, –C6F5-meta), –159.5 (t, ppm. 77Se NMR (DMSO, 76.4 MHz): δ 43.9 (s, 2 Se) ppm.
3JFF = 20.1 Hz, 2 F, –C6F5-para), –116.6 (m, 4 F, –C6F5-ortho) ppm.
[Au2(C6F5)6(Pbis)] (8): Compound 8 was synthesised by the same
77Se NMR (DMSO, 76.4 MHz): δ –17.5 (s, 2 Se) ppm.
procedure described for
5 using [Au(C6F5)3(tht)] (0.181 g,
0.23 mmol) and Pbis (0.045 g, 0.115 mmol); yield 87%, 0.18 g.
C49H20Au2F30N4Se2 (1787.887): calcd. C 32.89, H 1.13, N 3.13;
[Au2(C6F5)2(Ebis)] (3): Compound 3 was synthesised by the same
procedure described for using [Au(C6F5)(tht)] (0.045 g,
0.10 mmol) and Ebis (0.017 g, 0.05 mmol) in CH2Cl2 (20 mL); yield
46%, 0.04 g. C22H14Au2F10N4Se2 (1077.872): calcd. C 24.49, H
1.31, N 5.21; found C 24.69, H 1.36, N 5.43. 1H NMR [DMSO,
400 MHz]: δ = 3.82 (s, 6 H, –CH3), 4.80 (s, 4 H, –CH2–CH2–), 7.49
1
1
found C 32.83, H 1.20, N 3.22,. H NMR (DMSO, 400 MHz): δ =
3
1.16 [m, 2 H, –(CH2)5–], 1.71 [t, JHH = 6.8 Hz, 4 H, –(CH2)5–],
3
3.70 (s, 6 H, –CH3), 4.07 [t, JHH = 6.2 Hz, 4 H, –(CH2)5–], 7.68
3
3
(d, JHH = 1.9 Hz, 2 H, –CH=CH–), 7.69 (d, JHH = 1.9 Hz, 2 H,
–CH=CH–) ppm. 19F NMR (DMSO, 376.48 MHz): δ = –161.7 (m,
4 F, –C6F5-meta), –161.0 (m, 8 F, –C6F5-meta), –157.4 (m, 6 F,
–C6F5-para), –122.3 (m, 4 F, –C6F5-ortho), –119.9 (m, 8 F, –C6F5-
ortho), 77Se NMR (DMSO, 76.4 MHz): δ 49.6 (s, 2 Se) ppm.
and 7.65 (s,
4
H, –CH=CH–) ppm. 19F NMR [DMSO,
3
376.48 MHz]: δ = –162.8 (m, 4 F, –C6F5-meta), –161.5 (t, JFF
=
21.2 Hz, 2 F, –C6F5-para), –114.5 (m, 4 F, –C6F5-ortho), 77Se NMR
(DMSO, 76.4 MHz): δ –23.4 (s, 2 Se) ppm.
[Au2(OTf)2(PPh3)2(Bbit)] (9): To a solution of [Au(OTf)(PPh3)]
(0.172 g, 0.28 mmol), which has been obtained by reaction of
[AuCl(PPh3)] with Ag(OTf) in CH2Cl2 (20 mL) and used in situ,
was added Bbit (0.04 g, 0.14 mmol) and stirred for 1 h at room
temperature. The white solution was concentrated under reduced
pressure and precipitated with hexane. The product was collected
by filtration and recrystallized from acetone/n-hexane (1:5, v/v);
yield 74%, 0.15 g. C50H48Au2F6N4O6P2S4 (1498.1167): calcd. C
40.06, H 3.23, N 3.74, S 8.54; found C 40.60, H 3.43, N 3.80, S
8.65. 1H NMR (DMSO, 400 MHz): δ = 1.78 [br. s, 4 H,
–(CH2)4–], 3.72 (s, 6 H, –CH3), 4.21 [br. s, 4 H, –(CH2)4–], 7.58 (m,
30 H, P–C6H5, 4 H, –CH=CH–) ppm. 13C NMR (CDCl3,
[Au2(C6F5)2(Pbis)] (4): Compound 4 was synthesised by the same
procedure described for
1
using [Au(C6F5)(tht)] (0.121 g,
0.26 mmol) and Pbis (0.052 g, 0.13 mmol); yield 86%, 0.13 g.
C25H20Au2F10N4Se2 (1119.919): calcd. C 26.79, H 1.80, N 5.00;
1
found C 26.97, H 1.72, N 5.18. H NMR [DMSO, 400 MHz]: δ =
1.19 [m, 2 H, – (CH2)5–], 2.09 [m, 4 H, – (CH2)5–], 3.99 (s, 6 H,
–CH3), 4.42 [m, 4 H, –(CH2)5–], 7.66 (m, 4 H, –CH=CH–) ppm.
19F NMR [DMSO, 376.48 MHz]: δ = –162.8 (m, 4 F, –C6F5-meta),
3
–161.6 (t, JFF = 21.2 Hz, 2 F, –C6F5-para), –114.6 (m, 4 F, –C6F5-
ortho), 77Se NMR (DMSO, 76.4 MHz): δ –24.9 (s, 2 Se) ppm.
[Au2(C6F5)6(Bbit)] (5): To a solution of [Au(C6F5)3(tht)] (0.167 g,
0.21 mmol) in CH2Cl2 (20 mL) was added Bbit (0.03 g, 0.10 mmol)
and the mixture was stirred for 1 h at room temperature. The white
solution was concentrated under reduced pressure and precipitated
with hexane. The product was collected by filtration and recrys-
tallized from acetone/n-hexane (1:5, v/v); yield 60%, 0.1 g.
C48H18Au2F30N4S2 (1677.982): calcd. C 34.33, H 1.08, N 3.34, S
100.6 MHz): δ = 26.07 [s, –(CH2)4–], 36.31 (s, –CH3), 48.20 [s,
1
–(CH2)4–], 121.12 and 122.12 (s, –CH=CH–), 127.90 (d, JPC
=
3
60.5 Hz, P–C6H5-ipso), 129.67 (d, JPC = 11.7 Hz, P–C6H5-meta),
2
132.40 (s, P–C6H5-para), 134.01 (d, JPC = 13.5 Hz, P–C6H5-ortho)
–
ppm. 19F NMR (DMSO, 376.48 MHz): δ = –77.7 (s, 6 F, CF3SO3 )
ppm. 31P NMR (DMSO, 161.9 MHz): δ = 35.7 (s, 2 P, PPh3) ppm.
1
3.81; found C 34.25, H 1.30, N 3.29, S 3.85. H NMR [(CD3)2CO,
[Au2(OTf)2(PPh3)2(Mbis)]·2C3H6O (10): Compound 10 was syn-
thesised by the same procedure described for 9 using [Au(OTf)-
(PPh3)] (0.146 g, 0.24 mmol) and Mbis (0.04 g, 0.12 mmol); yield
76%, 0.14 g. C47H42Au2F6N4O6P2S2Se2·2C3H6O (1668.042): calcd.
C 38.13, H 3.26, N 3.36, S 3.83; found C 38.38, H 2.96, N 2.86, S
400 MHz]: δ = 1.90 [br. s, 4 H, –(CH2)4–], 3.88 (s, 6 H, –CH3), 4.31
3
[br. s, 4 H, –(CH2)4–], 7.54 (d, JHH = 2.2 Hz, 2 H, –CH=CH–),
3
7.55 (d, JHH = 2.2 Hz, 2 H, –CH=CH–) ppm. 19F NMR [(CD3)2-
CO, 376.48 MHz]: δ = –122.7 (m, 8 F, –C6F5-ortho), –124.0 (m, 4
F, –C6F5-ortho), –160.5 (t, 3JFF = 19.4 Hz, 4 F, –C6F5-para), –161.1
1
3.71. H NMR (DMSO, 400 MHz): δ = 3.79 (s, 6 H, –CH3), 6.77
3
(t, JFF = 19.5 Hz, 2 F, –C6F5-para), –162.0 (m, 8 F, –C6F5-meta),
(s, 2 H, –CH2–), 7.63 (m, 30 H, P–C6H5, 4 H, –CH=CH–) ppm.
–165.0 (m, 4 F, –C6F5-meta) ppm.
13C NMR NMR (DMSO, 100.6 MHz): δ = 37.64 (s, –CH3), 61.20
1
[s, –CH2–], 122.89 and 124.82 (s, –CH=CH–), 127.95 (d, JPC
=
[Au2(C6F5)6(Mbis)] (6): Compound 6 was synthesised by the same
3
58.8 Hz, P–C6H5-ipso), 129.63 (d, JPC = 11.4 Hz, P–C6H5-meta),
procedure described for
5 using [Au(C6F5)3(tht)] (0.211 g,
2
132.32 (s, P–C6H5-para), 133.63 (d, JPC = 13.7 Hz, P–C6H5-ortho)
0.26 mmol) and Mbis (0.045 g, 0.13 mmol); yield 64%, 0.16 g.
C45H12Au2F30N4Se2 (1731.824): calcd. C 31.18, H 0.70, N 3.23;
–
ppm. 19F NMR (DMSO, 376.48 MHz): δ = –77.7 (s, 6 F, CF3SO3 )
ppm. 31P NMR (DMSO, 161.9 MHz): δ = 36.0 (s, 2 P, PPh3), 77Se
NMR (DMSO, 76.4 MHz): δ 4.6 (s, 2 Se) ppm.
1
found C 31.33, H 0.53, N 3.39. H NMR [DMSO, 400 MHz]: δ =
3.68 (s, 6 H, –CH3), 6.45 (s, 2 H, –CH2–), 7.78 (s, 2 H, br,
–CH=CH–), 7.89 (s, 2 H, br, –CH=CH–) ppm. 19F NMR [DMSO,
376.48 MHz]: δ = –161.5 (m, 4 F, –C6F5-meta), –160.7 (m, 8 F,
–C6F5-meta), –157.1 (t, 3JFF = 21.1 Hz, 2 F, –C6F5-para), –156.8 (t,
3JFF = 20.5 Hz, 4 F, –C6F5-para), –122.1 (m, 4 F, –C6F5-ortho),
–120.2 (m, 8 F, –C6F5-ortho), 77Se NMR (DMSO, 76.4 MHz): δ
75.8 (s, 2 Se) ppm.
[Au2(OTf)2(PPh3)2(Ebis)]·(0.5)C6H14 (11): Compound 11 was syn-
thesised by the same procedure described for 9 using [Au(OTf)-
(PPh3)] (0.122 g, 0.20 mmol) and Ebis (0.035 g, 0.10 mmol); yield
44%, 0.07 g. C48H44Au2F6N4O6P2S2Se2·0.5C6H14 (1609.029):
calcd. C 38.03, H 3.19, N 3.48, S 3.97; found C 37.49, H 2.88, N
3.36, S 3.46. 1H NMR (CDCl3, 400 MHz): δ = 3.87 (s, 6 H, –CH3),
4.94 (s, 4 H, –CH2–CH2–), 7.48 (m, 30 H, P–C6H5, 4 H, –CH=CH–
) ppm. 13C NMR (CDCl3, 100.6 MHz): δ = 38.21 (s, –CH3), 49.61
[Au2(C6F5)6(Ebis)] (7): Compound 7 was synthesised by the same
procedure described for
5 using [Au(C6F5)3(tht)] (0.157 g,
[s, – (CH2)2–], 123.11 and 124.98 (s, –CH=CH–), 129.66 (d, 3JPC
=
=
0.20 mmol) and Ebis (0.035 g, 0.10 mmol); yield 64%, 0.16 g.
C46H14Au2F30N4Se2 (1745.840): calcd. C 31.61, H 0.81, N 3.21;
2
8.7 Hz, P–C6H5-meta), 132.47 (s, P–C6H5-para), 133.84 (d, JPC
11.1 Hz, P–C6H5-ortho), 140.59 (s, –C=Se) ppm. 19F NMR
1
found C 31.34, H 0.58, N 3.28. H NMR [DMSO, 400 MHz]: δ =
–
(CDCl3, 376.48 MHz): δ = –78.1 (s, 6 F, CF3SO3 ) ppm. 31P NMR
3
3.58 (s, 6 H, –CH3), 4.51 (s, 4 H, –CH2–CH2–), 7.48 (d, JHH
=
{1H} (CDCl3, 161.9 MHz): δ = 37.8 (s, 2 P, PPh3) ppm. 77Se NMR
(DMSO, 76.4 MHz): δ = 8.2 (1s, 2 Se) ppm.
3
1.8 Hz,
4
H, –CH=CH–), 7.63 (d, JHH
=
2.1 Hz,
4
H,
–CH=CH–) ppm. 19F NMR [(CD3)2CO, 376.48 MHz]: δ = –164.9
3
(m, 4 F, –C6F5-meta), –164.0 (m, 8 F, –C6F5-meta), –161.1 (t, JFF [Au2(OTf)2(PPh3)2(Pbis)] (12): Compound 12 was synthesised by
= 19.5 Hz, 2 F, –C6F5-para), –160.5 (t, 3JFF = 19.4 Hz, 4 F, –C6F5- the same procedure described for 9 using [Au(OTf)(PPh3)] (0.118 g,
Eur. J. Inorg. Chem. 2011, 2884–2894
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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2891

M. C. Gimeno et al.
7.95 [m, 2 H, H3(py)], 8.79 [d, JHH = 4.3 Hz, 1 H, H6(py)] ppm.
FULL PAPER
3
0.20 mmol) and Pbis (0.038 g, 0.10 mmol); yield 71%, 0.11 g.
C51H50Au2F6N4O6P2S2Se2 (1606.89): calcd. C 38.06, H 3.13, N 19F NMR (DMSO, 376.48 MHz): δ = –77.7 (s, 6 F, CF3SO3 ) ppm.
–
3.48, S 3.98; found C 38.42, H 3.17, N 3.44, S 4.15. 1H NMR
31P NMR (DMSO, 161.9 MHz): δ = 36.6 (s, 2 P, PPh3), 77Se NMR
(DMSO, 76.4 MHz): δ 2.1 (s, 2 Se) ppm.
(CDCl3, 400 MHz): δ = 1.33 [m, 2 H, – (CH2)5–], 1.85 [m, 4 H,
3
– (CH2)5–], 3.87 (s, 6 H, –CH3), 4.27 [t, JHH = 7.0 Hz, 4 H,
[Ag2(OTf)2(PPh3)2(Bbit)] (17): Compound 17 was synthesised by
the same procedure described for 5 using [Ag(OTf)(PPh3)] (0.147 g,
0.28 mmol) and Bbit (0.04 g, 0.14 mmol); yield 54% 0.10 g.
C50H48Ag2F6N4O6P2S4 (1317.994): calcd. C 45.47, H 3.67, N 4.24,
–(CH2)5–], 7.57 (m, 30 H, P–C6H5, 4 H, –CH=CH–) ppm. 13C
NMR (CDCl3, 100.6 MHz): δ = 22.62 and 28.85 [s, –(CH2)5–],
37.84 (s, –CH3), 50.00 [s, – (CH2)5–], 122.64 and 123.72 (s,
1
–CH=CH–), 128.17 (d, JPC = 58.9 Hz, P–C6H5-ipso), 129.54 (d,
1
S 9.70; found C 44.60, H 3.43, N 3.80, S 9.65. H NMR (DMSO,
3JPC = 11.7 Hz, P–C6H5-meta), 132.30 (s, P–C6H5-para), 133.91 (d,
400 MHz): δ = 1.73 [br. s, 4 H, –(CH2)4–], 3.42 (s, 6 H, –CH3), 3.96
[br. s, 4 H, –(CH2)4–], 7.31 (m, 12 H, P–C6H5-ortho, 4 H,
–CH=CH–), 7.44 (dd, JHH = 7.0 Hz, 12 H, P–C6H5-meta), 7.52
2JPC
=
13.6 Hz, P–C6H5-ortho) ppm. 19F NMR (CDCl3,
376.48 MHz): δ = –78.1 (s, 6 F, CF3SO3 ) ppm. 31P NMR (CDCl3,
161.9 MHz): δ = 37.2 (s, 2 P, PPh3) ppm. 77Se NMR (CDCl3,
76.4 MHz): δ = –1.7 (s, 2 Se) ppm.
–
3
(dd, JHH = 7.0 Hz, 6 H, P–C6H5-para) ppm. 13C NMR (DMSO,
100.6 MHz): δ = 24.24 [s, –(CH2)4–], 34.80 (s, –CH3), 46.09 [s,
3
[Au2(OTf)2(PPh2py)2(Bbit)] (13): To
a
solution of [Au(OTf)-
–(CH2)4–], 118.36 and 120.38 (s, –CH=CH–), 129.10 (d, JPC
=
=
1
(PPh2py)] (0.086 g, 0.14 mmol), which was obtained by reaction of
[AuCl(PPh2py)] with Ag(OTf) in CH2Cl2 (20 mL) and used in situ,
was added Bbit (0.02 g, 0.07 mmol) and stirred for 1 h at room
temperature. The solution was concentrated under reduced pressure
and precipitated with hexane. The product was collected by fil-
tration and recrystallized from acetone/n-hexane (1:5, v/v); yield
75%, 0.08 g. C48H46Au2F6N6O6P2S4 (1500.107): calcd. C 38.40, H
3.09, N 5.60, S 8.52; found C 38.63, H 3.07, N 5.55, S 8.41. 1H
NMR (CDCl3, 400 MHz): δ = 1.90 [m, 4 H, –(CH2)4–], 3.87 (s, 6
9.5 Hz, P–C6H5-meta), 130.66 (s, P–C6H5-para), 131.49 (d, JPC
2
26.6 Hz, P–C6H5-ipso), 133.23 (d, JPC = 16.2 Hz, P–C6H5-ortho),
155.77 (s, –C=S) ppm. 19F NMR (DMSO, 376.48 MHz): δ = –77.7
(s, 6 F, CF3SO3 ) ppm. 31P NMR (DMSO, 161.9 MHz): δ = 8.6 (s,
–
2 P, PPh3) ppm.
[Ag4(OTf)4(PPh3)4(Mbis)3] (18): Compound 18 was synthesised by
the same procedure described for 5 using [Ag(OTf)(PPh3)] (0.088 g,
0.17 mmol) and Mbis (0.042 g, 0.125 mmol) in acetone; yield 85%,
0.11 g. C103H96Ag4F12N12O12P4S4Se6·2C6H12 (3247.798): calcd. C
42.49, H 3.72, N 5.17, S 3.94; found C 42.59, H 3.35, N 5.62, S
3
H, –CH3), 4.32 [s, 4 H, –(CH2)4–], 7.27 (d, JHH = 2.0 Hz, 4 H,
3
–CH=CH–), 7.49 (m, 20 H, P–C6H5, 4H py), 7.86 [dd, JPH = 7.6,
1
3.40. H NMR [DMSO, 400 MHz]: δ = 3.56 (s, 18 H, –CH3), 6.54
3JHH = 7.4 Hz, 2 H, H3(py)], 8.81 [d, JHH = 4.0 Hz, 2 H, H6(py)]
3
(s, 6 H, –CH2–), 7.52 (m, 60 H, P–C6H5, 12 H, –CH=CH–) ppm.
ppm. 19F NMR (CDCl3, 376.48 MHz): δ = –78.1 (s, 6 F, CF3SO3 )
–
13C NMR (DMSO, 100.6 MHz): δ = 37.07 (s, –CH3), 59.88 [s,
ppm. 31P NMR {1H} (CDCl3, 161.9 MHz): δ = 36.3 (s, 2 P,
PPh2py) ppm.
3
–CH2–], 121.01 and 123.25 (s, –CH=CH–), 129.14 (d, JPC
=
=
1
9.5 Hz, P–C6H5-meta), 130.68 (s, P–C6H5-para), 131.57 (d, JPC
2
[Au2(OTf)2(PPh2py)2(Mbis)] (14): Compound 14 was synthesised
by the same procedure described for 13 using [Au(OTf)(PPh2py)]
(0.061 g, 0.10 mmol) and Mbis (0.017 g, 0.05 mmol) in acetone
(20 mL); yield 51%, 0.04 g. C45H40Au2F6N6O6P2S2Se2 (1553.949):
calcd. C 34.81, H 2.60, N 5.41, S 4.11; found C 35.30, H 2.93, N
5.43, S 3.54. 1H NMR (DMSO, 400 MHz): δ = 3.76 (s, 6 H, –CH3),
6.76 (s, 2 H, –CH2–), 7.66 (m, 20 H, P–C6H5, 4H py + 4 H,
27.6 Hz, P–C6H5-ipso), 133.26 (d, JPC = 16.4 Hz, P–C6H5-ortho),
148.61 (s, –C=Se) ppm. 31P NMR (DMSO, 161.9 MHz): δ 8.2 (4P,
s, PPh3). 77Se NMR (DMSO, 76.4 MHz): δ –48.9 (s, 2 Se).
Synthesis [Ag2(OTf)2(PPh3)2(Ebis)] (19): Compound 19 was syn-
thesised by the same procedure described for 5 using [Ag(OTf)-
(PPh3)] (0.104 g, 0.20 mmol) and Ebis (0.035 g, 0.10 mmol) in ace-
tone (20 mL); yield 61%, 0.08 g. C48H44Ag2F6N4O6P2S2Se2·C3H6O
(1443.893): calcd. C 42.38, H 3.48, N 3.88, S 4.43; found C 42.43,
3
3
–CH=CH–), 7.95 [dd, JPH = 7.2, JHH = 7.1 Hz, 2 H, H3(py)],
3
8.79 [d, JHH = 4.0 Hz, 1 H, H6(py)] ppm. 19F NMR (DMSO,
1
H 3.00, N 3.98, S 3.74. H NMR (DMSO, 300 MHz): δ = 3.40 (s,
–
376.48 MHz): δ = –77.7 (s, 6 F, CF3SO3 ) ppm. 31P NMR (DMSO,
3
6 H, –CH3), 4.66 (s, 4 H, –CH2–CH2–), 7.30 (dd, JHH = 7.8 Hz,
161.9 MHz): δ = 35.3 (s, 2 P, PPh2py) ppm. 77Se NMR (DMSO,
76.4 MHz): δ = 30.6 (s, 2 Se) ppm.
3
12 H, P–C6H5-meta), 7.41 (dd, JHH = 7.8 Hz, 12 H, P–C6H5-or-
tho), 7.49 (m, 6 H, P–C6H5-para, 4 H, –CH=CH–) ppm. 13C NMR
(DMSO, 100.6 MHz): δ = 36.61 (s, –CH3), 46.70 [s, –(CH2)2–],
121.06 and 122.50 (s, –CH=CH–), 129.06 (d, JPC = 9.4 Hz, P–
[Au2(OTf)2(PPh2py)2(Ebis)] (15): Compound 15 was synthesised by
the same procedure described for 13 using [Au(OTf)(PPh2Py)]
(0.122 g, 0.20 mmol) and Ebis (0.035 g, 0.10 mmol); yield 57%,
0.09 g. C46H42Au2F6N6O6P2S2Se2 (1567.965): calcd. C 35.20, H
2.70, N 5.36, S 4.08; found C 35.13, H 2.79, N 5.48, S 3.55. 1H
1
C6H5-meta), 130.57 (s, P–C6H5-para), 131.71 (d, JPC = 25.7 Hz,
2
P–C6H5-ipso), 133.24 (d, JPC = 16.4 Hz, P–C6H5-ortho), 147.57
(s, –C=Se) ppm. 19F NMR (DMSO, 376.48 MHz): δ = –77.7 (s, 6
NMR (DMSO, 400 MHz): δ = 3.77 (s, 6 H, –CH3), 4.82 (s, 4 H, F, CF3SO3 ) ppm. 31P NMR {1H} (DMSO, 161.9 MHz): δ = 7.1
–
–CH2–CH2–), 7.61 (m, 20 H, P–C6H5, 2H py + 4 H, –CH=CH–),
(s, 2 P, PPh3) ppm. 77Se NMR (DMSO, 76.4 MHz): δ –73.9 (s, 2
3
3
3
7.95 [dd, JPH = 7.4, JHH = 7.1 Hz, 2 H, H3(py)], 8.79 [d, JHH
=
Se).
3.5 Hz, 1 H, H6(py)] ppm. 19F NMR (DMSO, 376.48 MHz): δ =
[Ag2(OTf)2(PPh3)2(Pbis)] (20): Compound 20 was synthesised by
the same procedure described for 5 using [Ag(OTf)(PPh3)] (0.106 g,
0.20 mmol) and Pbis (0.04 g, 0.10 mmol); yield 34%, 0.05 g.
C51H50Ag2F6N4O6P2S2Se2 (1427.898): calcd. C 42.86, H 3.53, N
–77.7 (s, 6 F, CF3SO3 ) ppm. 31P NMR {1H} (DMSO, 161.9 MHz):
–
δ = 36.0 (s, 2 P, PPh2py) ppm. 77Se NMR (DMSO, 76.4 MHz): δ
= 18.5 (s, 2 Se) ppm.
[Au2(OTf)2(PPh2py)2(Pbis)] (16): Compound 16 was synthesised by
the same procedure described for 13 using [Au(OTf)(PPh2py)]
(0.086 g, 0.14 mmol) and Pbis (0.027 g, 0.07 mmol); yield 78%,
0.086 g. C49H48Au2F6N6O6P2S2Se2 (1610.011): calcd. C 36.58, H
3.00, N 5.22, S 3.97; found C 37.04, H 3.26, N 5.44, S 3.75. 1H
3.92, S 4.48; found C 43.32, H 3.50, N 3.67, S 4.24. 1H NMR
3
[(CD3)2CO, 400 MHz]:
δ
=
1.36 [q, JHH
=
7.2 Hz,
2
H,
–(CH2)5–], 1.89 [m, 4 H, –(CH2)5–], 3.64 (s, 6 H, –CH3), 4.21 [t,
3JHH = 7.1 Hz, 4 H, –(CH2)5–], 7.22 (m, 24 H, P–C6H5-ortho,
meta), 7.50 (m, 4 H, –CH=CH–; 6 H, P–C6H5-para) ppm. 13C
NMR [CO(CD3)2, 100.6 MHz): δ = 24.01 [s, –(CH2)5–], 38.91 (s,
NMR (DMSO, 400 MHz): δ = 1.23 [m, 2 H, –(CH2)5–], 1.78 [m, 4
3
H, – (CH2)5–], 3.71 (s, 6 H, –CH3), 4.10 [t, JHH = 7.1 Hz, 4 H, –CH3), 51.05 and 55.96 [s, –(CH2)5–], 123.07 and 124.69 (s,
– (CH2)5–], 7.58 (m, 20 H, P–C6H5, 2 H py + 4 H, –CH=CH–),
2892
–CH=CH–), 131.09 (d, 3JPC = 9.6 Hz, P–C6H5-meta), 132.72 (s, P–
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© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2011, 2884–2894

Group 11 Complexes with Imidazoline Derivatives
1
1
C6H5-para), 133.28 (d, JPC = 27.8 Hz, P–C6H5-ipso), 135.44 (d,
19F NMR (DMSO, 376.48 MHz): δ = –70.1 (d, JPF = 711.3 Hz,
12 F, PF6 ) ppm.
2JPC = 16.0 Hz, P–C6H5-ortho), 147.93 (s, –C=Se) ppm. 19F NMR
–
[(CD3)2CO, 376.48 MHz]: δ = –80.1 (s, 6 F, CF3SO3 ) ppm. 31P
–
[Cu2(Ebis)2](PF6)2 (27): Compound 27 was synthesised by the same
procedure described for 25 using [Cu(CH3CN)4]PF6 (0.037 g,
0.10 mmol) and Ebis (0.035 g, 0.10 mmol) in CH2Cl2 (20 mL); yield
38%, 0.04 g. C10H14CuF6N4PSe2 (557.848): calcd. C 21.51, H 2.53,
N 10.04; found C 21.19, H 2.29, N 9.82. 1H NMR (DMSO,
400 MHz): δ = 3.59 (s, 6 H, –CH3), 4.73 (s, 4 H, –CH2–CH2–), 7.35
NMR [(CD3)2CO, 161.9 MHz]: δ = 10.3 (s, 2 P, PPh3) ppm. 77Se
NMR [DMSO, 76.4 MHz]: δ –98.6 (s, 2 Se) ppm.
[Ag2(OTf)2(Bbit)] (21): To
a solution of Ag(OTf) (0.065 g,
0.25 mmol) in acetone (20 mL) was added Bbit (0.035 g,
0.125 mmol) and the mixture stirred for 1 h at room temperature.
The white solution was concentrated under reduced pressure and
precipitated with hexane; yield 85%, 0.085 g. C14H18Ag2F6N4O6S4
(793.811): calcd. C 21.16, H 2.28, N 7.06, S 16.11; found C 21.03,
H 2.16, N 7.00, S 15.91. 1H NMR (DMSO, 400 MHz): δ = 1.83
[m, 4 H, –(CH2)4–], 3.62 (s, 6 H, –CH3), 4.13 [m, 4 H, – (CH2)4–],
7.46 (m, 4 H, –CH=CH–) ppm. 19F NMR (DMSO, 376.48 MHz):
3
3
(d, JHH = 1.6 Hz, 2 H, –CH=CH–), 7.48 (d, JHH = 1.6 Hz, 2 H,
–CH=CH–) ppm. 31P NMR {1H} (DMSO, 161.9 MHz): δ = –143.7
ppm. 19F NMR (DMSO, 376.48 MHz): δ = –70.6 (d, JPF
=
1
711.2 Hz) ppm.
[Cu2(Pbis)2](PF6)2 (28): Compound 28 was synthesised by the same
procedure described for 25 using [Cu(CH3CN)4]PF6 (0.02 g,
0.05 mmol) and Pbis (0.019 g, 0.05 mmol); yield 83%, 0.025 g.
C13H20CuF6N4PSe2 (599.895): calcd. C 26.00, H 3.36, N 9.34;
found C 25.49, H 3.02, N 9.02. H NMR (DMSO, 400 MHz): δ =
1.22 [q, JHH = 7.1 Hz, 2 H, –(CH2)5–], 1.87 [m, 4 H, –(CH2)5–],
–
δ = –77.7 (s, 6 F, CF3SO3 ) ppm.
[Ag2(OTf)2(Mbis)] (22): Compound 22 was synthesised by the same
procedure described for 21 using Ag(OTf) (0.061 g, 0.23 mmol) and
Mbis (0.04 g, 0.12 mmol); yield 85%, 0.09 g. C11H12Ag2F6N4-
O6S2Se2 (847.653): calcd. C 15.57, H 1.43, N 6.61, S 7.54; found C
15.36, H 1.31, N 6.15, S 7.42. 1H NMR (DMSO, 400 MHz): δ =
3.78 (s, 6 H, –CH3), 6.73 (s, 2 H, –CH2–), 7.84 (s, 4 H, br,
–CH=CH–) ppm. 19F NMR (DMSO, 376.48 MHz): δ = –77.7 (s,
1
3
3
3.73 (s, 6 H, –CH3), 4.20 [t, JHH = 7.0 Hz, 4 H, –(CH2)5–], 7.67
(m, 4 H, –CH=CH–) ppm. 19F NMR (DMSO, 376.48 MHz): δ =
1
–70.6 (d, JPF = 711.2 Hz) ppm.
–
6 F, CF3SO3 ), 77Se NMR (DMSO, 76.4 MHz): δ –131.2 (s, 2 Se)
Crystal Structures: Cell refinement gave cell constants correspond-
ing to monoclinic or orthorhombic cells whose dimensions are
given in Table 1 along with other experimental parameters. Crystals
of Pbis, 2, 7, 13 and 18 were mounted in inert oil on a glass fibre
and transferred to the cold gas stream of an Xcalibur Oxford Dif-
fraction diffractometer equipped with a low-temperature attach-
ment. Data were collected using monochromated Mo-Kα radiation
(λ = 0.71073 Å). Scan type ω. Absorption correction based on mul-
tiple scans were applied with the program SADABS.[31] The struc-
tures were refined on F2 using the program SHELXL-97.[32] All
of the non-hydrogen atoms were treated anisotropically. Hydrogen
atoms were included in idealized positions with isotropic thermal
parameters set at 1.2 times that of the carbon atom to which they
were attached. The drawings were created with the DIAMOND
program.[33]
ppm.
[Ag2(OTf)2(Ebis)] (23): Compound 23 was synthesised by the same
procedure described for 21 using Ag(OTf) (0.051 g, 0.20 mmol) and
Ebis (0.035 g, 0.10 mmol); yield 65%, 0.05 g. C12H14Ag2F6N4-
O6S2Se2 (861.669): calcd. C 16.72, H 1.64, N 6.50, S 7.42; found C
17.36, H 1.50, N 6.74, S 7.68. 1H NMR (DMSO, 400 MHz): δ =
3
3.76 (s, 6 H, –CH3), 4.63 (s, 4 H, –CH2–CH2–), 7.68 (d, JHH
=
3
1.9 Hz,
2
H, –CH=CH–), 7.74 (d, JHH
=
1.9 Hz,
2
H,
–CH=CH–) ppm. 19F NMR (DMSO, 376.48 MHz): δ = –77.7 (s,
6 F, CF3SO3 ), 77Se NMR (DMSO, 76.4 MHz): δ –160.6 (s, 2 Se)
–
ppm.
[Ag2(OTf)2(Pbis)]·(0.5)C3H6O (24): Compound 24 was synthesised
by the same procedure described for 21 using Ag(OTf) (0.039 g,
0.15 mmol) and Pbis (0.03 g, 0.076 mmol); yield 72%, 0.05 g.
C15H20Ag2F6N4O6S2Se2 (903.716): calcd. C 19.92, H 2.23, N 6.19,
CCDC-799270 (for Pbis), -799271 (for 2), -799272 (for 7), -799273
(for 13), -799274 (for 18) contain the supplementary crystallo-
graphic data for this paper. These data can be obtained
free of charge from the Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
1
S 7.07; found C 20.35, H 2.13, N 6.66, S 6.68. H NMR (DMSO,
3
400 MHz): δ = 1.22 [q, JHH = 6.7 Hz, 2 H, –(CH2)5–], 1.87 [m, 4
3
H, – (CH2)5–], 3.73 (s, 6 H, –CH3), 4.20 [t, JHH = 6.7 Hz, 4 H,
–(CH2)5–], 7.67 (m, 4 H, –CH=CH–) ppm. 19F NMR (DMSO,
376.48 MHz): δ = –77.7 (s, 6 F, CF3SO3 ), 77Se NMR (DMSO,
–
76.4 MHz): δ –154.6 (s, 2 Se) ppm.
Acknowledgments
[Cu2(Bbit)2](PF6)2 (25): To a solution [Cu(CH3CN)4]PF6 (0.03 g,
0.08 mmol) in acetone (20 mL) was added Bbit (0.023 g,
0.08 mmol) and the mixture stirred for 30 min at room temperature.
The solution was concentrated under reduced pressure and precipi-
tated with hexane; yield 84%, 0.04 g. C12H18CuF6N4PS2·C3H6O
(548.033): calcd. C 32.84, H 4.41, N 10.22, S 11.66; found C 32.76,
The authors thank the Ministerio de Educación y Ciencia (MEC)
(grant number CTQ2010-20500-C02-01) for financial support.
M. K. thanks the MEC (CSIC JAE-Doc Junta para la Ampliación
¨
de Estudios ). Special thanks go to Professor Cristian Silvestru for
¨
help with the graphics in this article.
1
H 4.11, N 10.44, S 11.01. H NMR (DMSO, 400 MHz): δ = 1.75
[m, 4 H, –(CH2)4–], 3.57 (s, 6 H, –CH3), 4.09 [m, 4 H, –(CH2)4–],
[1] G. Roy, M. Nethaji, G. Mugesh, J. Am. Chem. Soc. 2004, 126,
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7.34 (m, 4 H, –CH=CH–) ppm. 19F NMR (DMSO, 376.48 MHz):
1
–
δ = –70.1 (d, JPF = 711.3 Hz, 12 F, PF6 ) ppm.
[2] G. Roy, G. Mugesh, J. Am. Chem. Soc. 2005, 127, 15207.
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[Cu2(Mbis)2](PF6)2 (26): Compound 26 was synthesised by the
same procedure described for 25 using [Cu(CH3CN)4]PF6 (0.012 g,
0.03 mmol) and Mbis (0.011 g, 0.03 mmol); yield 83%, 0.015 g.
C9H12CuF6N4PSe2 (543.833): calcd. C 19.86, H 2.22, N 10.30;
1
found C 19.43, H 2.20, N 9.92. H NMR (DMSO, 400 MHz): δ =
3
3.61 (s, 6 H, –CH3), 6.80 (s, 2 H, –CH2–), 7.64 (d, JHH = 2.1 Hz,
3
2 H, –CH=CH–), 7.78 (d, JHH = 2.1 Hz, 2 H, –CH=CH–) ppm.
Eur. J. Inorg. Chem. 2011, 2884–2894
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
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Received: February 4, 2011
Published Online: May 18, 2011
2894
www.eurjic.org
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2011, 2884–2894