Disilver(I) coordination complexes: Synthesis, reaction chemistry, and their potential use in CVD and spin-coating processes for silver deposition

Article abstract of DOI:10.1002/ejic.201000159

The synthesis of complexes [Ag₂X] [X = O₂CCO ₂ (3a), C₄O₄ (3b), O₂CCH ₂CO₂ (3c), O₂C(CH₂J ₂CO₂ (3d), cis-O₂CCH= CHCO₂ (3e), trans-O₂CCH=CHCO₂ (3f), para-O₂CC ₆H₄CO₂ (3g)] and [(R₃P) _mAgXAg(PR₃)_m] [R = Ph, X = C₄O ₄, m = 2 (10a), m = 3 (10b); R = nBu, X = O₂CCH ₂CO₂, m = 2 (10c), m = 3 (10d); X = O₂C(CH ₂J₂CO₂, m = 1 (10e), m = 2 (10f), m = 3 (10g); X = cis-O₂CCH=CHCO₂, m = 1. (10h), m = 2 (101), m = 3 (10j); X = trans-O₂CCH=CHCO₂, m = 1 (10k), m = 2 (101), m = 3 (10m); X = para-O₂CC₆H₄CO₂, m = 2 (10n)] is reported. Compoundds 3a-3g are accessible by the reaction of [AgNO₃] (1) with H₂X (2a-2g), while 10a-10n can be prepared by treatment of 3a-3g with PR₃ (9a, R = Ph; 9b, R = nBu) in the ratios of 1:2, 1:4, or 1:6. When [{Ag(bipym)(NO₃)H ₂O)_n] (6) (bipym = bipyrimidine) reacts with (HNEt ₃J₂(O₂CCO₂) (7), [{Ag(bipym)Ag(O₂CCO₂)·4H₂O} _n] (5) and [{(bipym)(Ag(O₂CCO₂H)) ₂}_n] (8) are formed. The molecular structures for 5, 6, and 8 in the solid state are reported. For 5, the formation of a 3D network is characteristic, in which ID chains of {Ag(bipym) Ag (O₂CCO ₂)}_n interact with each other through π-π interactions between the bipym ligands to extend in one direction, while H ₂O molecules act as connectivities thorugh the intermolecular H-bridge formation to extend in the other direction. Polymeric 6 consists of 2D layers formed, by individual ID chains of {Ag(bipym)Ag(bipym)}_n with π-π interactions between the bipym ligands. In 8, {(HO₂CCO ₂)Ag(bipym)Ag(O₂CCO₂H)} units undergo intermolecular H-bridge formation, to create 2D layers, π π interactions between, individual bipym ligands produce a 3D network. The use of 1 Od as a CVD precursor in the deposition of Ag on glass by using a direct liquid injection system is discussed. The Ag films show a rough appearance and contain C impurities. The use of 10e and 10f as spin-coating precursors for the deposition of Ag on TiN-coated oxidized Si wafers is reported.

Full text of DOI:10.1002/ejic.201000159

FULL PAPER
DOI: 10.1002/ejic.201000159
Disilver(I) Coordination Complexes: Synthesis, Reaction Chemistry, and Their
Potential Use in CVD and Spin-Coating Processes for Silver Deposition
Alexander Jakob,[a] Tobias Rüffer,[a] Heike Schmidt,[a] Patrice Djiele,[a] Kathrin Körbitz,[a]
Petra Ecorchard,[a] Thomas Haase,[b] Katharina Kohse-Höinghaus,[b] Swantje Frühauf,[c]
Thomas Wächtler,[c] Stefan Schulz,[c] Thomas Gessner,[c] and Heinrich Lang*[a]
Keywords: Silver / Phosphanes / Dicarboxylate ligands / Thin films / Chemical vapor deposition
The synthesis of complexes [Ag2X] [X = O2CCO2 (3a), C4O4
(3b), O2CCH2CO2 (3c), O2C(CH2)2CO2 (3d), cis-O2CCH=
CHCO2 (3e), trans-O2CCH=CHCO2 (3f), para-O2CC6H4CO2
(3g)] and [(R3P)mAgXAg(PR3)m] [R = Ph, X = C4O4, m = 2
(10a), m = 3 (10b); R = nBu, X = O2CCH2CO2, m = 2 (10c), m
= 3 (10d); X = O2C(CH2)2CO2, m = 1 (10e), m = 2 (10f), m =
3 (10g); X = cis-O2CCH=CHCO2, m = 1 (10h), m = 2 (10i), m
= 3 (10j); X = trans-O2CCH=CHCO2, m = 1 (10k), m = 2 (10l),
m = 3 (10m); X = para-O2CC6H4CO2, m = 2 (10n)] is reported.
Compoundds 3a–3g are accessible by the reaction of
[AgNO3] (1) with H2X (2a–2g), while 10a–10n can be pre-
pared by treatment of 3a–3g with PR3 (9a, R = Ph; 9b, R =
nBu) in the ratios of 1:2, 1:4, or 1:6. When [{Ag(bipym)(NO3)·
H2O}n] (6) (bipym = bipyrimidine) reacts with (HNEt3)2-
(O2CCO2) (7), [{Ag(bipym)Ag(O2CCO2)·4H2O}n] (5) and
[{(bipym)(Ag(O2CCO2H))2}n] (8) are formed. The molecular
structures for 5, 6, and 8 in the solid state are reported. For
5, the formation of a 3D network is characteristic, in which
1D chains of {Ag(bipym)Ag(O2CCO2)}n interact with each
other through π–π interactions between the bipym ligands to
extend in one direction, while H2O molecules act as connec-
tivities thorugh the intermolecular H-bridge formation to ex-
tend in the other direction. Polymeric 6 consists of 2D layers
formed by individual 1D chains of {Ag(bipym)Ag(bipym)}n
with π–π interactions between the bipym ligands. In 8,
{(HO2CCO2)Ag(bipym)Ag(O2CCO2H)} units undergo inter-
molecular H-bridge formation to create 2D layers, π–π inter-
actions between individual bipym ligands produce a 3D net-
work. The use of 10d as a CVD precursor in the deposition
of Ag on glass by using a direct liquid injection system is
discussed. The Ag films show a rough appearance and con-
tain C impurities. The use of 10e and 10f as spin-coating pre-
cursors for the deposition of Ag on TiN-coated oxidized Si
wafers is reported.
or photo-induced energy-transfer processes.[3] In addition,
they offer diverse applications in the field of new materials,
e.g., smart system integration, and they can be used as ma-
terials for micro- and nanosystems, nanostructures, and de-
vices.[4]
CVD (chemical vapor deposition), ALD (atomic layer
deposition), and spin-coating processes are considered to be
alternatives for or supplementing technologies to, e.g., PVD
(physical vapor deposition) and electrochemical metal de-
position procedures for use in future technology areas for
the fabrication of micro- and nanoelectronics.[5]
In this context, silver as a noble metal exhibits the lowest
resistivity and highest thermal conductivity of all metals.[6]
For this reason, the design of silver(I) coordination com-
plexes is of potential interest because they are promising
candidates for the deposition of thin silver films on different
substrates. Lately, there have been some reports on the syn-
thesis of novel volatile phosphane and phosphite silver(I)
carboxylates and their use as CVD precursors for the depo-
sition of silver on different (structured) wafer materials.[1b,7]
Additional silver(I) metal–organic complexes that can suc-
cessfully be applied as MOCVD precursors include LmAg
carboxylates, LmAg β-diketonates, and R3PAgC5H5 (R =
Introduction
Dicarboxylic acids and squaric acid (3,4-dihydroxy-
cyclobut-3-ene-1,2-dione) have been well known for quite
some time, and hence, there exists a versatile number of
literature reports on their synthesis, reaction chemistry,
structures, and ligand properties.[1] Recently, dicarboxylates
became of considerable interest in transition-metal coordi-
nation chemistry because they can act as planar bridging
units between metal centers, to form homo- or heterodimet-
allic or even two- and three-dimensional polymeric struc-
tures for molecular recognition.[2] Such modular con-
structed assemblies may be used as representative model
compounds in the fundamental study of electron-transfer
[a] Technische Universität Chemnitz, Fakultät für
Naturwissenschaften,
Institut für Chemie, Lehrstuhl für Anorganische Chemie,
Straße der Nationen 62, 09111 Chemnitz, Germany
Fax: +49-371-531-21219
E-mail: heinrich.lang@chemie.tu-chemnitz.de
[b] Universität Bielefeld, Physikalische Chemie I,
Postfach 100131, 33501 Bielefeld, Germany
[c] Technische Universität Chemnitz, Fakultät für Elektrotechnik
und Informationstechnik, Zentrum für Mikrotechnologien,
Reichenhainerstr. 70, 09126 Chemnitz, Germany
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H. Lang et al.
FULL PAPER
alkyl, aryl; L = trialkyl-/triarylphosphane, alkene, diene, bi-
The silver salts 3a–3g are very stable species with the
pyridine; m = 1, 2, 3).[7] The gas-phase decomposition be- exception of 3b, which decomposes within days at ambient
havior of such compounds was studied by applying tem- temperature. Thus, they should best be stored at –30 °C to
perature-programmed and in situ mass spectrometry.[8]
We report here on the synthesis of disilver(I) dicarboxyl-
prevent decomposition.
The low solubility of 3a–3g is associated with the aggre-
ates and on the related species thereof. The use of selected gated structural form of these assemblies.[9] To obtain solu-
samples for metal deposition is discussed.
ble materials the oligo- or polymeric structures of these
metal–organic compounds must be broken to produce
lower aggregated or even monomolecular species. This can
be achieved by the addition of Lewis bases. Thus, complex
3a was treated with bipyrimidine (bipym) (4) in a 1:1 molar
ratio in chloroform at 25 °C. However, this reaction formed
a coordination polymer with the composition [(bipym)Ag-
(O2CCO2)Ag]n (5). Because of the low basicity of bipym
only small amounts of 5 could be isolated. A more efficient
synthesis methodology to prepare 5 is the reaction of [(bi-
pym)AgNO3] (6)[11] with the ammonium salt [HNEt3]2-
[O2CCO2] (7) [Reaction (2)]. It was found that the highest
yield is obtained when 7 was used in a twofold excess (Ex-
perimental Section). After appropriate workup, polymeric
5 could be isolated as a pale yellow solid. The disilver coor-
dination complex 8 was formed as a side product in which
the bipym building block connects two Ag(O2CCO2H)
building blocks [Reaction 2, Experimental Section].
Results and Discussion
Syntheses and Characterization of Disilver Carboxylates
The synthesis of the Lewis base disilver(I) dicarboxylates
and squarates 5, 8, and 10a–10n (Lewis base = phosphane,
phosphite, bipyrimidine) (reactions 1–3, Table 1 and
Table 4) requires the accessibility of the appropriate silver
salts [Ag2X] (3a–3g), which can easily be prepared by re-
acting 2 equiv. [AgNO3] (1) with the dicarboxylic and
squaric acids H2X [H2X = oxalic acid (2a), squaric acid
(2b), malonic acid (2c), succinic acid (2d), maleic acid (2e),
fumaric acid (2f), terephthalic acid (2g)] in a mixture of
ethanol/acetonitrile (30:1, v/v) in the presence of NEt3 at
ambient temperature [Reaction (1)]. The silver salts [Ag2X]
[X = O2CCO2 (3a),[1b,9a] C4O4 (3b),[9b] O2CCH2CO2 (3c),[9c]
O2C(CH2)2CO2 (3d),[9d] cis-O2CCH=CHCO2 (3e),[9e] trans-
O2CCH=CHCO2 (3f),[9f] para-O2C-C6H4-CO2 (3g)][9g] pre-
cipitate as colorless or off-white to pale yellow solids, while
[HNEt3]NO3 remains in solution. After decanting the su-
pernatant solution and washing the residue thoroughly with
cold ethanol and then with petroleum ether, 3a–3g were ob-
tained in the analytically pure form and in high yield (see
Experimental Section and Table 1).
The identity of 5 was confirmed by elemental analysis
and IR spectroscopy. The molecular structures of 5, 6, and
8 in the solid state were additionally solved by single X-ray
structure analysis, thus confirming the structural assign-
ments made from spectroscopic analysis.
Most characteristic in the IR spectra of 5[10] and 8 are
their ν , ν
and ν
vibrations found between 1312–
˜
˜
˜
CO C=C
1701 cm–1, the ν
C=N
vibrations at 3044 and 3064 cm–1,
˜
CH
respectively, and the broad ν
absorption at 3368 (5) and
˜
OH
3448 cm–1 (8) from the crystal water that is part of the hy-
drogen-bonded network (Figures 1, 3, Figures 6, 8, vide in-
fra). For complex 6, a very strong absorption band at
1384 cm–1 is observed which proves the presence of a nitrate
anion,[11] and hence points to a polymeric structure as
partly evidenced by conductivity measurements.[12]
The molecular structures of 5, 6, and 8 in the solid state
were established by single X-ray crystallographic studies
(Figures 1–8). Suitable crystals were obtained by slow con-
centration of water solutions containing the appropriate
transition-metal complexes at ambient temperature.
ORTEP diagrams, selected bond lengths (Å) and angles (°)
are given in Figures 1–8 as well as in Tables 2 and 3, while
the crystal and structure refinement data are presented in
Table 5 (Experimental Section).
Table 1. Synthesis of the silver salts [Ag2X] (3a–3g).
Compound
X
Yield[a][%]
Refs.
[1b,9a]
[9b]
[9c]
3a
3b
3c
3d
3e
3f
O2CCO2
C4O4
O2CCH2CO2
O2C(CH2)2CO2
cis-O2CCH=CHCO2
trans-O2CCH=CHCO2
para-O2CC6H4CO2
96
87
90
85
90
98
95
[b]
[9d]
[9e]
[9f]
[9g]
3g
[a] On the basis of 2a–2g. [b] C4O4 = squarate.
(1)
(2)
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Disilver(I) Coordination Complexes
Complex 5 crystallized in the centrosymmetric space posed 1D chains. Eventually, the silver(I) ions possess a co-
¯
group P1 to form a 3D network consisting of 1D coordina- ordination number of 5 in a distorted square-pyramidal
tion polymers with repeating units {Ag(bipym)Ag- N2O3 coordination setup.
(O2CCO2)}n, in which the bipyrimidine building blocks and
the oxalato anions act as flexidentate alternating ligands.
Within the 1D coordination polymer the alternating
{Ag(O2CCO2)Ag} and {Ag(bipym)Ag} metal–organic
moieties, which consist of the atoms Ag1, Ag1b, O1, O2,
O1b, O2b, C5, C5b (unit I) and Ag1b, Ag1c, N1c, N2c,
N1b, N2b, C1c–C4c, C1b–C4b (unit II), respectively, are
planar as determined from the calculation of mean planes
(unit I: r.m.s.d. = 0.021 Å, unit II: r.m.s.d. = 0.058 Å)
(r.m.s.d. = root means square deviation) (Figure 1). The 1D
coordination polymer is planar as the dihedral angle be-
tween units I and II is 6.3°.
Figure 2. Graphical representation of the connection of 1D chains
of 5 in the crystal structure induced by π–π interactions between
bipym and oxalate ligands, Ͻ) refers to the interplanar angle, d
gives the shortest distance of interacting π-conjugated units, the
intermolecular hydrogen bonds and interchain Ag···O contacts are
shown. Labels “a–i” refer to the first to the ninth symmetry-gener-
ated asymmetric unit of 5. All hydrogen atoms, except for the O-
bonded ones, have been omitted for clarity.
Table 2. Intermolecular hydrogen bond lengths (Å) and angels (°)
within the molecular structure of 5.[a]
No.
D–H
A
D···A
D–H···A
I
II
III
IV
O3–H1o
O4–H3o
O3–H2o
O4–H4o
O1
2.868(3)
2.763(3)
2.762(4)
2.773(4)
159(4)
167(3)
165(4)
172(7)
Figure 1. ORTEP diagram (50% probability level) of a part of the
1D strain formed by 5 in the solid state. All hydrogen atoms, except
for the O-bonded hydrogen atoms, have been omitted for clarity.
Labels “a–c” refer to atoms of the first to the third symmetry-
generated asymmetric unit of 5. Selected distances (Å) and angles
(°): Ag1–O1 2.2957(17), Ag1–N1 2.336(2), Ag1–N2a 2.421(2),
Ag1–O2b 2.4810(19), C1–C1a 1.505(5), C5–C5a 1.575(5); O1–
Ag1–N1 126.94(7), O1 Ag1–N2a 161.19(7), N1–Ag1–N2a 70.08(8),
O1–Ag1–O2b 69.39(6), N1–Ag1–O2b 163.63(7), N2a–Ag1–O2b
93.61(7), C1–N1–Ag1 118.22(17), C2–N1–Ag1 124.42(17), C1–N2–
Ag1 115.92(17), C4a–N2a–Ag1 127.00(17), C5–O1–Ag1
121.09(16), C5–O2b–Ag1 114.80(16).
O2a
O4[a]
O3a
[a] I–IV = number of the hydrogen-bridging bond; D = donor, A
= acceptor.
As can be seen from Figure 3, the hydrogen atoms lab-
eled with H4o and symmetry-related hydrogen atoms are
not involved in the formation of 2D layers. It is these hydro-
gen atoms that are responsible for the connection between
the 2D layers to form an overall 3D network through inter-
The silver(I) ion possesses an intrachain coordination molecular hydrogen bond number IV (Table 2). A represen-
number of 4 and the bipym and oxalate ligands are chelate- tative part of the 3D network is shown in Figure 3.
bonded to the group 11 metal ion, which results in a dis-
Recently, the crystal structure of a chemically identical
torted square-planar geometry around the silver atom compound was reported, denoted as [Ag2(µ2-bpm)(µ2-ox)]n·
(r.m.s.d. deviation from planarity of the AgN2O2 atoms 4nH2O (5a).[10] While the synthesis of 5a differs from that of
0.08 Å). The cis angles are 69.39(6) (O1–Ag1–O2b) and 5, the structural features of both compounds are certainly
126.94(7)° (O1–Ag1–N1), while the trans angles are identical, although 5a crystallizes in a different centrosym-
¯
161.19(7) (O1–Ag1–N2a) and 163.63(7)° (N1–Ag1–O1b). metric P1 unit cell when compared with 5. All bond lengths
The water molecules are hydrogen-bonded to all four ox- and angles of 5 are similar to those of 5a. Furthermore, it
alate oxygen atoms (Figure 2, Table 2), with bond numbers should be noted that the silver(I) ions in 5a do have, as
I and II. The remaining water hydrogen atoms also form observed for 5, an interchain coordination number of 5 in
intermolecular hydrogen bonds and create a 3D network a distorted square-pyramidal N2O3 coordination environ-
structure (Figures 2 and 3). As shown in Figure 2, the water ment, but they do not possess a distorted N2O4 geometry,
molecules are bonded to each other through hydrogen bond as reported. In addition, 5a forms, as observed for 5, a 3D
number III (Table 2) and connect to form 1D chains super- network and not a “quasi two-dimensional (2D) network”,
imposed on each other. Between these superimposed 1D as reported.
chains π–π interactions are additionally observed between
Complex 6 crystallizes in the noncentrosymmetric ortho-
the bipym and oxalate moieties as well as short Ag···O in- rhombic space group Pna21. The asymmetric unit of 6 con-
terchain distances of 2.817(2) Å (Figure 2). As shown in sists of two silver atoms, two bipym moieties, two nitrate
Figure 2, an Ag···O interchain contact is observed between anions, and one water molecule (Figure 4). 2D layers of in-
two adjacent 1D chains only but not between the superim- dividual 1D coordination polymers with the repeating unit
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H. Lang et al.
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Figure 3. Top (left) and side view (right) of the 3D network structure formed by 5 in the solid state. Labels “a–i” refer to the first to the
ninth symmetry-generated asymmetric unit of 5. All hydrogen atoms, except for the O-bonded ones, have been omitted for clarity.
{Ag(bipym)Ag(bipym)}n are formed, which are connected 3.24 Å.[13] Furthermore, a water molecule is hydrogen
through π–π interactions between adjacent bipym moieties bonded to both a coordinated and a noncoordinated nitrate
(Figures 4 and 5). As shown in Figure 4, a nitrate ion is anion (Table 3).
weakly bonded to one of the two crystallographically inde-
Within the 1D coordination polymer, the {Ag(bipym)-
pendent silver ions (Ag1) (d(Ag1–O6) = 2.958 Å), as the Ag(bipym)}n repeating units, which consist of the atoms
sum of the van der Waals radii of silver(I) and oxygen is Ag1, Ag2, N1–N4, C1–C8 (unit I) and Ag1A, Ag2, N5–N8,
Figure 4. ORTEP diagram (50% probability level) of a part of the 1D polymer formed by 6. The alignment of the nitrate anions and the
water molecule towards the 1D polymer is presented for one representative case, Ͻ) is the interplanar angle of the calculated mean planes
of adjacent bipym ligands. All hydrogen atoms, except for the O-bonded ones, have been omitted for clarity. Label “a” refers to atoms
of a second asymmetric unit. Selected distances (Å) and angles (°): Ag1–N1 2.357(4), Ag1–N2 2.284(4), Ag2–N3 2.243(3), Ag2–N4
2.397(4), Ag2–N5 2.257(4), Ag2–N6 2.396(5), Ag1–N7a 2.297(4), Ag1–N8a 2.346(4), C5–C4 1.501(6); N3–Ag2–N5 145.04(14), N3–Ag2–
N6 137.46(14), N5–Ag2–N6 72.95(14), N3–Ag2–N4 71.95(12), N5–Ag2–N4 130.92(13), N6–Ag2–N4 96.24(12), N2–Ag1–N7a 128.94(13),
N2–Ag1–N8a 145.68(14), N7a–Ag1–N8a 71.66(15), N2–Ag1–N1 71.74(13).
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Disilver(I) Coordination Complexes
Figure 5. Graphical representation of 2D layers formed from 1D chains of 6 in the crystal structure induced by π–π interactions between
adjacent 1D polymers (left), together with details of the interaction; Ͻ) gives the interplanar angle, and d gives the centroid–centroid
distance of interacting bipym ligands (right). Labels “a–e” refer to the first to the fifth symmetry-generated asymmetric unit of 6. The
nitrate anions, the water molecules, and all hydrogen atoms are omitted for clarity.
Table 3. Intermolecular hydrogen bond lengths (Å) and angels (°)
within the molecular structure of 6.[a]
As described above, the 1D coordination polymers of 6
interact with each other by means of π–π interactions be-
tween the bipym units to lead to 2D layers. A representative
part of one 2D layer with geometrical details is illustrated
in Figure 5.
Complex 8 crystallizes in the monoclinic space group
P21/n in the form of centrosymmetric homodimetallic [Ag2-
(bipym)(O2CCO2H)2] entities, with a crystallographic im-
posed inversion center in the middle of the C1–C1a bond.
The molecular structure is shown in Figure 6, and the crys-
tallographic data are summarized in Table 5. For complex
8, the formation of a 3D network is observed in the solid
state. The {(HO2CCO2)Ag(bipym)Ag(O2CCO2H)} build-
ing blocks interact with each other, which results in the for-
mation of 2D layers based on intermolecular hydrogen
bridges. These layers are connected to the 3D network by
π–π interactions between bipym ligands.
D–H
A
D···A
D–H···A
O7–H7A
O7–H7A
O7–H7B
O6
O1
O3
2.860(7)
3.308(3)
3.346(9)
161.3(6)
153.0(3)
148.6(5)
[a] D = donor, A = acceptor.
C9–C16 (unit II), are planar (mean plans; unit I: r.m.s.d. =
0.087 Å, unit II: r.m.s.d. = 0.059 Å). However, the 1D chain
is not planar, as is shown by the dihedral angles of the
neighboring bipym ligands (Figure 4). The silver atoms in 6
are coordinated either by four N-donor atoms of two bipym
building blocks to form an AgN4 entity (Ag2) or by four
N-donor atoms and the weakly bonded oxygen atom of one
nitrate anion to create an AgN4O subunit (Ag1). The coor-
dination geometry of the silver atom in the AgN4 assembly
The bipym units in 8 act as flexidentate ligands as al-
can best be described as strong tetrahedrally distorted and ready observed for 5 and 6 (vide supra). However, as the
with small N–Ag–N angles induced by the “biting” of the oxalate dianions become protonated during the formation
bipym ligands [N5–Ag2–N6 73.0(2) and N3–Ag2–N4 of 5 (vide supra) and as the anion [O2CCO2H]–acts as a
72.0(1)°]; the remaining angles range from 96.2(1) (N6– monodenate ligand, the silver(I) ions set up AgN2O arrays.
Ag2–N4) to 145.0(2)° (N3–Ag2–N5). The coordination ge- The bond angles of the AgN2O units range from 70.27(6)
ometry around the silver atom of the AgN4O moieties can (N1–Ag1–N2A) to 154.60(6)° (O1–Ag1–N2), and the
best be described as distorted square pyramidal with O6 at r.m.s.d. from planarity of the calculated mean plane of
the apex of the basal AgN4 plane. The τ parameter of atoms O1, Ag1, N1A, and N2 is 0.157 Å. Thus, the coordi-
0.22[14] affirms the description of the coordination geome- nation geometry at silver can best be described as trigonal
try; however, the interaction of the nitrate anion towards planar. Molecules of 8 are superimposed on each other in
Ag1 should not be overstressed. By neglecting the nitrate the solid state through π–π interactions between the bipym
anion, the coordination geometry around Ag1 closely re- moieties (Figure 7). As shown in Figure 7, the oxygen atom
sembles that of Ag2 (Figure 4).
O1 of symmetry-generated equivalents of 8 comes closer to
Eur. J. Inorg. Chem. 2010, 2975–2986
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H. Lang et al.
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Figure 6. ORTEP diagram (50% probability level) of homodi-
metallic 8 in the solid state. All hydrogen atoms, except for the O-
bonded hydrogen atoms, are omitted for clarity. Selected distances
(Å) and angles (°): Ag1–O1 2.237(15), Ag1–N1a 2.4120(17), Ag1–
N2 2.3039(17), C1–C1a 1.492(4), C5–C6 1.545(3); O1–Ag1–N2
154.60(6), O1–Ag1–N1a 130.4834(12), N2–Ag1–N1a 70.27(6), C5–
O1–Ag1 108.34(12), C1–N2–Ag1 118.99(13), C4–N2–Ag1
124.44(13), C1–N1–Ag1a 115.85(13), C2–N1–Ag1a 127.05(14).
the Ag1 ions. The interatomic distance is 2.980(6) Å, which
is significantly shorter than the sum of the van der Waals
radii (3.24 Å) of Ag and O.[13] The Ag–O contacts in the
same range are usually considered as nonbonding.[15]
Figure 8. Graphical representation of a part of a plane induced by
intermolecular hydrogen bonds in the crystal structure of 8. Lables
“a–m” refer to the first to the twelfth symmetry-generated asym-
metric unit of 8. All hydrogen atoms, except for the O-bonded
atoms, have been omitted for clarity. Hydrogen interactions: do-
nor–H = O4–H1, acceptor = O1, D···A = 2.6017, D–H···A = 1.71.
Non-hydrogen intermolecular contact: atom I = Ag1, atom J = O1,
d(I–J) = 2.979.
CO2, m = 1 (10e), m = 2 (10f), m = 3 (10g); X = cis-
O2CCH=CHCO2, m = 1 (10h), m = 2 (10i), m = 3 (10j); X
= trans-O2CCH=CHCO2, m = 1 (10k), m = 2 (10l), m = 3
(10m); X = para-O2CC6H4CO2, m = 2 (10n)] could be iso-
lated as colorless to off-white liquids or solids in excellent
yields (see Reaction (3), Table 4, and the Experimental Sec-
tion). Complexes with m = 2 and 3 are more stable than
those assemblies with m = 1. While 3a–3g are practically
insoluble in common organic solvents (vide supra), the
phosphane silver complexes 10a–10n dissolve in most com-
mon nonpolar organic solvents.
Figure 7. Graphical representation of three superimposed mole-
cules of 8 involved in π–π interactions; Ͻ) gives the interplanar
angle, and d the centroid–centroid distance of interacting bipym
ligands. Labels “a–e” refer to the first to the fifth symmetry-gener-
ated asymmetric unit of 8. All hydrogen atoms, except for the O-
bonded hydrogen atoms, have been omitted for clarity.
(3)
Because of the carboxylic acid functionalities in 8, the
formation of intermolecular hydrogen bonds is observed in
the solid state, which gives rise to the formation of 2D
layers (Figure 8). The combination of π–π interactions (Fig-
The formation of 10a–10n was evidenced by elemental
ure 7) and the discussed intermolecular hydrogen bonds re- analysis and IR, 1H, 13C{1H}, and 31P{1H} NMR spec-
sults in the formation of a 3D network.
troscopy. Additionally, from selected samples, thermogravi-
Other Lewis bases that can be added to polymeric [Ag- metric and differential scanning calorimetric measurements
O2CCO2Ag]n (3a) are phosphanes, which may allow the ob- were carried out. In the IR spectra of 10a–10n, strong ν
˜
CO
tainment of lower-aggregated metal–organic species. Thus, vibrations from 1340 to 1586 cm–1 are found, as expected
3a–3g were treated with PR3 (9a, R = nBu; 9b, R = Ph) in for the dicarboxylate and squarate connectivities (Experi-
the ratios of 1:2, 1:4 or 1:6, respectively, in dichloromethane mental Section).[1c,7a,7d,7e]
1
or diethyl ether suspensions. After appropriate workup, the
In the H NMR spectra of 10a–10n, characteristic reso-
coordination compounds [(R3P)mAgXAg(PR3)m] [R = Ph, nance signals and coupling patterns are observed for the
X = C4O4, m = 1 (10a), m = 2 (10b); R = nBu, X = phosphane ligands and the bridging units X (Experimental
O2CCH2CO2, m = 1 (10c), m = 2 (10d); X = O2C(CH2)2- Section).[1b,7] The 31P{1H} NMR spectra of 10a–10n are
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Disilver(I) Coordination Complexes
Table 4. Synthesis of homodimetallic complexes 10a–10n.
Compound
X
R
m
Yield (%)[a]
10a
10b
10c
10d
10e
10f
10g
10h
10i
10j
10k
10l
10m
10n
C4O4
C4O4
O2CCH2CO2
O2CCH2CO2
O2C(CH2)2CO2
O2C(CH2)2CO2
O2C(CH2)2CO2
cis-O2CCH=CHCO2
cis-O2CCH=CHCO2
cis-O2CCH=CHCO2
trans-O2CCH=CHCO2
trans-O2CCH=CHCO2
trans-O2CCH=CHCO2
para-O2CC6H4CO2
Ph
Ph
2
3
2
3
1
2
3
1
2
3
1
2
3
2
97
97
86
88
93
83
87
93
89
95
93
95
92
96
nBu
nBu
nBu
nBu
nBu
nBu
nBu
nBu
nBu
nBu
nBu
nBu
Figure 9. TG trace of 10f (heating rate 8 Kmin–1, nitrogen atmo-
sphere, 20 dm3 h–1).
tion chamber. The deposition took place at temperatures
250–350 °C. Silver films with a thickness of 200–300 nm
could be obtained. According to XRD studies, silver was
obtained in the cubic modification (Figure 10). EDX mea-
surements show a carbon content of 30%. SEM images
show uneven films with a connected-island-like structure
(Figure 11).
[a] Based on 3a–3g.
very informative. Relative to free phosphanes PR3 (9a,
–32.3 ppm; 9b, –6.0 ppm),[16] the signals for the coordinated
phosphanes in the metal–organic compounds 10a–10n ap-
pear at a lower field (Experimental Section). In general, the
resonance signals are broad, which indicate thermal-de-
pendent exchange processes on the NMR time scale as dis-
cussed elsewhere.[17] However, this intermolecular ligand ex-
change process becomes fast on the NMR time scale for
10k and 10l. For 10k two doublets at –0.2 ppm [672 Hz
(J107Ag31P), 773 Hz (J109Ag31P)] and for 10l one broad singlet
at –7.4 ppm are found, because of the presence of 107Ag
and 109Ag isotopes [relative natural abundance of 107Ag
51.83% and 109Ag 48.17%].[18]
The thermal decomposition of selected coordination
complexes was studied by thermogravimetry (TG) and
differential scanning calorimetry (DSC) to determine their
suitability for spin-coating processing (vide infra). As an
example, the TG trace for 10f is shown in Figure 9. Experi-
ments were conducted at atmospheric pressure under a ni-
trogen atmosphere. For most of the complexes, their ther-
mal degradation starts at 47 °C and is completed above
357 °C (Experimental Section). The weight losses are ac-
companied by residues in the TG pan, the amount of which
is comparable to the theoretical percentage of metallic silver
present in the complex, although small amounts (0.2–2.1%,
except for 10k and 10m) of additional material are also
formed. Evidently, these complexes eliminate the ancillary
ligands L (vide supra) upon heating without significant vol-
atilization of the intact disilver–dicarboxylates and -squar-
ates, respectively. Thus, at atmospheric pressure, the ma-
jority of the studied disilver species 10a–10n are nonvolatile
complexes, and hence, are best suited for spin-coating depo-
sitions; however, one exception is 10d, which qualifies as a
CVD precursor (see below) as can be shown by tempera-
ture-programmed mass spectrometry.[8] The DSC traces are
characterized by at least two overlapping endothermic and
exothermic isotherms (Experimental Section).
Figure 10. XRD spectra of the silver film formed by 10d (300 °C
deposition temperature, bottom), and the calculated XRD spectra
of cubic silver (top).
Silver films were deposited on glass substrates from 10d
by using a vertical CVD reactor with a direct liquid injec-
tion system. The precursor was dissolved in ethanol, and
Figure 11. SEM images of the 240-nm-thick silver film formed by
the solution was injected through a nozzle in the evapora- using 10d as the precursor at deposition temperature of 300 °C.
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H. Lang et al.
FULL PAPER
Complexes 10e and 10f were subjected to spin-coating analysis shows that, in addition, carbon and oxygen impuri-
deposition experiments. For complex 10e conductive silver ties are present; the peak for oxygen is most probably attrib-
films could be obtained with a film resistivity of 3.4 µΩcm. uted to the wafer material (glass, oxidized silicon) because
The film thickness (mean value of about 2.5 µm, deter- the films obtained are not completely dense (Figure 13).
mined by profilometer) was not homogeneous because of The elimination of pores by optimizing the sample prepara-
the solvent used acetonitrile, i.e. in the wafer center the tion and the thermolysis conditions is important in order
thickness of the film was 3.2 µm. This effect can addition- to reduce the film resistivity.
ally be caused by a non-Newtonian sample flow. Adhesion
of the film was very good for the thin film segments. The
films were investigated by SEM studies (Figure 12). EDX
Conclusions
A straightforward synthetic methodology for the prepa-
ration of disilver–dicarboxylates and -squarates of type
[Ag2X] (X = oxalate, squarate, malonate, succinate, ma-
leicate, fumarate, and terephthalate), coordination polymers
[(bipym)Ag(O2CCO2)]n, [(bipym)(Ag(O2CCO2H))2]n (bi-
pym = bipyrimidine), and coordination complexes [(R3P)m-
AgXAg(PR3)m] (R = Ph, nBu) is discussed. The use of
[(nBu3P)3AgO2CCH2CO2Ag(PnBu3)3] as CVD and
[(nBu3P)AgO2C(CH2)2CO2Ag(PnBu3)] as well as [(nBu3P)2-
AgO2C(CH2)2CO2Ag(PnBu3)2] as spin-coating precursors
for the preparation of nanocrystalline silver films on glass
or pieces of TiN-coated oxidized silicon wafer materials is
possible. Conductive silver films with a thickness of 200–
300 nm could be deposited from [(nBu3P)2AgO2CCH2-
CO2Ag(PnBu3)2] on glass by using a vertical cold-wall CVD
reactor. For spin-coating, complexes [(nBu3P)AgO2-
C(CH2)2-
CO2AgP(nBu3)] and [(nBu3P)2AgO2C(CH2)2CO2AgP-
(nBu3)2] were applied. Heating of the deposited silver mate-
rials at a heating rate of 15 Kmin–1 to 450 °C gave silver
layers on TiN-coated oxidized silicon substrates. The EDX
analyses monitored silver films, which are contaminated
with traces of oxygen and carbon.
Figure 12. SEM images of the silver deposition obtained from 10e
(top) and 10f (bottom) as precursor materials.
Experimental Section
General: All reactions were carried out under an atmosphere of
nitrogen by using standard Schlenk techniques. Tetrahydrofuran,
diethyl ether, and n-hexane were purified by distillation from so-
dium/benzophenone ketyl; dichloromethane was purified by distil-
lation from calcium hydride. Celite (purified and annealed, Erg.
B.6, Riedel de Haen) was used for filtrations.
Instruments: Infrared spectra were recorded with a Perkin–Elmer
FTIR spectrometer Spectrum 1000. 1H NMR spectra were re-
corded with a Bruker Avance 250 spectrometer operating at
250.130 MHz in the Fourier transform mode; 13C{1H} NMR spec-
tra were recorded at 62.860 MHz. Chemical shifts are reported in
δ units (parts per million) downfield from tetramethylsilane with
the solvent as the reference signal [1H NMR: CDCl3 (99.8%), δ =
7.26; (CD3)2CO (99.9%), δ = 2.05; CD3CN (99.8%), δ = 1.94.
13C{1H} NMR: CDCl3 (99.8%), δ = 77.16; (CD3)2CO (99.9%), δ
=
29.84, 206.26]. 31P{1H} NMR spectra were recorded at
101.255 MHz in CDCl3 with P(OMe)3 as external standard [δ =
139.0, relative to H3PO4 (85%) with δ = 0.00]. Thermogravimetric
studies were carried out with a Perkin–Elmer System Pyris TGA
6 instrument with a constant heating rate of 8 Kmin–1 under N2
(20.0 dm3 h–1). DSC experiments were carried out with a Perkin–
Elmer System Pyris DSC 6 instrument with a constant heating rate
of 8 Kmin–1 under N2 (20.0 dm3 h–1). Melting points were deter-
Figure 13. EDX diagram of the silver deposition obtained from 10e
(top) and 10f (bottom) as precursors.
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Disilver(I) Coordination Complexes
mined using analytically pure samples sealed off in nitrogen purged
capillaries, on a Gallenkamp MFB 595 010 M melting point appa-
ratus. Microanalyses were performed with a C, H, N analyzer
FlashAE 1112 instrument (Thermo Company).
IR (KBr): ν = 1405, 1560, 1627, 1701 (s, C=C) (s, N=C) (s, C–O),
˜
3044, 3064, 3448 (OH) cm–1.
[(Ph3P)2AgC4O4Ag(PPh3)2] (10a): Complex 10a was prepared by
addition of 9a (2.18 g, 8.31 mmol) to a suspension of 3a (0.68 g,
2.08 mmol) in dichloromethane (30 mL) at 0 °C. After stirring for
2 h at this temperature, all volatile materials were removed by an
The CVD experiments were performed in a vertical cold-wall reac-
tor with a stagnation-point-flow geometry. The precursor was dis-
solved in tetrahydrofuran and introduced to the reactor by using a
pulsed spray evaporation technique that allows a control of the
feeding rate between 0.5 and 20 mLmin–1. The precursor solution
was mixed in a preheated flow of nitrogen in the heated evaporation
chamber. The inlet tube, with an inner diameter of 10 mm, was
maintained at a temperature slightly above the evaporation tem-
perature to prevent condensation. The glass substrates were cleaned
with hot sulfuric acid, acetone, and ethanol in an ultrasonic bath
and placed on a resistively heated ceramic block. The temperature
was measured with a thermocouple located directly at the substrate.
A rotary oil pump equipped with a cooling trap was used to keep
the reactor system at a pressure of 1 mbar during the deposition
process. The precursor solutions were prepared with tetra-
hydrofuran with analytical quality, and the nitrogen carrier gas was
dried by using standard methods before use. Evaporation tempera-
ture = 425 K, deposition temperature = 525–675 K, deposition
time = 30–50 min, and pressure = 1 mbar. The flow rate of the
carrier gas nitrogen was 40 sccm, and the concentration of the pre-
cursor solution in tetrahydrofuran was between 1.2 gL–1 and
3 gL–1. The thickness of the films was estimated gravimetrically by
assuming that the deposit has the density of bulk silver. The films
were inspected by using optical microscopy (Leica DM LM, magni-
fication 1500) and analyzed with X-ray diffraction (XRD) (X’pert
pro MRD, Phillips) and scanning electron microscopy (SEM)
(Hitachi S-450). The electrical resistivity was measured by using a
home-built four-point probe setup.
oil-pump vacuum.
A colorless solid remained. Yield: 2.8 g
(2.0 mmol, 97% based on 3a). Mp: 169 °C (decomposition).
C28H20Ag2O4P4 (1376.86): C 24.42, H 1.46; found C 24.81, H
1.73%. IR (KBr): ν = 1507 (s, C–O), 1560 (s, C–O) cm–1. 1H NMR
˜
(250 MHz, CDCl3, 25 °C): δ = 7.29–7.36 (m, 60 H, Ph) ppm.
13C{1H} NMR (62.9 MHz, CDCl3, 25 °C): δ = 128.9 (d, JCP
=
7 Hz, mC/Ph), 129.3 (oC/Ph) ppm; notice that the CO carbon atoms
could not be detected under the measurement conditions applied.
31P{1H} NMR (101.3 MHz, CDCl3, 25 °C): δ = –3.7 ppm.
[(Ph3P)3AgC4O4Ag(PPh3)3] (10b): The metal–organic compound
10b was prepared by the same reaction protocol as described for
10a: phosphane 9a (3.13 g, 11.93 mmol), disilver squarate 3a
(0.65 g, 1.99 mmol). After appropriate workup, complex 10b was
isolated as a colorless solid. Yield: 3.7 g (1.90 mmol, 97% based on
3a). Mp: 128 °C. C40H30Ag2O4P6 (1900.54): C 25.28, H 1.59; found
C 25.37, H 1.88%. IR (KBr): ν = 1340 (m, C–O), 1582 (s, C–O)
˜
cm–1. 1H NMR (250 MHz, CDCl3, 25 °C): δ = 7.29–7.34 (m, 90 H,
Ph) ppm. 13C{1H} NMR (62.9 MHz, CDCl3, 25 °C): δ = 128.0 (d,
JCP = 8 Hz, mC/Ph), 129.6 (oC/Ph), 134.2 (d, JCP = 18 Hz, iC) ppm;
note that the CO carbon atoms could be not detected under the
used conditions. 31P{1H} NMR (101.3 MHz, CDCl3, 25 °C): δ =
–2.3 ppm.
[(nBu3P)2AgO2CCH2CO2Ag(PnBu3)2] (10c): Complex 10c could be
synthesized by reacting 9b (2.42 g, 12.0 mmol) with 3c (0.95 g,
3.0 mmol) in tetrahydrofuran (30 mL) at 25 °C. The solution was
stirred for 2 h and afterwards filtered through a pad of Celite. All
volatile materials were removed by an oil-pump vacuum, whereby
10c was obtained as a pale brown oil. Yield: 2.92 g (2.59 mmol,
86% based on 3c). C51H110O4Ag2P4 (1127.06): C 54.35, H 9.84;
The spin-coating experiments were carried out on an industrial
spin-coating system (Suss Microtec Inc.) with a closed deposition
chamber. A precursor sample of 1.6 g of the complex was diluted
in 0.4 mL tetrahydrofuran and mixed for 2 min under a nitrogen
stream. Since tetrahydrofuran is highly volatile, a slow rotation
speed of 800 rpm was chosen. The sample was dispensed on the
precleaned TiN-coated Si-wafer, and after spin-off for 10 s, the film
was almost dry. The applied sintering parameters were: heating rate
15 Kmin–1, maximum sintering temperature 450 °C, and dwell time
0.5 h. The film resistivity was determined by using a four-point
resistance instrument from Omnimap company.
found C 54.77, H 9.82%. IR (NaCl): ν = 1417 (s, C–O), 1558 (vs,
˜
1
3
C–O) cm–1. H NMR (250 MHz, CDCl3, 25 °C): δ = 0.87 [t, JHH
= 6.6 Hz, 36 H, P(CH2)3CH3], 1.39–1.58 [m, 72 H, P(CH2)3CH3],
3.16 (s, 2 H, O2CCH2CO2) ppm. 13C{1H} NMR (62.9 MHz,
CDCl3, 25 °C): δ = 13.7 [P(CH2)3CH3], 18.9 (O2CCH2CO2), 24.4
[d, JCP
= 13 Hz, P(CH2)2CH2CH3], 25.1 (d, JCP = 14 Hz,
PCH2CH2CH2CH3), 27.6 [PCH2(CH2)2CH3], 174.3 (CO) ppm.
31P{1H} NMR (101.3 MHz, CDCl3, 25 °C): δ = –6.8 ppm. TGA
(8 K/min): Tstart = 100 °C, Tend = 315 °C, ∆m = 79.2%. DSC (8 K/
min): peak 1: T = 74 °C, ∆H1 = 1.9 J/g; peak 2: T = 145 °C, ∆H2
= –12.6 J/g; peak 3: T = 234 °C, ∆H3 = 11.5 J/g; peak 4: T =
352 °C, ∆H4 = –6.9 J/g.
Reagents: Bipyrimidine[19] and [(bipym)AgNO3][20] were prepared
according to published procedures. Complexes 3a–3g were synthe-
sized by the preparation protocol given in the literature.[1b] All
other chemicals were purchased by commercial suppliers and were
used without further purification.
[(nBu3P)3AgO2CCH2CO2Ag(PnBu3)3] (10d): Compound 10d was
[(bipym)AgO2CCO2Ag]n (5) and [HO2CCO2Ag(bipym)AgO2- synthesized in the same manner as 10c. Thus, 9b (3.64 g,
CCO2H] (8): Compound 5 was synthesized by mixing a hot water
solution (30 mL) containing 6 (472 mg, 0.72 mmol) with 7 (210 mg,
18.0 mmol) was treated with 3c (0.95 g, 3.0 mmol). After appropri-
ate workup, 10d was isolated as a colorless oil. Yield: 4.08 g
0.36 mmol) dissolved in water (20 mL). After stirring the reaction (2.66 mmol, 88% based on 3c). C75H164O4Ag2P6 (1531.70): C
mixture for 1 h at 25 °C, complex 5 precipitated as a colorless to
pale yellow solid, which is poorly soluble in water and insoluble in
common organic solvents including tetrahydrofuran, dimethylsulf-
oxide, and dichloromethane. Complex 8 was separated as a by-
product in the course of washing the precipitate with water
(3ϫ30 mL, 70 °C). Yield: 5, 169 mg (0.34 mmol, 47% based on 6);
8, 4 mg (0.01 mmol, 1.4% based on 6). Complex 5:
C10H6Ag2N4O4·H2O (497.946): C 24.12, H 2.02, N 11.25; found C
58.81, H 10.79; found C 58.59, H 10.62%. IR (NaCl]): ν = 1416
˜
(s, C–O), 1552 (vs, C–O) cm–1. 1H NMR (250 MHz, CDCl3, 25 °C):
3
δ = 0.86 [t, JHH = 6.7 Hz, 54 H, P(CH2)3CH3], 1.34–1.56 [m, 108
H, P(CH2)3CH3], 3.06 (s, 2 H, O2CCH2CO2) ppm. 13C{1H} NMR
(62.9 MHz, CDCl3, 25 °C):
δ = 13.9 [P(CH2)3CH3], 19.2
(O2CCH2CO2), 24.6 [d, JCP = 13 Hz, P(CH2)2CH2CH3], 25.4 (d,
JCP
=
12 Hz, PCH2CH2CH2CH3), 27.6 [d, JCP
PCH2(CH2)2-
= 5 Hz,
24.45, H 1.90, N 11.37. IR (KBr): ν = 1312, 1406, 1560, 1596, 1602,
CH3], 173.4 (CO) ppm. 31P{1H} NMR (101.3 MHz, CDCl3,
˜
1608 (s, C=C) (s, N=C) (s, C–O), 3368 (s, OH) cm–1. Complex 8: 25 °C): δ = –9.5. TGA (8 K/min): Tstart = 99 °C, Tend = 356 °C, ∆m
Eur. J. Inorg. Chem. 2010, 2975–2986
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2983

H. Lang et al.
20 Hz,
FULL PAPER
= 85.7%. DSC (8 K/min): peak 1: T = 154 °C, ∆H1 = 6.6 J/g; peak
2: T = 165 °C, ∆H2 = 7.1 J/g; peak 3: T = 284 °C, ∆H3 = –65.3 J/g.
14 Hz,
P(CH2)2CH2CH3],
25.3
(d,
JCP
=
PCH2CH2CH2CH3), 28.0 [d, JCP = 3 Hz, PCH2(CH2)CH3], 130.7
[O2C(CH)2CO2], 175.3 (CO) ppm. 31P{1H} NMR (101.3 MHz,
[(nBu3P)AgO2C(CH2)2CO2Ag(PnBu3)] (10e): Complex 10e was
synthesized by applying the same preparation procedure as dis-
cussed for 10a: 9b (0.12 g, 0.58 mmol), 3d (0.097 g, 0.29 mmol). Af-
ter appropriate workup, 10e was obtained as a yellow oil. Yield:
0.20 g (0.27 mmol, 93% based on 3d). C28H58Ag2O4P2 (736.45): C
1
CDCl3, 25 °C): δ = –2.3 (d, J109/107Ag31P = 677 Hz) ppm.
[cis-(nBu3P)2AgO2CCH=CHCO2Ag(PnBu3)2] (10i): Complex 10i
was prepared in the same manner as 10h by reacting 9b (127 mg,
6.3 mmol, 1.57 mL) with 3e (500 mg, 1.6 mmol) at 0 °C. Yield:
1.58 g (1.4 mmol, 89% based on 3e). C52H108Ag2O4P4 (1139.06): C
45.66, H 7.94; found C 45.78, H 7.99%. IR (NaCl): ν = 1380 (s,
˜
C–O), 1553 (vs, C–O) cm–1. H NMR (250 MHz, CDCl3, 25 °C):
54.83, H 9.73; found C 55.09, H 7.64%. IR (NaCl): ν = 1208 (s,
1
˜
δ = 0.84 [t, JHH = 7.0 Hz, 18 H, P(CH2)3CH3], 1.27–1.55 [m, 36 C–O), 1580 (vs, C–O) cm–1. H NMR (250 MHz, CDCl3, 25 °C):
3
1
H, P(CH2)3CH3], 2.50 [br. s, 4 H, O2C(CH2)2CO2] ppm. 13C{1H}
δ = 0.87 [t, JHH = 5.6 Hz, 36 H, P(CH2)3CH3], 1.43–1.66 [m, 72
3
NMR (62.9 MHz, CDCl3, 25 °C): δ = 14.0 [P(CH2)3CH3], 24.7 [d, H, P(CH2)3CH3], 6.07 [s, 2 H, O2C(CH)2CO2] ppm. 13C{1H} NMR
JCP 15 Hz, P(CH2)2CH2CH3], 25.6 (d, JCP 19 Hz, (62.9 MHz, CDCl3, 25 °C): δ = 13.9 [P(CH2)3CH3], 24.6 [d, JCP
PCH2CH2CH2CH3), 28.2 [PCH2(CH2)2CH3], 31.3 [O2C(CH2)2- 13 Hz, P(CH2)2CH2CH3], 25.3 (d, JCP 14 Hz, PCH2CH2-
CO2], 174.7 (CO) ppm. 31P{1H} NMR (101.3 MHz, CDCl3,
CH2CH3), 28.0 [d, JCP 3 Hz, PCH2(CH2)2CH3], 130.5
25 °C): δ = –0.4 ppm. TGA (8 K/min): Tstart = 151 °C, Tend
=
=
=
=
=
=
[O2C(CH)2-
411 °C, ∆m = 69.1%. DSC (8 K/min): peak 1: T = 253 °C, ∆H1 =
CO2], 175.0 (CO) ppm. 31P{1H} NMR (101.3 MHz, CDCl3,
3.5 J/g.
25 °C): δ = –5.3 ppm.
[(nBu3P)2AgO2C(CH2)2CO2Ag(PnBu3)2] (10f): Complex 10f was [cis-(nBu3P)3AgO2CCH=CHCO2Ag(PnBu3)3] (10j): Complex 10j
synthesized by the reaction protocol described for the synthesis of
10c: 9b (2.42 g, 12.0 mmol), 3d (0.99 g, 3.0 mmol). After appropri-
ate workup, 10f was obtained as a pale brown oil. Yield: 2.86 g
(2.51 g, 83% based on 3d). C52H112Ag2O4P4 (1141.09): C 54.73, H
was prepared as discussed for 10h: 9b (368 mg, 1.82 mmol,
0.45 mL), 3e (100 mg, 0.30 mmol). Yield: 445 mg (0.29 mmol, 95%
based on 3e). C76H164Ag2O4P6 (1543.69): C 59.13, H 10.71; found
C 58.87, H 10.83%. IR (NaCl): ν = 1463 (m, C–O), 1564 (m, C–
˜
1
9.89; found C 54.94, H 9.81%. IR (NaCl): ν = 1383 (s, C–O), 1555
O), 1685 (w, C=C) cm–1. H NMR (250 MHz, CDCl3, 25 °C): δ =
˜
(vs, C–O) cm–1. 1H NMR (250 MHz, CDCl3, 25 °C): δ = 0.63 [t, 0.78 [t, JHH = 7.5 Hz, 54 H, P(CH2)3CH3], 1.22–1.51 [m, 108 H,
3
3JHH = 6.8 Hz, 36 H, P(CH2)3CH3], 1.11–1.30 [m, 72 H, P(CH2)3- P(CH2)3CH3], 6.10 (s, 2 H, CH) ppm. 13C{1H} NMR (62.9 MHz,
CH3], 2.28 [s,
(62.9 MHz, CDCl3, 25 °C): δ = 13.9 [P(CH2)3CH3], 24.6 [d, JCP
12 Hz, P(CH2)2CH2CH3], 25.4 (d, JCP 12 Hz,
4
H, O2C(CH2)2CO2] ppm. 13C{1H} NMR CDCl3, 25 °C): δ = 13.8 [P(CH2)3CH3], 24.5 [d, JCP = 13 Hz,
=
P(CH2)2CH2CH3], 25.3 (d, JCP = 11 Hz, PCH2CH2CH2CH3), 27.6
[d, JCP = 5 Hz, PCH2(CH2)2CH3], 135.9 [O2C(CH)2CO2], 169.0
=
PCH2CH2CH2CH3), 25.8 [O2C(CH2)2CO2], 27.7 [PCH2(CH2)2- (CO) ppm. 31P{1H} NMR (101.3 MHz, CDCl3, 25 °C): δ =
CH3], 179.3 (CO) ppm. 31P{1H} NMR (101.3 MHz, CDCl3,
25 °C): δ = –7.9 ppm. TGA (8 K/min): Tstart = 125 °C, Tend
–9.5 ppm.
=
[trans-(nBu3P)AgO2CCH=CHCO2Ag(PnBu3)] (10k): To a suspen-
sion of 3f (0.14 g, 0.41 mmol) in dichloromethane (20 mL) was
added 9b (0.16 g, 0.2 mL, 0.81 mmol) in a single portion. At the
time the reaction mixture became clear, stirring was continued for
400 °C, ∆m = 80.6%. DSC (8 K/min): peak 1: T = 86 °C, ∆H1 =
2.6 J/g; peak 2: T = 243 °C, ∆H2 = 15.1 J/g; peak 3: T = 274 °C,
∆H3 = –5.3 J/g.
[(nBu3P)3AgO2C(CH2)2CO2Ag(PnBu3)3] (10g): Complex 10g was 1 h and then the reaction mixture was filtered through a pad of
synthesized as described for 10c; 9b (3.64 g, 18.0 mmol), 3d (0.99 g,
3.0 mmol). After appropriate workup, complex 10g could be iso-
lated as a colorless oil. Yield: 4.06 g (2.62 mmol, 87% based on
3d). C76H166O4Ag2P6 (1545.73): C 59.06, H 10.82; found C 59.33,
Celite. Afterwards, all volatiles were removed by an oil-pump vac-
uum, and 10k was obtained as a yellow oil. Yield: 0.28 g
(0.38 mmol, 93% based on 3f). C28H56Ag2O4P2 (734.48): C 45.78,
H 7.69; found C 45.98, H 7.81%. IR (NaCl): ν = 1360 (m, C–O),
˜
H 11.01%. IR (NaCl): ν = 1376 (s, C–O), 1561 (vs, C–O) cm–1. 1H 1568 (m, C–O), 1695 (w, C=C) cm–1. 1H NMR (250 MHz, CDCl3,
˜
NMR (250 MHz, CDCl3, 25 °C): δ = 0.83 [t, 3JHH = 6.5 Hz, 54 H, 25 °C): δ = 0.84 (t, JHH = 7.0 Hz, 18 H, CH3), 1.27–1.55 (m, 36
3
3
P(CH2)3CH3], 1.33–1.45 [m, 108 H, P(CH2)3CH3], 2.47 [s, 4 H,
H, CH2), 6.83 (d, JHH = 1 Hz, 2 H, CH) ppm. 13C{1H} NMR
O2C(CH2)2CO2] ppm. 13C{1H} NMR (62.9 MHz, CDCl3, 25 °C):
(62.9 MHz, CDCl3, 25 °C): δ = 14.1 [P(CH2)2CH3], 24.7 [d, JCP
=
δ = 13.6 [P(CH2)3CH3], 24.3 [d, JCP = 12 Hz, P(CH2)2CH2CH3], 12 Hz, P(CH2)2CH2CH3], 25.6 (d, JCP
=
12 Hz, PCH2CH2-
23.6 [O2C(CH2)2CO2], 25.3 (PCH2CH2CH2CH3) 27.3 [PCH2- CH2CH3), 27.9 [PCH2(CH2)2CH3], 135.6 (CH), 174.7 (CO) ppm.
(CH2)2CH3], 177.3 (CO) ppm. 31P{1H} NMR (101.3 MHz, CDCl3, 31P{1H} NMR (101.3 MHz, CDCl3, 25 °C): δ = –0.2 (d, J107Ag31P
25 °C): δ = –14.4 ppm. TGA (8 K/min): Tstart = 101 °C, Tend
349 °C, ∆m = 83.9%. DSC (8 K/min): peak 1: T = 264 °C, ∆H1 =
–83.7 J/g; peak 2: T = 273 °C, ∆H2 = 41.4 J/g.
=
= 672 Hz), –0.2 (d, J109Ag31P = 773 Hz) ppm. TGA (8 K/min): Tstart
= 112 °C, Tend = 358 °C, ∆m = 80.3%. DSC (8 K/min): peak: T =
264 °C, ∆H = 46.5 J/g.
[cis-(nBu3P)AgO2CCH=CHCO2Ag(PnBu3)] (10h): For the synthe-
sis of 10h, complex 9b (584 mg, 2.9 mmol, 0.72 mL) was treated
with 3e (500 mg, 1.5 mmol) in dichloromethane (30 mL) at 0 °C.
The reaction solution was stirred for 2 h at 0 °C and afterwards
filtered through a pad of Celite. All volatiles were removed by an
oil-pump vacuum, and 10h was obtained as a pale brown oil. Yield:
1.04 g (1.4 mmol, 93% based on 3e). C28H56Ag2O4P2 (734.43): C
[trans-(nBu3P)2AgO2CCH=CHCO2Ag(PnBu3)2] (10l): The synthe-
sis of 10l was performed as discussed for the preparation of 10k.
Thus 3f (137 mg, 0.42 mmol) was treated with 9b (329 mg, 0.40 mL,
1.66 mmol). Complex 10l was obtained as a colorless oil. Yield:
460 mg (0.4 mmol, 95% based on 3f). C52H110Ag2O4P4 (1139.07):
C 54.83, H 9.73; found C 54.17, H 9.50%. IR (NaCl): ν = 1377 (s,
˜
C–O), 1586 (s, C–O), 1705 (m, C=C) cm–1. 1H NMR (250 MHz,
3
45.79, H 7.69; found C 45.34, H 7.52%. IR (NaCl): ν = 1556 (vs, CDCl3, 25 °C): δ = 0.88 [t, JHH = 7.0 Hz, 36 H, P(CH2)3CH3],
˜
1
C–O), 1638 (m, C=C) cm–1. H NMR (250 MHz, CDCl3, 25 °C):
1.41–1.57 [m, 72 H, P(CH2)3CH3], 6.71 (s, 2 H, CH) ppm. 13C{1H}
3
δ = 0.85 [t, JHH = 7.0 Hz, 18 H, P(CH2)3CH3], 1.37–1.58 [m, 36 NMR (62.9 MHz, CDCl3, 25 °C): δ = 14.1 [P(CH2)3CH3], 24.8
H, P(CH2)3CH3], 6.06 [s, 2 H, O2C(CH)2CO2] ppm. 13C{1H} NMR [P(CH2)2CH2CH3], 25.6 (PCH2CH2CH2CH3), 27.9 [PCH2(CH2)2-
(62.9 MHz, CDCl3, 25 °C): δ = 14.0 [P(CH2)3CH3], 24.6 [d, JCP
2984
=
CH3], 135.9 (CH), 173.4 (CO) ppm. 31P{1H} NMR (101.3 MHz,
www.eurjic.org
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2010, 2975–2986

Disilver(I) Coordination Complexes
1
CDCl3, 25 °C): δ = –7.4 ppm. TGA (8 K/min): Tstart = 74 °C, Tend δ = –8.4. (d, 1J
= 447 Hz), –8.4 (d, J
107Ag31
P
109Ag31
P = 516 Hz) ppm.
= 330 °C, ∆m = 67.4%. DSC (8 K/min): peak: T = 216 °C, ∆H =
TGA (4 K/min): Tstart = 100 °C, Tend = 300 °C, ∆m = 81.1%.
22.2 J/g.
Crystal Structure Determination: Crystal data for 5, 6, and 8 are
presented in Table 5. All data were collected with a Oxford Gemini
5 diffractometer at 100(2) K by using Mo-Kα radiation (λ =
0.71073 Å). The structures were solved by direct methods by using
SHELXS-97[20] and refined by full-matrix least-square procedures
on F2 with SHELXL-97.[21] All non-hydrogen atoms were refined
anisotropically, and a riding model was employed in the refinement
of the hydrogen atom positions. CCDC-704873 for 5, CCDC-
704875 for 6, and CCDC-704874 for 8 contain the supplementary
crystallographic data for this paper. These data can be obtained
free of charge from The Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data_request/cif.
[trans-(nBu3P)3AgO2CCH=CHCO2Ag(PnBu3)3] (10m): Complex
10m was synthesized as described for 10k: 3f (126 mg, 0.38 mmol),
9b (454 mg, 0.55 mL, 2.29 mmol). After appropriate workup, 10m
could be isolated as a colorless oil. Yield: 540 mg (3.5 mmol, 92%
based on 3f). C76H164Ag2O4P6 (1543.71): C 59.13, H 10.71; found
C 59.29, H 10.95%. IR (NaCl): ν = 1377 (m, C–O), 1567 (m, C–
˜
O), 1706 (s, C=C) cm–1. H NMR (250 MHz, CDCl3, 25 °C): δ =
1
3
0.90 [t, JHH = 7.0 Hz, 54 H, P(CH2)3CH3], 1.42–1.55 [m, 108 H,
P(CH2)3CH3], 6.69 (s, 2 H, CH) ppm. 13C{1H} NMR (62.9 MHz,
CDCl3, 25 °C): δ = 14.0 [P(CH2)3CH3], 24.6 [d, JCP = 15 Hz,
P(CH2)2CH2CH3], 25.5 (d, JCP = 10 Hz, PCH2CH2CH2CH3), 27.7
[d, JCP = 6 Hz, PCH2(CH2)2CH3], 134.3 (CH), 173.9 (CO) ppm.
31P{1H} NMR (101.3 MHz, CDCl3, 25 °C): δ = –12.2 ppm. TGA
(8 K/min): Tstart = 100 °C, Tend = 484 °C, ∆m = 79.7%. DSC (8 K/
min): peak: T = 311 °C, ∆H = –34.3 J/g.
Acknowledgments
We are grateful to the Deutsche Forschungsgemeinschaft (DFG,
Schwerpunktprogramm SPP 1119, International Research Training
Group GRK 1215, “Materials and Concepts for Advanced Inter-
connects”) and the Fonds der Chemischen Industrie (FCI) for fin-
ancial support.
[(nBu3P)2AgO2C-1-C6H4-4-CO2Ag(n-PBu3)2] (10n): Complex 10n
was synthesized by addition of 9b (610 mg, 0.74 mL, 3.0 mmol) to
a suspension of 3g (300 mg, 0.8 mmol) in diethyl ether (40 mL) at
25 °C. After stirring for 2 h, the reaction mixture was filtered
through a pad of Celite, and all volatiles were removed by an oil-
pump vacuum. A yellow hygroscopic solid remained. Yield: 860 mg
(0.7 mmol, 96%, based on 3g). Mp: 27 °C. C56H112Ag2O4P4
[1] a) W.-P. Wu, Y.-Y. Wang, C.-J. Wang, Y.-P. Wu, P. Liu, Q.-Z.
Shi, Inorg. Chem. Commun. 2006, 9, 645; b) A. Jakob, H.
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M. E. Brown, H. Kelly, A. K. Galwey, M. A. Mohamed,
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Heidelberg, New York.
(1189.14): C 56.56, H 9.49; found 56.39, H 946. IR (KBr): ν = 1370
˜
(s, C–O), 1565 (s, C–O), 1931 (w, C=C) cm–1. 1H NMR
3
(250.1 MHz, CDCl3, 25 °C): δ = 0.79 [t, JHH = 6.9 Hz, 36 H,
P(CH2)3CH3], 1.28–1.65 [m, 72 H, P(CH2)3CH3], 7.93 (s, 4 H, Ph)
ppm. 13C{1H} NMR (62.9 MHz, CDCl3, 25 °C):
[P(CH2)3-
δ = 13.3
CH3], 24.1 [d, JCP = 11 Hz, P(CH2)2CH2CH3], 25.0 (d, JCP
=
12 Hz, PCH2CH2CH2CH3), 27.2 [PCH2(CH2)2CH3], 128.2 (CH),
139.0 (iC), 172.3 (CO) ppm. 31P{1H} NMR (101.3 MHz, CDCl3,
25 °C): δ = –8.4 ppm. 31P{1H} NMR (101.3 MHz, CDCl3, –60 °C):
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ˇ
G. Süss-Fink, P. Steˇpnicˇka, J. Ludvík, J. Organomet. Chem.
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Table 5. Crystal and intensity collection data for 5, 6, and 8.
5
6
8
Formula
Fw
C5H7Ag1N2O4 C10H14Ag2N4O8 C6H4AgN2O4
267.00
674.11
275.98
Crystal system
Space group
a (Å)
b (Å)
c (Å)
triclinic
P1
orthorhombic monoclinic
¯
Pna21
P21/n
5.7165(8)
6.8605(12)
9.6419(13)
89.357(12)
93.956(11)
100.074(13)
371.42(10)
2
14.553(3)
22.849(4)
6.2866(12)
3.5770(3)
9.9954(6)
19.6856(18)
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110, 13759; b) A. Thirumurugan, S. Natarajan, Eur. J. Inorg.
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references cited therein.
α (°)
β (°)
γ (°)
94.508(8)
Volume (Å3)
Z
2090.5(7)
4
701.65(10)
4
F(000)
260
2.387
1320
2.142
532
2.613
?
293(2)
2.91–26.00
6404
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ala, Chem. Vap. Deposition 2007, 13, 408; b) N. Bahlawane,
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Dcalcd. (gcm–3)
Crystal size (mm)
T (K)
0.2ϫ0.1ϫ0.03 0.2ϫ0.1ϫ0.05
293(2)
3.02–26.09
100
2θ ranges (°)
2.80–26.09
28431
4145
No. reflections collected 3350
No. reflections observed 1442
1381
R1, wR2[a]
0.0416, 0.0575 0.0264, 0.0385 0.0187, 0.0376
0.535, –0.521 0.919, –0.480
–
Final difference (eÅ–3)
Flack x[22]
0.286, –0.339
–
–0.03(3)
[a] R1 = [Σ(||Fo| – |Fc|)/Σ|Fo|]; wR2 = [Σ(w(Fo – Fc ) )/Σ(wFo4)]1/2. S [7] a) H. Schmidt, Y. Shen, M. Leschke, Th. Haase, K. Kohse-
2
2 2
= [Σw(Fo – Fc ) n – pp]1/2. n = number of reflections, p = param-
Höinghaus, H. Lang, J. Organomet. Chem. 2003, 669, 25; b)
A. Jakob, H. Schmidt, P. Djiele, Y. Shen, H. Lang, Microchim.
2
2 2
eters used.
Eur. J. Inorg. Chem. 2010, 2975–2986
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
2985

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Received: February 9, 2010
Published Online: May 19, 2010
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