Lewis-base stabilized N-silver(I) succinimide complexes: Synthesis, crystal structures and their use as CVD-precursors

Article abstract of DOI:10.1002/zaac.201100072

Four Lewis-base stabilized N-silver(I) succinimide complexes of type [L_n·R_m·AgNC₄H₄O ₂] (L = N,N,N′,N′-tetramethylethylenediamine (TMEDA), n = 1, m = 0, 2a; L = P(OEt)₃, n = 2, m = 0, 2b; L

Full text of DOI:10.1002/zaac.201100072

ARTICLE
DOI: 10.1002/zaac.201100072
Lewis-Base Stabilized N-Silver(I) Succinimide Complexes: Synthesis, Crystal
Structures and Their Use as CVD-Precursors
Xian Tao,[a] Ke-Cheng Shen,[a] Yu-Long Wang,[a] and Ying-Zhong Shen*[a]
Keywords: Silver; Succinimide; X-ray diffraction; MOCVD; Vapor deposition
Abstract. Four Lewis-base stabilized N-silver(I) succinimide com- ion pair {[Ag(TMEDA)2]+[Ag(NC4H4O2)2]–} in the solid state and
plexes of type [Ln·Rm·AgNC4H4O2] (L = N,N,N',N'-tetramethylethyl- complex 2c is a monomer with the three-coordinate silver atom. Com-
enediamine (TMEDA), n = 1, m = 0, 2a; L = P(OEt)3, n = 2, m = 0, plex 2b was used as precursor in the deposition of silver for the first
2b; L = PPh3, m = 0, n = 2, 2c; L = P(OMe)3, R = TMEDA, n = 1, time by using MOCVD technique. The silver films obtained were char-
m = 1, 2d) were prepared by a “one-pot” synthesis methodology and acterized using scanning electron microscopy (SEM) and energy-dis-
characterized. The molecular structures of 2a and 2c have been deter- persion X-ray analysis (EDX). SEM and EDX studies show that the
mined by using X-ray single crystal analysis. Complex 2a exists as dense and homogeneous silver films could be obtained.
crystal structures of 2a and 2c were determined and discussed
Introduction
as well.
In recent years, owing to the highest electrical conductivity
and the lowest contact resistance among all metals,[1–5] silver
has been widely used in many fields include: optical devices,[6]
components in high temperature superconductor materials,[7]
magnetic,[8] bactericidal coatings[9] and interconnect material
in microelectronics.[10] Various methods have been used for
the growth of silver thin films, such as sputtering,[11] thermal
evaporation,[12] electron-beam evaporation,[13] and chemical
vapor deposition (CVD).[14] Metal Organic Chemical Vapor
Deposition (MOCVD) is a very effective technique for the
growth of high quality metal films due to the high deposition
rates with good step coverage[15–18] and higher aspect ratio in
the multilevel metallization structure.[19]
Results and Discussion
Synthesis
The Lewis-base stabilized N-silver(I) succinimide complexes
of type [Ln·Rm·AgNC4H4O2] (L = N,N,N',N'-tetramethylethyl-
enediamine (TMEDA), n = 1, m = 0, 2a; L = P(OEt)3, n = 2,
m = 0, 2b; L = PPh3, m = 0, n = 2, 2c; L = P(OMe)3, R =
TMEDA, m = 1, n = 1, 2d) were prepared by using the consec-
utive reaction of [AgNO3], auxiliary donor ligands, succinim-
ide and Et3N by a “one-pot” synthesis methodology (Experi-
mental Section) (Scheme 1). The complexes were isolated in
high yield as colorless solids (2a, 2c) or colorless liquids (2b,
2d). Complexes 2a–2c are stable under inert atmosphere for
months at room temperature, but complex 2d is sensitive to
temperature and must be stored at 0 °C. On exposure to air
they all decompose within minutes (2a, 2d) or hours (2b, 2c)
to form brown products. All products obtained gave satisfac-
tory elemental analysis results and were characterized by FT-
The key to achieve success for MOCVD, however, is the
selection of suitable precursors. As the precursors for
MOCVD, the complexes should have good volatility, thermal
stability, high purity and a suitable thermal decomposition
mechanism.[20,21] Before, the research of silver precursors has
focused mainly on silver(I) β-diketonates or structurally related
complexes,[22–26] silver(I) carboxylates,[27–31] with various Le-
wis-base ancillary ligands. However, the precursors are not
sufficiently available and the decomposition mechanism(s) are
unclear. The development of new silver precursors is indispen-
sable. In this paper, we describe different synthesis methodolo-
gies and properties of four Lewis-base stabilized N-silver(I)
succinimide complexes which were used as precursor for the
growth of silver by using MOCVD techniques. The single
1
IR, H NMR and 13C {H} NMR spectroscopy, respectively.
* Prof. Dr. Y.-Z. Shen
Fax: +86-25-52112626
E-Mail: yz_shen@nuaa.edu.cn
[a] Applied Chemistry Department
School of Material Science & Engineering
Nanjing University of Aeronautics & Astronautics
Nanjing 210016, P. R. China
Scheme 1. Synthesis of Complexes 2a–2d.
© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Z. Anorg. Allg. Chem. 2011, 637, 1394–1400
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Lewis-Base Stabilized N-Silver(I) Succinimide Complexes
The complexes also could be prepared by using auxiliary shifts of all carbonyl are found in the range of 191–192 ppm,
donor ligands reacting with N-silver(I) succinimide in dichlo- which are similar to those of other metal succinimide
romethane in stoichiometry at 0 °C in relation to the reported complexes.[32] In complex 2d, the alkyl carbon resonances of
synthesis procedures (Equation (1)),[32] or by reaction of TMEDA and trimethylphosphite are in the range of 47–
[AgNO3] with auxiliary donor ligands and [KNC4H4O2] in di- 58 ppm. However, the carbon resonances of ancillary ligands
ethyl ether at 0 °C (Equation (2)). The disadvantage of the in 2a–2d are easily distinguished from the resonance of –CH2–
synthesis procedures described in Equation (1) for 2a–2d is on C4H4NO2– (31.8–32.5 ppm).
the low yield of N-silver(I) succinimide (Yield: 40 % based on
Ag2O) given by using succinimide reacting with an excess of
Ag2O in boiling water.[32] Another adversarial aspect is the use
of N-silver(I) succinimide with no coordinated ligand, since it
shows the tendency to decompose on prolonged storage. The
disadvantage of the synthesis procedures described in Equation
(2) for 2a–2d is the purification because some products may
contain traces of chloride which is detrimental to their use as
CVD precursors in microtechnology. Therefore, we developed
a “one-pot“ synthesis methodology to prepare Lewis-base sta-
bilized N-silver(I) succinimide complexes. These preparative
studies show that an economical and straightforward synthesis
route was presented.
Structural Analysis
The molecular structures of 2a and 2c are depicted in Fig-
ure 1 and Figure 2, and selected bond lengths /Å and bond
angles /° are given in Table 1 and Table 2, respectively.
Figure 1. Molecular structure and atom numbering scheme for 2a. The
hydrogen atoms are omitted for clarity.
The spectra of metal succinimide complexes were investi-
gated by Woldbaek, Klaeboe, and Christensen.[33] In the IR
spectra, the broad N–H stretching band (~3170 cm–1) of suc-
cinimide disappeared in the complexes, as well as the sharp
out-of-plane N–H bending band (~820 cm–1).[33] Due to the
delocalization of the anionic charge to the ring and carbonyl
groups, thus decreasing the C=O bond order.[32] In the N-sil-
ver(I) succinimide complexes, the in-phase and out-of-phase
stretching vibrations of the C=O groups are observed between
1700–1710 cm–1 and 1590–1619 cm–1, respectively. In com-
plexes 2b and 2d, the P–O stretching vibration in organophos-
phine ligands shifted to higher frequencies in the complexes
provides the good evidence that the occurrence of the organo-
phosphine ligands coordinating to silver ion.
The NMR spectra (1H and 13C{H}) were recorded for all
1
four complexes at room temperature. In H NMR spectra, the
Figure 2. Molecular structure and atom numbering scheme for 2c. The
integration area ratios are in agreement with the stoichiome-
tries of the complexes. The chemical shifts of –CH2– protons
in C4H4NO2– appeared at δ = 2.50–2.63 ppm, which agrees
well with a previous report.[32] In complex 2d, the chemical
hydrogen atoms are omitted for clarity.
Complex 2a crystallizes in a monoclinic in the space group
shifts of alkyl protons of TMEDA [δ = 2.31 (s, 12 H, P21/c. Ion pair {[Ag(TMEDA)2]+[Ag(NC4H4O2)2]–} exhibits
(CH3)2N), δ = 2.43 (s, 4 H, NCH2)] and P(OMe)3 [δ = 3.71 no contact distances between anion and cation in the solid state
(d, 9 H, CH3O, JPH = 13.1 Hz)] shifted to downfield compared (Figure 1). In the cation, the silver(I) atom [Ag(2)] is presented
to free ancillary ligands. In the 13C NMR spectra, the chemical with four nitrogen atoms of two TMEDA ligands occupying
Z. Anorg. Allg. Chem. 2011, 1394–1400
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Table 1. Selected bond lengths /Å and angles /° for 2a.
meric succinimide complex, the three-coordinate nature of the
silver seems to be quite a satisfactory bonding environment.
The Ag–P bond length in complex 2c [2.443(8) Å] is almost
the same to the sum of covalent radii of the phosphorus and
silver atoms (2.44 Å).[36] The N–Ag distance in 2a and 2c is
2.084(2) Å, 2.083(2) Å and 2.220(3) Å, respectively, which
are all shorter than that of [(Ph3P)3·AgNC4H4O2]
[2.313(4) Å].[32] The average distances of C–O (1.216 Å), of
which the oxygen atoms do not chelate to the silver, is obvi-
ously shorter than those of [(MeO)3P·AgNC4H4O2]2 [(C(1)–
O(1): 1.243(4) Å; C(5)–O(3): 1.233(5) Å].[37] Comparison to
complex [(MeO)3P·AgNC4H4O2]2,[37] which has an Ag–O
bond, complexes 2a and 2c have the symmetrically centered
Ag–N with equidistant separations between the silver and oxy-
gen.
Bond lengths /Å
Ag(1)–N(2)
Ag(1)–N(1)
Ag(2)–N(4)
Ag(2)–N(6)
Ag(2)–N(5)
2.083(2) Ag(2)–N(3)
2.084(2) C(6)–O(4)
2.369(2) C(3)–O(1)
2.369(2) C(5)–O(3)
2.388(2) C(4)–O(2)
2.389(2)
1.218(3)
1.215(4)
1.214(3)
1.216(4)
Bond angles /°
N(2)–Ag(1)–N(1)
N(4)–Ag(2)–N(6)
N(4)–Ag(2)–N(5)
N(6)–Ag(2)–N(5)
N(4)–Ag(2)–N(3)
N(6)–Ag(2)–N(3)
N(5)–Ag(2)–N(3)
177.9(9) C(11)–N(4)–Ag(2)
128.9(8) C(12)–N(4)–Ag(2)
130.5(8) C(10)–N(4)–Ag(2)
77.6(8) C(5)–N(2)–Ag(1)
77.7(8) C(6)–N(2)–Ag(1)
127.4(8) C(4)–N(1)–Ag(1)
122.3(8) C(3)–N(1)–Ag(1)
112.3(18)
107.4(17)
106.6(15)
128.6(18)
121.1(17)
124.7(18)
124.5(19)
In general, silver(I) salts of structural type [AgX] (X = or-
ganic or inorganic group) are highly aggregated.[38–40] These
building blocks can be broken-down to lower aggregated spe-
cies by the addition of Lewis-bases.
Table 2. Selected bond lengths /Å and angles /° for 2c.
Bond lengths /Å
Silver(I) succinimide [AgNC4H4O2]n with no auxiliary donor
ligands have been shown to form oligomers with a variety of
structural motifs,[40,41] but including mainly dimers with crude
flat eight-membered rings A, the arrangement of which is
clearly codetermined by forming of Ag–O bonds (Scheme 2).
With donor ligands P (P = PPh3 or P(OMe)3), the ring systems
of 1:2 complexes [(P)2AgNC4H4O2]n and 1:3 complexes
[(P)3AgNC4H4O2]n cannot remain intact except 1:1 complexes
[(P)AgNC4H4O2]n.[32,37] The coordination number (CN) of the
metal atoms increase to 3 or 4 in these complexes, which lose
the Ag···Ag contacts as in B and C,[32] or preserve metallo-
philic bonding as in D.[37] However, with donor ligands N N
(N N = bipy or N,N,N’,N’-tetramethylethylenediamine), the
ring systems of 1:1 complexes [(N N)AgNC4H4O2]n are de-
stroyed with the different coordination number (CN) of the
metal atoms from 2 to 4 as E[42] and F. The special structure
as F exhibits no contact distances between anion and cation
with the two kinds of silver atoms which coordination number
Ag(1)–N(1)
Ag(1)–P(1)
O(1)–C(19)
2.220(3) C(19)–C(20)
2.443(8) C(20)–C(20)a
1.217(4) N(1)–C(19)
1.506(5)
1.503(7)
1.364(4)
Bond angles /°
N(1)–Ag(1)–P(1)
P(1)a–Ag(1)–P(1)
C(19)a–N(1)–C(19)
C(19)–N(1)–Ag(1)
107.3(18) O(1)–C(19)–N(1)
145.4(4) O(1)–C(19)–C(20)
110.6(4) N(1)–C(19)–C(20)
124.7(19) C(20)a–C(20)–C(19)
124.0(3)
125.5(3)
110.4(3)
104.1(2)
Symmetry operation: a = –x–1; y; –z – 3/2
four coordination sites, forming a distorted tetrahedral arrange-
ment. The two perpendicular planes of the [Ag(TMEDA)2]+,
defined by [N(3), Ag(2), N(4)] and [N(5), Ag(2), N(6)], re-
spectively, are almost vertical as indicated by the dihedral an-
gle (86.4°), which is close to the ideal value (90°). The atoms
[N(1), Ag(1), N(2)] of the [Ag(NC4H4O2)2]– cluster anion core,
approximately form a line with an angle of 177.9(9)°. The di-
hedral angle of two roughly planar succinimide rings is 115.9°.
The average distances of Ag–N (2.379 Å) is longer than that
of [Ag(hfac)(TMEDA)] [2.255(5) Å].[34] Three groups of the
average angle of N–Ag(2)–N (129.7°, 77.6°, 124.8°) are close
to that of [Ag(1b)2OTf] (132.7°, 76.3°, 123.7°) (1b =
C16H14N2Br2).[35]
Complex 2c has a crystallographic C2 symmetry axis passing
through the Ag(1)–N(1) vector. (Figure 2) It crystallizes in a
monoclinic in the space group C2/c, and a three-coordinate
silver(I) ion is presented with two phosphorus atoms from
PPh3 ligands occupying two coordination sites (PP) and the
nitrogen atom from succinimide occupying the third site. Four
atoms [P(1), N(1), P(1)a, Ag(1)] are in the same plane, forming
an isosceles triangle geometry around silver. The C(55)–
C(56)–C(57)–C(58) plane and P(1)–N(1)–P(1)a–Ag(1) plane
are roughly perpendicular to each other and the dihedral angle
is 80.3°. The P–Ag–P angle [145.4(5)°] is much larger than
that of [(Ph3P)2AgPI] [116.6(3)°] (PI = C8H4NO2), but the N–
Ag–P angle [107.3(18)°] is much smaller than that of
Scheme 2. Schematic representation of structural type A–F
[(Ph3P)2AgPI] [121.7(2)°] (PI = C8H4NO2).[33] In this mono- molecules.[30,38,44]
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Lewis-Base Stabilized N-Silver(I) Succinimide Complexes
(CN) are 2 and 4, respectively. It should be noted that the morphology and composition of the silver film were character-
structural chemistry of the silver succinimide is entirely differ- ized by scanning electron microscopy (SEM) and energy-dis-
ent. Only large ligands and the numbers of auxiliary donor persion X-ray analysis (EDX). SEM (Figure 4) studies show
ligands may prevent the close approach necessary for bonding that the dense and homogeneous silver layer was formed. The
Ag···Ag contacts and the forming of oligomers.
film is composed of many well isolated, granular genuine
pearls spreading all over the substrate. The sizes of silver
grains are in the range of 40–60 nm.
Thermal Analysis
Themogravimetry (TG) and Differential Scanning Calorime-
try (DSC) studies are required to optimize the temperature at
which the respective silver precursor should be maintained
during the CVD experiments. For an example, the TG and
DSC curves of complex 2c are shown in Figure 3. It can be
seen from the DSC curve of 2c that one apparent endothermic
process with the peak temperatures at 208 °C, which could be
attributed to the melting process of complex. There are two
continuous exothermic/endothermic processes from 210 °C to
261 °C with the peak temperatures at 237 °C and 255 °C. Seen
from the TG curve of 2c, it is very difficult to distinguish from
one step to another and know the sequence of decomposition
of PPh3 and succinimide. The final percentage of the residue
is 16.06 %, which is little higher than the theoretical value of
silver (14.77 %). The thermal measurement is in good agree-
ment with the structural analysis.
Figure 4. SEM spectrum of the silver film deposited from 2b (Ts =
350 °C, ptotal = 7.0 × 10–4 bar; carrier gas N2; flow rate = 20 sccm).
The EDX spectrum (Figure 5) of the deposited film shows
silver as the main component. Next to silver, silicon as sub-
strate component was detected which is due to the discontinu-
ous silver particles and the relatively high penetration depth of
the electron beam during the EDX analysis. The other light
elements, such as carbon, oxygen, phosphorus, which might be
present as impurities or due to a surface oxidation of silver,
are below the detection limit.
Figure 3. TG and DSC curves of 2c (heating rate 10 °C· min–1, argon
atmosphere).
MOCVD Depositions
On the basis of the thermal properties obtained from the TG
and DSC studies and Ref.,[32] we find these complexes may be
promising precursors for the growth of silver films. The com-
plex 2b has been successfully applied to deposit silver on sili-
con substrates by MOCVD. In a typical CVD experiment sil-
ver was deposited onto silicon substrate at 350 °C. The
evaporation temperature was maintained at 80 °C with a nitro-
gen flow rate at 20 sccm. The run time was 1.5 h and the total
pressure was kept at 7.0 × 10–4 bar. No reducing reagent such
as H2 was used in the deposition process. The average film
Figure 5. EDX spectrum of the silver film deposited from 2b (Ts =
350 °C, ptotal = 7.0 × 10–4 bar; carrier gas N2; flow rate = 20 sccm).
The result of this deposition experiment shows that complex
thickness was about 0.9 μm, giving a growth rate of 2b is a promising candidate for further MOCVD process of
0.6 μm·h–1. The layer deposited is silver colored. The surface silver nanocluster or silver films.
Z. Anorg. Allg. Chem. 2011, 1394–1400
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X. Tao, K.-C. Shen, Y.-L. Wang, Y.-Z. Shen
ARTICLE
Yield: 1.09 g (85 % based on AgNO3). Mp.: 165 °C dec.
C20H40O4Ag2N6: C, 37.28; H, 6.26. Found: C, 37.16; H, 6.02. 1H
NMR (CDCl3): δ = 2.51 (s, 12 H, CH3/(CH3)2N–H), δ = 2.52 (s, 4 H,
Conclusions
Four Lewis-base stabilized N-silver(I) succinimide com-
plexes has been synthesized by a “one-pot” synthesis method- NCH2–H), 2.63 (s, 4 H, CH2–). 13C{H} NMR (CDCl3): δ = 32.2
(CH2), δ = 48.1 (CH3), δ = 58.0 (CH2/NCH2–), δ = 191.6 (C=O). IR
(KBr) data: 3432 (m), 2928 (w), 1701 (m), 1619 (s), 1439 (m), 1359
(s), 1296 (s), 1249 (s), 827 (w), 669 (m), 570 (w), 451 (w) cm–1.
ology which is economical and straightforward. Complex 2a
exists as ion pair {[Ag(TMEDA)2]+[Ag(NC4H4O2)2]–} in the
solid state and complex 2c is a monomer with the three-coordi-
nate silver atom. In deposition experiments complex 2b was
used as MOCVD precursor to grow silver layers on silicon
substrates at 350 °C deposition temperature, carrier gas flow
20 sccm, and a total pressure of 7.0 × 10–4 bar, respectively.
{[(EtO)3P]2·AgNC4H4O2} (2b): Complex 2b was obtained by follow-
ing the above procedure, only using triethylamine (0.5059 g,
5.00 mmol), triethylphosphite (1.6620 g, 10.00 mmol), succinimide
(0.4955 g, 5.00 mmol) and AgNO3 (0.8494 g, 5.00 mmol) instead.
The film is composed of many well isolated, granular genuine After appropriate work-up, complex 2b was obtained as a colorless
liquid. Yield: 2.26 g (84 % based on AgNO3). C16H34O8AgNP2: C,
pearls spreading all over the substrate. The EDX results
showed that the obtained layer composed of pure silver within
the detection limit of EDX.
1
35.70; H, 6.37. Found: C, 35.57; H, 6.38. H NMR (CDCl3): δ = 1.2
(t, 18 H, CH3/CH3CH2–, JHH = 7.0 Hz), δ = 2.5 (s, 4 H, CH2–H), 3.9
(m, 12 H, CH2/CH3CH2–). 13C{H} NMR (CDCl3): δ = 31.8 (CH2),
δ = 191.0 (C), 16.1 (JPC = 6.1 Hz, CH3/CH3CH2–), 60.0 (JPC = 5.7 Hz,
CH2/CH3CH2–). IR (KBr) data: 3440 (m), 2979 (s), 2934 (m), 2901
(m), 2358 (w), 1715 (m), 1612 (s), 1477 (m), 1441 (m), 1391 (s), 1348
(s), 1287 (s), 1245 (s), 1162 (m), 1097 (m), 1022 (s), 937 (s), 771 (s),
669 (m), 536 (s), 442 (m) cm–1.
Experimental Section
Materials and Methods
All operations were carried out under an atmosphere of purified nitro-
gen with standard Schlenk techniques. The solvent diethyl ether was
purified by distillation from sodium/benzophenone under N2 before
use. 1H NMR were recorded with a Bruker DRX500 NMR spectrome-
ter operating at 500.13 MHz in the Fourier transform mode; 13C{H}
NMR spectra were recorded at 125.76 MHz. Chemical shifts are re-
ported in δ units (parts per million) downfield from tetramethylsilane
(δ = 0.0) with the solvent as the reference signal (1H NMR, CDCl3 δ =
7.26; 13C{H} NMR, CDCl3 δ = 77.55). Infrared spectra were collected
on Bruker Vector 22 instrument as KBr pellets at room temperature.
Thermogravimetric (TG) and Differential Scanning Calorimetric
(DSC) studies were carried out with the NETZSCH STA 449 C with
a constant heating rate of 10 °C·min–1 under Argon (30 cm3·min–1).
Elemental analysis was performed with a Perkin–Elmer 240 C elemen-
tal analyzer. Melting points were measured in sealed capillaries and
were uncorrected. The MOCVD experiments were carried out vertical
quartz tube hot-wall MOCVD reactor with 60 mm in diameter. Heating
was achieved by a resistively heated tube oven (AICHUANG Com-
pany). The temperature was set by a temperature control FP 93 (SHI-
MADEN Company) and was calibrated with a thermocouple type SR
3 (SHIMADEN Company) digital thermometer. The precursor con-
tainer was heated with a heating band for evaporation of the precursor.
The precursor vapor was transported to the reactor tube by N2 carrier
gas. The carrier gas flow was regulated using a D07–7B (SEVEN-
STAR Company) mass flow controller which was connected to the
apparatus by a section of flexible stainless steel tubing. The pressure
control system consists of a cooling trap and a FT-110 (KYKY Com-
pany) molecular pump unit. The trap prevents the reactor effluents
from entering the vacuum pump. SEM images and EDX analysis were
carried out with Hitachi Model S-4800 with scanning electron micro-
scope and energy dispersive X-ray detector.
[(Ph3P)2·AgNC4H4O2] (2c): Complex 2c was synthesized following
the synthesis of 2a. In this respect, triethylamine (0.4048 g,
4.00 mmol) reacted with triphenylphosphine (2.0983 g, 8.00 mmol),
succinimide (0.3964 g, 4.00 mmol) and AgNO3 (0.6795 g,
4.00 mmol). After appropriate work-up, complex 2c was isolated as a
colorless solid. Yield: 2.46 g (84 % based on AgNO3). Mp.: 196 °C
dec. C40H34O2AgNP2: C, 65.77; H, 4.69. Found: C, 65.63; H, 4.63. 1H
NMR (CDCl3): δ = 2.60 (s, 4 H, CH2–H), 7.30–7.44 (m, 30 H, Ph–
H). 13C{H} NMR (CDCl3): δ = 32.5 (CH2), δ = 192.4 (C=O), 133.9
(JPC = 16.8 Hz, C6H5), 132.6 (JPC = 24.1 Hz, C6H5), 130.0 (C6H5),
128.7 (JPC = 9.5 Hz, C6H5). IR (KBr) data: 3655 (m), 3049 (m), 2962
(m), 2361 (w), 1700 (m), 1603 (s), 1583 (m), 1478 (m), 1434 (s), 1345
(s), 1285 (s), 1247 (s), 1183 (w), 1095 (s), 1026 (m), 996 (m), 803
(m), 746 (s), 695 (s), 512 (s), 436 (m) cm–1.
{[(MeO)3P]·AgNC4H4O2·(TMEDA)} (2d): Complex 2d was prepared
by using a similar method for 2a. In this respect, triethylamine
(0.5059 g, 5.00 mmol) reacted with N,N,N’,N’-tetramethylethylenedi-
amine (0.5811 g, 5 mmol), trimethylphosphite (0.6205 g, 5 mmol),
succinimide (0.4955 g, 5.00 mmol) and AgNO3 (0.8494 g,
5.00 mmol). After appropriate work-up, complex 2d was obtained as
a colorless ropy liquid. Yield: 1.92 g (86 % based on AgNO3).
C13H29O5AgN3P: C, 34.99; H, 6.55. Found: C, 34.63; H, 6.36. 1H
NMR (CDCl3): δ = 2.31 (s, 12 H, CH3/(CH3)2N–H), δ = 2.43 (s, 4 H,
NCH2–H), δ = 2.62 (s, 4 H, CH2–H), 3.71 (d, 9 H, CH3O–H, JPH
=
13.1 Hz). 13C{H} NMR (CDCl3): δ = 32.2 (CH2), δ = 47.4 (CH3), δ =
51.3 (JPC = 4.2 Hz, CH3/CH3O–), δ = 58.0 (CH2/NCH2–), δ = 191.7
(C=O). IR (KBr) data: 3441 (m), 2929 (m), 2836 (m), 1700 (m), 1618
(s), 1439 (m), 1359 (s), 1391 (s), 1269 (s), 1248 (s), 1182 (w), 1013
(m), 790 (m), 761 (w), 669 (m), 570 (w), 452 (w) cm–1.
Syntheses
Crystal Structure Determinations
{[Ag(TMEDA)2]+[Ag(NC4H4O2)2]–} (2a): To a solution of N,N,N’,N’- Single crystals of 2a and 2c could be obtained by cooling a saturated
tetramethylethylenediamine (0.4648 g, 4.00 mmol), succinimide diethyl ether solution to –20 °C. Suitable crystals for X-ray determina-
(0.3964 g, 4.00 mmol) and AgNO3 (0.6795 g, 4.00 mmol) in dry di- tion were placed in glue under N2 due to its sensitivities to oxygen and
ethyl ether (30 mL), triethylamine (0.4048 g, 4.00 mmol) was added. moisture. X-ray structure measurement was performed with a Rigaku
The clear solution was obtained by filtration through a pad of celite SCXmini CCD, detector equipped with graphite monochromatic Mo-
after stirring the reaction mixture for 6 h at 0 °C. A colorless solid Kα radiation (λ = 0.71073 Å), at room temperature. Date collection and
product was obtained after removing all volatiles in oil-pump vacuo. processing (cell refinement, data reduction and empirical absorption
1398
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© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2011, 1394–1400

Lewis-Base Stabilized N-Silver(I) Succinimide Complexes
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with anisotropic displacement parameters. Crystallographic data and
details on refinement are presented in Table 3. Crystallographic data
for the structural analyses of 2a and 2c were deposited with the Cam-
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2a
2c
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C20H40Ag2N6O4 C40H34AgNO2P2
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a /Å
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730.49
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P21/c
0.3 × 0.3 × 0.2
Monoclinic
C2/c
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5206
3909
4431
3199
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Acknowledgement
This work was supported by Natural Science Foundation of Jiangsu
Province (BK2007199), National Science and Technology of Major
Project (2009ZX02039101–02), Funding of Jiangsu Innovation Pro-
gram for Graduate Education (CX10B–100Z) and Outstanding Doc-
toral Dissertation in NUAA (BCXJ10–11) were also acknowledged.
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www.zaac.wiley-vch.de
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X. Tao, K.-C. Shen, Y.-L. Wang, Y.-Z. Shen
ARTICLE
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© 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2011, 1394–1400