Syntheses, spectroscopic and structural characterization of some (solvated) binuclear adducts of the form Ag(oxyanion):dpem(:S) (1:1(:x))2 (oxyanion = ClO4, F3CCO2, F3CSO 3; dpem = Ph2E(CH2)EPh2 (E = P, As))

Article abstract of DOI:10.1016/j.ica.2004.07.032

Syntheses, spectroscopic (IR, NMR and ESI MS) and single crystal X-ray structural characterizations are reported for a wide variety of adducts of Ag(oxyanion):dpem(:S) (1:1(:n))₂ (oxyanion = ClO₄, F ₃CCO₂ (tfa) F₃CSO₃ (tfs); dpem = Ph₂E(CH₂)EPh₂) stoichiometry among which the basic Ag(Ph₂E(CH₂)EPh₂)₂Ag core is diversely perturbed by interactions with anions and solvent molecules. ESI MS and ³¹P NMR spectroscopy indicated that dinuclear species also exist in solution.

Full text of DOI:10.1016/j.ica.2004.07.032

Inorganica Chimica Acta 358 (2005) 735–747
www.elsevier.com/locate/ica
Syntheses, spectroscopic and structural characterization of
some (solvated) binuclear adducts of the form
Ag(oxyanion):dpem(:S) (1:1(:x))2 (oxyanion = ClO4,
F3CCO2, F3CSO3; dpem = Ph2E(CH2)EPh2 (E = P, As))
c
a
c,
*
Effendy a,b, Corrado Di Nicola , Maksum Nitiatmodjo , Claudio Pettinari
,
b
Brian W. Skelton , Allan H. White
b
a
Jurusan Kimia, FMIPA Universitas Negeri Malang, Jalan Surabaya 6, Malang 65145, Indonesia
b
Chemistry M313, The University of Western Australia, Crawley, WA 6009, Australia
c
`
Dipartimento di Scienze Chimiche, Universita degli Studi di Camerino, via S. Agostino 1, 62032 Camerino MC, Italy
Received 5 July 2004; accepted 23 July 2004
Available online 3 September 2004
Abstract
Syntheses, spectroscopic (IR, NMR and ESI MS) and single crystal X-ray structural characterizations are reported for a wide
variety of adducts of Ag(oxyanion):dpem(:S) (1:1(:n))2 (oxyanion = ClO4, F3CCO2 (tfa) F3CSO3 (tfs); dpem = Ph2E(CH2)EPh2) sto-
ichiometry among which the basic Ag(Ph2E(CH2)EPh2)2Ag core is diversely perturbed by interactions with anions and solvent mol-
ecules. ESI MS and 31P NMR spectroscopy indicated that dinuclear species also exist in solution.
ꢀ 2004 Elsevier B.V. All rights reserved.
Keywords: Silver; 31P NMR; ESI MS; X-ray crystal structure; Diphosphine
1. Introduction
scribed for adducts of simple MX salts, notably
[Au4(l3-Br)2(dppm)4]2+ with gold(I) [2], and its Ag/O Æ
NO Æ O silver(I) counterpart [3], devoid of metal–metal
The preceding paper [1], in defining the nature of ad-
ducts of simple univalent coinage metal salts with chelat-
ing dpem ligands, Ph2E(CH2)EPh2, of stoichiometry
MX:dpem (m:n), E = P, As, after brief discussion of
the relatively few structurally characterized examples
with n > m, focussed on adducts of 1:1 stoichiometry,
bonding, and ꢀsquare planarꢁ [M4(l4-Y)(dppm)4]2+
,
Y = S, Se, Te, P with copper(I) and silver(I) [4–9]; con-
versely, simple mononuclear arrays such as [XM(dpem)]
appear non-existent. For simple (pseudo-) halide or oxo-
anions, the remainder are binuclear, of a limited number
of basic forms. In all of these, two metal atoms are
bridged by a pair of E-dpem-E0 ligands, the basis of
all structures being an [M(P-dppm-P0)2M0]2+ (in one
case, dpam) kernel, whereon a variety of interactions
may be superimposed, in a few cases between metals,
in other cases in diverse ways with the anions, which
may be found free or associated with one or both metals,
terminal or bridging, or solvent molecules. The simplest
form, relevant to the present context, is [M(P-dppm-
and, specifically among them, the species of highest
0
common nuclearity, the trimeric [X2M3(dpem)3]X( ) ar-
rays, describing the structural characterization of some
arrays of fundamental significance for copper(I) and sil-
ver(I). A few arrays of higher nuclearity have been de-
*
Corresponding author. Tel.: +39 0737 402234; fax: +39 0737
637345.
E-mail address: claudio.pettinari@unicam.it (C. Pettinari).
0020-1693/$ - see front matter ꢀ 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2004.07.032

736
Effendy et al. / Inorganica Chimica Acta 358 (2005) 735–747
P)2M]X2, devoid of metal–metal bonding in its M = Ag,
X = ClO4 adduct [10,11], with metal–metal bonding pos-
tulated in the M = Au, X = BF4 [12], NO3 [13], BH3CN
[14], AuGeCl4 (this with dpam) [15], but not SbF6 (this
with dpph) [16], adducts. A related type with the anions
bound to the metal, [XM(P-dppm-P)2MX], devoid of
metal–metal interactions, is recorded for M = Cu [17],
Ag [3,18], with X = ONO2, with metal–metal interac-
tions postulated for M = Au, X = Cl [19,20], Br [21].
In a number of compounds, the anion may bridge the
two metal atoms also: [M(l-X)(P-dppm-P0)2M0]+, as is
the case for M = Cu, X = O Æ COMe [22], without me-
tal–metal bond, and M = Au, X = I [14,21] with. Con-
temporaneous with some of the above, and in concert
with, and complementary to, the studies recorded in
the preceding paper, which pertain to the trinuclear ad-
ducts obtained with X = (pseudo-)halide systems
(X = NCO, Cl, Br, I), we have obtained a number of
new X = oxyanion arrays, again with silver(I) = M pri-
marily as our focus, which are (derivative) of the binu-
clear form(s) described above, which we record
hereunder for various MX:dpem (1:1)2 combinations,
some with interesting solvated variants. As in many of
our studies in this area, the simple oxyanion systems
chosen for study span a range of basicity, usually perchl-
orate, nitrate, carboxylate, represented here by perchlor-
ate and trifluoracetate (”tfa) (perchlorate and nitrate
examples having been previously recorded) and aug-
ometry (ESI-MS) were prepared using reagent grade
acetone or acetonitrile. For the ESI-MS data, masses
and intensities were compared to those calculated by
using the IsoPro isotopic abundance simulator version
2.1 [23]; peaks containing silver(I) and copper ions are
identified as the centers of isotopic clusters.
Safety note. Perchlorate salts of metal complexes with
organic ligands are potentially explosive! Only small
amounts of materials should be prepared, and these should
handed with great caution.
2.2. Syntheses
2.2.1. Syntheses of the silver complexes
The colourless complexes described were obtained by
crystallization, by slow evaporation and/or cooling, of
solutions of millimolar stoichiometry of AgX with dppm
or dpam in MeCN/MeOH or pyridine or ethanol
(X = ClO4) and ethanol or acetonitrile (X = tfa), and
ethanol (X = tfs) (see below).
2.2.1.1. Synthesis of AgClO4:dppm (1:1)2 (1). dppm
(0.384 g, 1.0 mmol) was added at room temperature to
an 1:1 MeCN/MeOH solution (20 ml) of AgClO4
(0.207 g, 1.0 mmol). After the addition, the solution
was stirred for 24 h and then filtered off. The clear
solution was then slowly evaporated until a colorless
micro-crystalline precipitate was obtained which was
recrystallised from CHCl3 to give complex 1 as a colour-
mented by tfs ðꢀ F3CSOꢁÞ.
3
1
less crystalline solid in 64% yield, mp 286 ꢁC. H NMR
(CDCl3, 293 K): d 3.91 (s, 4H, PCH2P), 6.9–7.5 (m, 40H,
C6H5). 13C NMR (CDCl3, 293 K): d 27.19s (CH2dppm),
129.7br, 131.7br 132.9br 133.7br (Carom). 31P{1H}
2. Experimental
1
2.1. Materials and methods
NMR (CDCl3, 293 K): d 10.70 (d br, J(31P, Ag) = 539
Hz). IR (nujol, cmꢁ1): 3052w (CHarom), 2300br,
1586w, 1573w, 1482 (Cꢂ ꢂ ꢂC); 518s, 504s, 472s, 447s,
420m, 352m, 279w, 225w, 193w, 151w, 120w, 105w,
98w, 88w, 73m. ESI MS (+): 492 [100] [Ag(dppm)]+;
1084 [25] [Ag2(ClO4)(dppm)2]+. Anal. Calc. for C50H44-
Ag2Cl2O8P4: C, 50.75; H; 3.75. Found: C, 50.59; H,
4.00%. Km(CH2Cl2, 10ꢁ3 M): 33 Xꢁ1 mol2 cmꢁ1. The
X-ray specimen was obtained from chloroform.
All syntheses and handling were carried out under an
atmosphere of dry oxygen-free dinitrogen, using stand-
ard Schlenk techniques, although the compounds gener-
ally are not air-sensitive. All chemicals were purchased
from Aldrich and Lancaster and used without further
purification. Elemental analyses (C, H, N) were per-
formed in house with a Fisons Instruments 1108
CHNS–O Elemental Analyser. IR spectra were recorded
from 4000 to 100 cmꢁ1 with a Perkin–Elmer System
2.2.1.2. Synthesis of AgClO4:dppm:MeCN (1:1:1)2 (2).
Compound 2 has been obtained from the dissolution of
1 in acetonitrile. The clear solution was then slowly
evaporated until a colorless micro-crystalline precipitate
was obtained in 95% yield, mp 286 ꢁC. 1H NMR
(CDCl3, 293 K): d 2.01 (s, 6H, CH3CN), 3.92 (m, 6H,
PCH2P), 7.2–7.6 (m, 40H, C6H5). 13C NMR (CDCl3,
293 K): d 16.0 (CH3MeCN) 27.08s (CH2dppm), 129.7br,
131.7br 132.9br 133.7br (Carom). 31P{1H} NMR
1
2000 FT-IR instrument. H-, 13C and 31P-NMR spectra
were recorded on a VXR-300 Varian spectrometer (300
MHz for 1H, 75.0 MHz for 13C and 121.4 MHz for 31P).
H and C chemical shifts are reported in ppm vs. SiMe4,
P chemical shift in ppm vs. H3PO4 85%. The electrical
conductances of the acetone, dichloromethane, DMSO
and acetonitrile solutions were measured with a Crison
CDTM 522 conductimeter at room temperature. Posi-
tive and negative electrospray mass spectra were ob-
1
(CDCl3, 293 K): d 0.5 (d br, J(31P, Ag) = 495 Hz). IR
tained with
a
Series 1100 MSI detector HP
(nujol, cmꢁ1): 3052w (CHarom), 1482 (Cꢂ ꢂ ꢂC); 518s,
504s, 472s, 447s, 420m, 352m, 279w, 225w, 193w,
151w, 120w, 105w, 98w, 88w, 73m. ESI MS (+): 492
spectrometer, using an acetonitrile mobile phase. Solu-
tions (3 mg/ml) for electrospray ionization mass spectr-

Effendy et al. / Inorganica Chimica Acta 358 (2005) 735–747
737
[100] [Ag(dppm)]+; 1084 [25] [Ag2(ClO4)(dppm)2]+; (–):
99 [100] [ClO4]ꢁ. Anal. Calc. for C54H50Ag2Cl2N2O8P4:
C, 51.25; H, 3.98; N, 2.21. Found: C, 51.21; H, 4.05;
18.63s (CH3EtOH), 27.08s (CH2dpam), 58.70s (CH2EtOH),
129.0br, 130.7br, 131.4br, 132.9br (Carom). IR (nujol,
cmꢁ1): 3051w (CHarom), 1650m, 1579m (py), 1482w
(Cꢂ ꢂ ꢂC) 591s, 475s, 458s, 410s, 316s, 266m, 193w,
115w, 92w, 80w, 72w. ESI MS (+): 189 [60] [Ag
(MeCN)2]+; 580 [85] [Ag(dpam)]+; 621 [100] [Ag2
ClO4)(py)2(Et2O)2]+; 1053 [40] [Ag2(ClO4)(MeCN)2-
(EtOH)4(dpam)2]+; 1260 [70] [Ag2(ClO4)(dpam)2]+.
Anal. Calc. for C58H62Ag2As2Cl2N2O10: C, 45.43; H;
4.08; N, 1.83. Found: C, 45.20; H, 3.93; N, 1.56%.
N, 2.01%. Km(CH2Cl2, 10ꢁ3 M): 30 Xꢁ1 mol2 cmꢁ1
.
2.2.1.3. Synthesis of AgClO4:dpam (1:1)2 (3). dpam
(0.472 g, 1.0 mmol) was added at room temperature to
a EtOH/CH3CN solution (20 ml) of AgClO4 (0.207 g,
1.0 mmol). After the addition, the solution was stirred
for 24 h and then filtered off. The clear solution was then
slowly evaporated until a colorless micro-crystalline pre-
cipitate was obtained which was filtered off and washed
with ethanol to give complex 3 as a colourless micro-
crystalline solid in 72% yield, mp 288 ꢁC. 1H NMR
(CDCl3, 293 K): d 3.57 (s, br 4H, PCH2P), 7.2–7.6 (m,
40H, C6H5). 13C NMR (CDCl3, 293 K): d 24.3br
(CH2dppm), 129.6br, 130.7br, 132.3br, 133.2br (Carom).
IR (nujol, cmꢁ1): 3052w (CHarom), 1579w, 1481m
(Cꢂ ꢂ ꢂC), 588s, 472s, 459s, 334s, 318s, 268m, 245w,
204w, 195w, 179w, 100m, 91m, 72m, 62w (AgAs). ESI
MS (+): 190 [20] [Ag(MeCN)2]+, 580 [100] [Ag(d-
pam)]++, 621 [100] [Ag(dpam)(MeCN)]+ 1260 [60] [Ag2-
(ClO4)(dpam)2]+. Anal. Calc. for C50H44Ag2As4Cl2O8:
C, 44.18; H; 3.26. Found: C, 44.06; H, 3.44%.
Km(CH2Cl2, 10ꢁ3 M): 31 Xꢁ1 mol2 cmꢁ1. The X-ray
specimen was obtained from chloroform/ethanol.
Km(CH2Cl2, 10ꢁ3 M): 30 Xꢁ1 mol2 cmꢁ1
.
2.2.1.6. Synthesis of Ag(tfa):dppm (1:1)2 (6). dppm
(0.384 g, 1.0 mmol) was added at room temperature to
an ethanol solution (20 ml) of Ag(tfa) (0.221 g, 1.0 mmol).
After the addition, a colorless micro-crystalline precipi-
tate immediately formed. The solution was stirred for
24 h and then filtered off. The precipitate was washed with
a small quantity of ethanol to give complex 6 as a colour-
less micro-crystalline solid in 71% yield, mp 246–248 ꢁC.
1H NMR (CDCl3, 293 K): d 3.37 (s, 4H, PCH2P), 6.8–
7.5 (m, 40H, C6H5). 13C NMR (CDCl3, 293 K): d 28.91
(CH2dppm), 129.0s, 130.81s, 133.51s, 133.66s (Carom).
31P{1H} NMR (CDCl3, 293 K): d +6.4 (d br,
1J(31P, Ag) = 495 Hz). IR (nujol, cmꢁ1): 3052w, 3048w
(C–Harom), 1661s br (CF3COO) 1586w, 1481m (Cꢂ ꢂ ꢂC),
515s, 503m, 480s, 471s, 445m, 425w, 414w, 333w, 268m,
211w, 178w, 153w, 119w, 113w, 106w, 88w, 73w (AgP).
ESI MS (+): 1020 [30] [Ag2Cl(dppm)2]+; 1097 [100] [Ag2(t-
fa)(dppm)2]+. Anal. Calc. for C54H44Ag2F6O4P4: C,
53.58; H, 3.66. Found: C, 53.15; H, 3.55%. Km(CH2 Cl2,
10ꢁ3 M): 12 Xꢁ1 mol2 cmꢁ1. The X-ray specimen was ob-
tained from acetonitrile.
2.2.1.4. Synthesis of AgClO4:dpam:py (1:1:1)2 (4).
dpam (0.472 g, 1.0 mmol) was added at room tempera-
ture to a pyridine (py) solution (5 ml) of AgClO4 (0.207
g, 1.0 mmol). After the addition, the solution was stirred
for 48 h and then ethyl ether was added until a colorless
precipitate was obtained which was filtered off and
washed with diethyl ether to give complex 4 as a colour-
1
less solid in 68% yield, mp 286 ꢁC. H NMR (CDCl3,
293 K): d 3.50 (s, 4H, PCH2P), 7.19–7.70 (m, 40H,
C6H5), 8.55, 7.60, 7.20 (m, 10H, py). 13C NMR (CDCl3,
293 K): d 24.04s, (CH2dpam), 124.5s, 137.0s, 150.9s
(CHpy), 129.5br, 130.5br, 132.8br, 133.0br (Carom). IR
(nujol, cmꢁ1): 3051w (CHarom), 1650m, 1589m, 1579m
(py), 1482w (Cꢂ ꢂ ꢂC) 591s, 475s, 458s, 410s, 316s,
266m, 193w, 115w, 92w, 80w, 72w. ESI MS (+): 189
[60] [Ag(py)]+; 580 [85] [Ag(dpam)]+; 621 [100] [Ag2-
(ClO4)(py)2(Et2O)2]+; 1260 [45] [Ag2(ClO4)(dpam)2]+.
Anal. Calc. for C60H54Ag2As4Cl2N2O8: C, 47.56; H;
3.60; N, 1.85. Found: C, 47.26; H, 3.67; N, 2.16%.
Km(CH2Cl2, 10ꢁ3 M): 30 Xꢁ1 mol2 cmꢁ1. The X-ray
specimen was obtained from pyridine.
2.2.1.7. Synthesis of Ag(tfa):dpam:MeCN (1:1:1)2 (7).
dpam (0.472 g, 1.0 mmol) was added at room tempera-
ture to an acetonitrile solution (10 ml) of Ag(tfa) (0.221
g, 1.0 mmol). After the addition, the solution was stirred
for 24 h and then filtered off. A colorless micro-crystal-
line precipitate was obtained which was filtered off and
washed with acetonitrile to give complex 7 as a colourless
micro-crystalline solid in 63% yield, mp 160–165 ꢁC. 1H
NMR (CDCl3, 293 K): d 1.87 (s, 6H, CH3CN), 3.00 (s,
4H, PCH2P), 7.2–7.4 (m, 40H, C6H5). 13C NMR (CDCl3,
293 K): d 23.95s (CH2dpam), 129.6br, 130.9br, 132.4br,
132.8br (Carom). IR (nujol, cmꢁ1): 3065w, 3052w (CHar-
om), 1664s, 1631s, 1615s (CF3COO) 1482s (Cꢂ ꢂ ꢂC),
594s, 521s, 505sh, 476s, 470m, 460s, 333sh, 318s, 285s,
268m, 194s br, 155w, 130m, 121m, 90w, 71m, 60w
(AgP). ESI MS (+): 148 [15] [Ag(MeCN)]+; 189 [100]
[Ag(MeCN)2]+; 801 [8] [Ag2(tfa)(dpam)]+; 1273 [20]
[Ag2(tfa)(dpam)2]+; 1494 [8] [Ag3(tfa)2(dpam)2]+. Anal.
Calc. for C58H50Ag2As4F6N2O4: C, 47.44; H, 3.43; N,
1.91. Found: C, 47.42; H, 3.41; N, 2.00%. Km(CH2Cl2,
2.2.1.5. Synthesis of AgClO4:dpam:MeCN:EtOH
(1:1:1:1)2 (5). This complex was obtained by recrystal-
lization of the compound 3 from MeCN/EtOH. 84%
1
yield, mp 290 ꢁC. H NMR (CDCl3, 293 K): d 1.25 (t,
6H, CH3EtOH), 2.02 (s, 6H, CH3CN), 3.61 (s, 4H,
PCH2P), 3.73 (q, 4H, CH2EtOH), 7.2–7.5 (m, 40H,
C6H5). 13C NMR (CDCl3, 293 K): d 16.2 (CH3MeCN),
10ꢁ3 M): 10 Xꢁ1 mol2 cmꢁ1
.

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Effendy et al. / Inorganica Chimica Acta 358 (2005) 735–747
2.2.1.8. Synthesis of Ag(tfs):dppm:EtOH (1:1:1)2 (8).
dpam (0.384 g, 1.0 mmol) was added at room tempera-
ture to an ethanol solution (20 ml) of Ag(tfs) (0.256 g,
1.0 mmol). After the addition, the solution was stirred
for 24 h and then filtered off. A colorless micro-crystal-
line precipitate was obtained which was filtered off and
washed with ethanol to give complex 8 as a colourless
micro-crystalline solid in 62% yield, mp 248–251 ꢁC.
1H NMR (CDCl3, 293 K): d 1.22 (t, 6H, CH3EtOH),
3.53 (s, 4H, PCH2P), 3.95 (q, 4H, CH2EtOH), 7.0–7.5
(m, 40H, C6H5). 13C NMR (CDCl3, 293 K): d 18.63s
(CH3EtOH), 27.04s (CH2dppm), 58.69s (CH2EtOH),
129.1br, 129.6br, 130.8br, 131.7br 133.5br (Carom).
31P{1H} NMR (CDCl3, 293 K): d +10.13 (d br,
1J(31P, Ag) = 530 Hz); +0.4 (d br, 1J(31P, Ag) = 474
Hz). IR (nujol, cmꢁ1): 3411br (OH) 3052w (CHarom),
1587w, 1483w (Cꢂ ꢂ ꢂC), 573m, 514s, 505s, 480s, 447m,
436m, 351w, 341w, 210w, 188w, 152w, 98w, 73m, 63w
(AgP). ESI MS (+): 492 [100] [Ag(dppm)]++; 1133 [40]
[Ag2(tfs)(dppm)2]+. ESI MS (–): 149 [100] [tfs]ꢁ. Anal.
Calc. for C56H56Ag2F6O8P4S2: C, 48.98; H, 4.11; S,
4.66. Found: C, 48.41; H, 3.67; S, 5.10%. Km(CH2Cl2,
2.3.1. Crystal/refinement data
2.3.1.1. AgClO4:dppm (1:1)2 (1). C50H44Ag2Cl2O8P4,
M = 1183.4.
Monoclinic,
space
group
P21/n
ðC52h; No: 14; variantÞ, a = 10.654(1), b = 17.364(2),
3
˚
˚
c = 13.914(2) A, b = 104.601(1)ꢁ, V = 2491 A . Dc
(Z = 2 dimers) = 1.578 g cmꢁ3. lMo = 10.7 cmꢁ1; speci-
men: 0.37 · 0.35 · 0.32 mm; Tmin/max = 0.91. 2hmax
=
54ꢁ; Nt = 18714, N = 5127 (Rint = 0.017), No = 4165;
R = 0.034, Rw = 0.041. jDqmaxj = 0.81(2) e Aꢁ3. CCD
˚
instrument, T ꢃ 300 K.
Variata. Phenyl ring 12 was modelled as rotationally
disordered over a pair of locations of equal occupancy.
2.3.1.2. AgClO4:dppm:MeCN (1:1:1)2 (2). C54H50Ag2-
Cl2N2O8P4, M = 1265.6. Monoclinic, space group P21/
c
ðC52h; No: 14Þ, a = 11.448(3), b = 15.179(4),
3
˚
˚
c = 17.694(5) A, b = 117.47(4)ꢁ, V = 2728 A . Dc (Z =
2 dimers) = 1.540 g cmꢁ3. lMo = 8.9 cmꢁ1; specimen:
0.45 · 0.41 · 0.30 mm; Tmin/max = 0.94 (gaussian correc-
tion). 2hmax = 50ꢁ; N = 4787, No = 3200; R = 0.040,
Rw = 0.041. jDqmaxj = 0.5 e Aꢁ3. Single-counter instru-
˚
ment, T ꢃ 295 K.
10ꢁ3 M): 42 Xꢁ1 mol2 cmꢁ1
.
2.3.1.3. AgClO4:dpam (1:1)2 (3). C50H44Ag2As4Cl2O8,
1
ꢀ
M = 1359.2. Triclinic, space group P1 ðCi ; No: 2Þ,
2.2.1.9. Synthesis of Ag(tfs):dpam:EtOH (1:1:1)2 (9).
dpam (0.472 g, 1.0 mmol) was added at room tempera-
ture to an ethanol solution (10 ml) of Ag(tfs) (0.256 g,
1.0 mmol). After the addition, the solution was stirred
for 12 h and then filtered off. A colorless micro-crystal-
line precipitate was obtained which was filtered off and
washed with acetonitrile to give complex 9 as a colour-
less micro-crystalline solid in 67% yield, mp 276–278
˚
a = 11.014(2), b = 11.276(2), c = 11.483(2) A, a =
3
˚
74.892(2), b = 64.630(2), c = 70.286(3)ꢁ, V = 1202 A .
Dc (Z = 1 dimer) = 1.878 g cmꢁ3. lMo = 37 cmꢁ1; speci-
men: 0.2 · 0.15 · 0.15 mm; Tmin/max = 0.70. 2hmax = 50ꢁ;
Nt = 12917, N = 4222 (Rint = 0.053), No = 3297; R =
0.056, Rw = 0.064. jDqmaxj = 2.09(7) e Aꢁ3. CCD instru-
˚
ment, T ꢃ 153 K.
1
ꢁC. H NMR (CDCl3, 293 K): d 1.24 (t, 6H, CH3EtOH),
3.49 (s, 4H, PCH2P), 3.72 (q, 4H, CH2EtOH), 7.1–7.5 (m,
40H, C6H5). 13C NMR (CDCl3, 293 K): d 18.63s (CH3E-
tOH), 24.37s (CH2dpam), 58.70s (CH2EtOH), 129.6br,
130.7br, 133.0br (Carom). IR (nujol, cmꢁ1): 3405br
(OH), 3054w (CHarom), 1579m, 1484m (Cꢂ ꢂ ꢂC), 592s,
573s, 516s, 473s, 457s, 354w, 348w, 328m, 318s, 267m,
194m, 170w, 151w, 131w, 80w, 73m, 57m. ESI MS
(+): 189 [10] [Ag(MeCN)2]+; 580 [100] [Ag(dpam)]+;
621 [100] [Ag(dpam)(MeCN)]+ 1053 [25] [Ag(dpam)2]+
1309 [85] [Ag(tfs)(dpam)2]+. Anal. Calc. for C56H56A-
g2As4F6O8S2: C, 43.38; H, 3.64; S, 4.14. Found: C,
43.09; H, 3.42; S, 4.04%. Km(CH2Cl2, 10ꢁ3 M): 39
2.3.1.4. AgClO4:dpam:py (1:1:1)2 (4). C60H54A-
g2As4Cl2N2O8, M = 1517.5. Orthorhombic, space group
16
2h
Pnma ðD ; No: 62Þ, a = 19.483(6), b = 21.882(3),
3
˚
˚
c = 13.805(3) A, V = 5885 A . Dc (Z = 4 dimers) = 1.712
g cmꢁ3. lMo = 30 cmꢁ1; specimen: 0.34 · 0.32 · 0.12 mm;
Tmin/max = 0.80 (analytical correction). 2hmax = 50ꢁ;
N = 5056, No = 2960; R = 0.039, Rw = 0.040. jDqmaxj =
0.83(3) e Aꢁ3. Single-counter instrument, T ꢃ 295 K.
˚
2.3.1.5. AgClO4:dpam:MeCN:EtOH (1:1:1:1)2 (5). C58
H62Ag2As4Cl2N2O10, M = 1533.5. Monoclinic, space
group
P21/c,
a = 16.913(4),
b = 19.647(2),
Xꢁ1 mol2 cmꢁ1
.
3
˚
˚
c = 21.959(10) A, b = 121.03(3)ꢁ, V = 6252 A . Dc
(Z = 4 dimers) = 1.629 g cmꢁ3. lMo = 29 cmꢁ1; speci-
men: 0.36 · 0.30 · 0.51 mm; Tmin/max = 0.71 (gaussian
2.3. Structure determinations
correction).
2hmax = 50ꢁ; N = 10745, No = 6085;
R = 0.041, Rw = 0.040. jDqmaxj = 0.74(4) e Aꢁ3. Single-
˚
General procedural details are outlined in the preced-
ing paper [1]. Full cif. depositions reside with the Cam-
bridge Crystallographic Data Centre, # 241108–241116.
Specific details are as follows (individual variations in
procedure (difficulties, anomalies, etc.) are cited as
ꢀvariataꢁ):
counter instrument, T ꢃ 295 K.
2.3.1.6. Agtfa:dppm (1:1)2 (6). C54H44Ag2F6O4P4,
ꢀ
M = 1210.6. Triclinic, space group P1, a = 10.846(2), b =
˚
14.448(2), c = 17.129(2) A, a = 82.775(4), b = 86.114(4),

Effendy et al. / Inorganica Chimica Acta 358 (2005) 735–747
739
3
˚
c = 72.625(4)ꢁ, V = 2540 A . Dc (Z = 2 dimers) = 1.583
g cmꢁ3. lMo = 9.6 cmꢁ1; specimen: 0.44 · 0.13 · 0.05 mm;
Tmin/max = 0.84. 2hmax = 58ꢁ; Nt = 37593, N = 13337,
These compounds are generally air-stable, colorless
materials, soluble in polar solvents such as acetonitrile,
dimethylformamide and dimethylsulfoxide. They are
however, insoluble in water, ether and tetrahydrofuran
but exhibit good solubility in the chlorinated hydrocar-
bons CH2Cl2 and CHCl3. Solid samples of these com-
pounds show generally no sensitivity to light, but they
are unstable in solution, their chlorinated solvent solu-
tions often darkening after 24 h. The solubilities of the
perchlorate derivatives are generally lower than those
found for the trifluoroacetate and trifluoromethanesulf-
onate species. Conductivity measurements, as expected,
indicated that the perchlorate and trifluoromethanesulf-
onate complexes are electrolytes in dichloromethane
solution, the values for the dppm complexes being high-
er than those found for the dpam species and typical of a
1:2 electrolyte and consistent with a weak interaction be-
tween Ag and dpam (relative to dppm), allowing the
counter-ion to associate more strongly in solutions of
the dpam derivatives. The conductivity values found
for the trifluoroacetate derivatives suggest a partial ionic
dissociation in solution in accordance with the occur-
rence of the following equilibrium, also supported from
the ESI MS data (see below).
ꢁ3
˚
No = 10287; R = 0.057, Rw = 0.089. jDqmaxj = 1.81(7) e A
.
CCD instrument, T ꢃ 153 K.
Variata. The fluorine atoms of anion 2 were modelled
as rotationally disordered over two sets of sites of equal
occupancy, those of anion 1 over two sets, occupancies
0.87(2) and complements.
2.3.1.7. Agtfa:dpam:MeCN (1:1:1)2 (7). C58H50A-
ꢀ
g2As4F6N2O4, M = 1468.4. Triclinic, space group P1,
˚
3
a = 13.153(3),
b = 12.001(4),
c = 11.208(4)
A,
˚
a = 77.42(3), b = 67.94(3), c = 64.12(3)ꢁ, V = 1472 A .
Dc (Z = 1 dimer) = 1.656 g cmꢁ3. lMo = 30 cmꢁ1; speci-
men: 0.22 · 0.31 · 0.39 mm; Tmin/max = 0.68 (analytical
correction).
2hmax = 50ꢁ;
N = 5169,
No = 3713;
˚
R = 0.035, Rw = 0.035. jDq maxj = 0.43(5) e Aꢁ3. Sin-
gle-counter instrument, T ꢃ 295 K.
Variata. (x, y, z, Uiso)H were refined (acetonitrile ex-
cepted). The fluorine atoms of the anion were modelled
as rotationally disordered over two sets of sites of equal
occupancy.
½Ag2ðdpemÞ ðXÞ ꢄ ꢀ ½Ag2ðdpemÞ Xꢄþ þ Xꢁ
ð1Þ
2
2
2
2.3.1.8. Agtfs:dppm:EtOH (1:1:1)2 (8). C56H56Ag2-
F6O8P4S2, M = 1374.8. Monoclinic, space group P21/n,
˚
A,
a = 11.532(1),
b = 21.273(2),
3
c = 12.011(1)
3.1. Spectroscopy
˚
b = 100.550(1)ꢁ, V = 2897 A . Dc (Z = 2 dimers) = 1.576
g cmꢁ3. lMo = 9.3 cmꢁ1; specimen: 0.24 · 0.18 · 0.14
The infrared spectra of 1–9 (see Section 2) are consist-
ent with the formulations proposed, showing all of the
bands required by the presence of the counter-ion and
of the phosphorus or arsenic donor [24]. The bands
due to the phosphine and arsine ligands are only slightly
shifted with respect to those of the free donors. In the
far-IR spectra of derivatives 1–4 we have assigned, on
the basis of a previous report on phosphino silver(I)
derivatives [25], the broad absorptions near 500 cmꢁ1
and those at 450–400 cmꢁ1 to Whiffenꢁs y and t vibra-
tions, respectively. Some bands in the region 300–200
cmꢁ1, similar to those described in the literature for
other silver(I)-oxyanion derivatives [26], can be tenta-
tively assigned to m(Ag–O).
mm;
N = 7362
Tmin/max = 0.79.
(Rint = 0.036),
2hmax = 58ꢁ;
No = 6020;
Nt = 33996,
R = 0.031,
Rw = 0.037. jDqmaxj = 0.99(5) e Aꢁ3. CCD instrument,
˚
T ꢃ 153 K (x, y, z, Uiso H
) refined.
2.3.1.9. Agtfs:dpam:EtOH (1:1:1)2 (9). C56H56Ag2As4-
F6O8S2, M = 1550.6. a = 11.887(2), b = 21.215(4),
3
˚
˚
c = 12.071(2) A, b = 101.516(3)ꢁ, V = 2983 A . Dc
(Z = 2 dimers) = 1.726 g cmꢁ3. lMo = 30 cmꢁ1; speci-
men:
0.37 · 0.21 · 0.15
mm;
Tmin/max = 0.61.
2hmax = 58ꢁ; Nt = 34356, N = 7551 (Rint = 0.060),
No = 5967; R = 0.042, Rw = 0.051. jDqmaxj = 1.65(7)
e Aꢁ3. CCD instrument, T ꢃ 153 K (x, y, z, Uiso H
)
re-
˚
The spectroscopic behaviour of the counter-ion in
compounds 1 and 2 is typical of an ionic outer-sphere
fined. The compound is isomorphous with its dppm ana-
logue (above) and was refined in the same cell and
coordinate setting.
ꢁ
group: in the case of an ionic ClO4 with Td geometry
only two vibrations (m3 and m4) are expected to be IR ac-
tive [27], as in fact found in 1 and 2, at ꢃ1090 and 620
cmꢁ1, in good accordance with the results found in the
solid state which suggest the existence of a weak pertur-
3. Results and discussion
ꢁ
bation of the ClO4 ion. On the other hand different
absorptions have been found in the case of the dpam
derivatives 3–5, a number of broad bands between
1120 and 1000 cmꢁ1 and two strong bands at 620 and
580 cmꢁ1, in accordance withꢁcoordinated unidentate
(3 and 5) or bidentate (4) ClO4 groups.
The reaction of AgX (X = ClO4, tfs or tfa) with equi-
molar bis(diphenylphosphino)methane (dppm) or
bis(diphenylarsino)methane ligand (dpam) at room tem-
perature in diverse solvents gave rise to the compounds
AgX:dpem (1:1) 1–9 according to Chart 1.

740
Effendy et al. / Inorganica Chimica Acta 358 (2005) 735–747
H2
++
H2
C
H2
C
C
Ph
P
Ph
P
Ph
As
Ph
As
Ph
Ph
Ph
P
Ph
P
Ph
Ph
Ph
Ph
Ph
Ph
Ph
MeCN
OClO3
OClO3
Ag
Ag
NCMe
Ag
Ag
2ClO4-
O3ClO
O3ClO
Ph
Ag
Ag
P
P
As
Ph
As
Ph
Ph
Ph
P
P
Ph
Ph
C
C
Ph
Ph
H2
C
H2
H2
2
1
3
+
+
H2
C
H2
C
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
As
As
O O
Cl
As
As
O
O
MeCN
MeCN
OHC2H5
N Ag
As
Ag N
H2
C
Ag
Ag
OClO3
Ph
Ph
Ph
Ph
P
P
As
Ph
Ph
As
Ph
As
Ph
Ph
Ph
Ph
O
Ph
C
C
C
3
O
C
H2
H2
F
Ag
Ag
C
O
F3C
O
-
-
O
O
P
P
Ph
Ph
Cl O
O
Cl O
O
Ph
Ph
C
O
O
H2
5
6
4
H2
C
H2
C
H2
C
Ph
As
Ph
As
Ph
P
Ph
Ph
As
Ph
As
Ph
Ph
Ph
Ph
Ph
Ph
P
O
O
F3CSO3
Ag
O3SCF3
F3CSO3
Ag
O3SCF3
C2H5HO
C2H5HO
O
F C
3
C
CF3
Ag
Ag
C
O
Ag
Ag
OHC2H5
Ph
OHC2H5
Ph
As
Ph
As
Ph
P
P
As
Ph
As
Ph
Ph
Ph
Ph
Ph
C
Ph
Ph
C
C
H2
H2
H2
8
9
7
Chart 1.
In the case of carboxylate derivatives it is generally ac-
Unambiguous assignment of the vibrational modes of
ꢁ
cepted [28] that it is possible to distinguish between ionic,
unidentate, chelating bidentate or bridging bidentate
groups on the basis of D values (where D = ma(COO) ꢁ ms-
(COO)), the trend generally accepted being:
CF3SO3 in 8 and 9 is not possible due to overlap of
CF3, SO3 and organic ligand vibrational modes. On
the basis of literature reports on silver triflate complexes
and the parent salt [29–31], we assign the bands at 1270,
1040 cmꢁ1 to m[SO3(E)] and m[SO3(A1)] and those at
ꢃ1240 and 1170 cmꢁ1 to m[CF3(A1)] and m[CF3(E)]
respectively, in accordance with an ionic formulation
Dunidentate > Dionic > Dbridging bidentate > Dchelating bidentate
In compounds 6 and 7 the D is ꢃ220 cmꢁ1 and 35
cmꢁ1, respectively in accordance with a unidentate coor-
dination of the trifluoroacetate group in 6 and a chelat-
ing bidentate coordination in 7 as also supported by the
X-ray data (see below).
ꢁ
or a weakly interacting CF3SO3 group.
In the 1H NMR spectra of 1–9 in CDCl3 (see Section 2),
the signals due to the diphosphine and diarsine ligands
show a different pattern relative to those found for the free

Effendy et al. / Inorganica Chimica Acta 358 (2005) 735–747
741
donors, confirming the existence of the complexes in solu-
tion. The bridging methylene resonances in 1–9 appear as
a broad singlet or resolved multiplet between 2.50 and
3.90 ppm generally downfield shifted with respect to those
found in the free donors.
31P chemical shifts (CDCl3 solution) and 31P–Ag cou-
pling-constants for derivatives 1, 2, 6 and 8, are reported
in Section 2. They have been found to be completely
independent of the dilution of the solutions. Our exper-
iments have been carried out at a concentration of 0.005
mol/l.
[Ag2(dppm)2(X)2] species (X = NO3 and NO2) [33].
The magnitude of the coupling constant and the chemi-
cal shift values indicated that also the counter-ion im-
pacts on the strength of the Ag–P bond: in fact the
greater coupling constant and D[=d(31Pcomplex) ꢁ
d(31Pfree donor)] values have been found for the perchlor-
ate and trifluoromethanesulfonate derivatives which
exist as ionic species in solution and containing effec-
tively two two-coordinate silver atoms, whereas the tri-
fluoroacetate and the acetonitrile adduct, which most
likely contain tricoordinate silver species, exhibit cou-
pling constant values of ꢃ490 Hz.
The 31P NMR spectra of compounds 1, 2, 6 and 8
support the persistence of a dinuclear structure also in
solution. Two broad multiplets or a broad doublet have
been found at room temperature, whereas the low tem-
The positive electrospray mass spectra of 1–9 (the
most relevant data are reported in Section 2 and two
typical spectra are reported in Fig. 2) further confirm
the existence of the dinuclear species also in solution.
The isotopic distribution is always in accordance with
the calculated composition. It is noteworthy that the
major peak in the positive spectra of the perchlorate
and trifluoromethanesulfonate species is always that
due to a binuclear dicationic species [Ag2(dpem)2]2+
formed upon loss of both X counter-ions. A different sit-
uation is found for the trifluoroacetate species where the
dominant aggregate is generally the [Ag2(tfa)(dpem)2]+
species, with the loss of only one tfa group. These data
are in good accordance with those derived from conduc-
tivity studies and further confirm the stronger interac-
tion between the tfa group and the silver center with
respect to ClO4 and tfs.
31
perature P spectra consist of AA0XX0A00A* patterns
(Fig. 1) [32] due to the non-equivalence of the phospho-
rus atoms (also consistent with the X-ray data) and
2
resulting from the large J(P–P), for the three possible
combinations of the two silver isotopes. This pattern,
has been found by us also for the well known
Another relevant feature found in the ESI MS spectra
is the presence of species containing coordinated solvent
molecules, always evident in the spectra of the dpam
derivatives, but not in those of the analogous dppm
compounds. This is in accordance with the weaker
donating ability of dpam relative to dppm which permits
coordinating solvents such as pyridine, MeCN and eth-
anol to interact more strongly with the silver cations.
The negative electrospray spectra are always domi-
nated by the presence of molecular peaks due to X
and AgXꢁ2 .
4. Single crystal X-ray studies
In the preceding paper [1], the predominance of the
0
trinuclear [M3X2(dpem)3]X( ) form was noted for ad-
ducts of MX:dpem (1:1) stoichiometry for M = CuI,
AgI wherein X was (pseudo-)halide; for the X = (simple)
oxyanion counterparts, the predominant form is binu-
clear [(Sn/X)M(E-dpem-E0)2M(X/Sn)], described hitherto
only for E = P. For the CuX:dppm array, the complex
[(MeCN2Cu(P-dppm-P0)2Cu(NCMe)2](ClO4)2 has been
described for X = ClO4 [34]; an adduct also described
for X2 = ac, BF4 [22] is also pertinent wherein the ace-
tate bridges a ꢁpair of planar three-coordinate metal
atoms, the BF4 being an unbound counterion, as also
Fig. 1. 31P NMR spectrum (218 K) of compound 2.

742
Effendy et al. / Inorganica Chimica Acta 358 (2005) 735–747
*MSD1 SPC, time=0.175:0.230 of PT\04033005.D API-ES, Pos, Scan, 30
Norm.
100
Max: 46242
80
60
40
20
0
(a)
1000
1025
1050
1075
1100
1125
1150
m/z
*MSD1 SPC, time=0.161:0.272 of PT\04033004.D API-ES, Pos, Scan, 30
Norm.
Max: 25735
100
80
60
40
20
0
(b)
200
400
600
800
1000
1200
1400
m/z
Fig. 2. ESI MS (ion positive) spectra of compound [Ag2(tfa)(dppm)2] 6 (a) and [Ag2(tfs)(dpam)2] 9 (b).
[(py)Cu(l-O Æ NO Æ O)(P-dppm-P0)2Cu(py)](NO3) Æ Me-
OH [35]. Counterpart adducts for M = Ag have been de-
scribed, all of the form [(X)Ag(P-dppm-P0)2Ag(X)] for
X = ClO4 (essentially uncoordinated) [10,11] and NO3
(unsolvated) [3] and chloroform solvated [36]), and ac
[37], the anions (semi-) chelating (rather than bridging)
each silver atom. Dimer core geometries are summarized
for these arrays in Table 1, together with those of com-
pounds defined in the present study; with only two
exceptions, the dimers tabulated therein all have crystal-
lographic inversion symmetry, one half of the dimer
comprising the asymmetric unit of the structure, with
elongated ꢀchairꢁ forms for the eight-membered rings;
of key importance is the definition of the unsolvated

Table 1
Selected geometries, MX:dpem(:S) (1:1(:n))2 symmetry-related atoms are primed
A
E(1) - CH4 - E(2)
B'
A'
η
θ
b
β
a
α
δ
M
M'
a'
γ
η'
c
E(2') - CH4
-
E(1')
B
M/E/X/(/S)Ref
A
B
a,a0
b
c
d
e
a
b
c
d
e
f
g,g0
h
s
Cu/P/ClO4/MeCNA
NCMe
NCMe
2.270(3), 2.283(3)
2.3998(8), 2.4059(8)
2.402(1), 2.406(1)
2.409(2), 2.410(2)
2.436(2), 2.417(2)
2.452(1), 2.422(1)
2.4346(9), 2.4536(9)
2.473(3), 2.437(3)
2.437(3), 2.441(2)
2.422(3), 2.435(3)
2.4110(7), 2.4196(6)
2.496(1), 2.506(2)
2.504(1), 2.526(1)
2.524(1), 2.521(1)
2.5195(9), 2.5126(9)
2.4993(7), 2.5123(7)
2.535(1); 2.550(1)
1.999(9)
2.878(9)
2.959(3)
3.075(7)(?)
2.416(5),
2.659(3),
2.475(3),
2.611(3),
2.377(7)
2.379(8)
2.519(2)
2.895(7)
2.425(4)
2.26(1)
2.16(1)
–
3.757(3)
3.082(4)
3.027(1)
3.037(2)
3.033(2)
3.026(2)
3.038(2)
3.022(1)
3.045(4)
2.9924(3)
3.0128(3)
3.0870(8)
3.187(1)
3.207(1)
3.172(1)
3.209(1)
3.2598(7)
3.220(1)
3.279(1)
119.9(1)
118.0(3)
90.97(2)
108.07(7)
79.6(1)
94.8(3)
–
96.1(4)
–
101.7(3)
–
117.0(3)
91.81(2)
88.81(3)
104.7(1)
116.8(1)
129.2(1)
99.33(8)
130.2(2)
102.2(2)
100.4(2)
99.47(5)
84.4(2)
116.4(3), 120.6(3)
114.59(9), 111.36(9)
111.4(1), 111.8(1)
112.4(1), 115.4(2)
111.6(2), 116.3(2)
109.8(2), 112.4(2)
113/6(1); 108.2(1)
107.5(3), 113.0(3)
109.3(1), 111.2(3)
111.5(3), 109.2(3)
117.79(7), 110.13(8)
114.9(3), 110.7(4)
116.2(2), 114.7(2)
117.5(2), 113.4(2)
115.8(2), 115.2(2)
120.7(1), 110.1(1)
119.1(3);121.6(3)
109.9(3)
111.3(2)
111.5(2)
111.7(3)
111.7(4)
110.5(2)
110.1(2)
111.6(5)
109.5(5)
111.6(5)
114.7(1)
108.5(4)
110.8(3)
109.0(4)
110.9(4)
113.4(2)
111.2(5)
113.7(1)
1
ꢀ
B
ꢀ
Ag/P/ClO4
(OClO3)
–
2.9006(5)
2.9532(7)
3.055(1)
3.085(1)
3.109(1)
3.1877(3)
3.194(2)
3.031(1)
3.104(1)
3.4348(3)
2.972(1)
3.515(1)
3.350(2)
–
173.49(3)
170.72(4)
174.95(6)
138.3(1)
149.4(1)
148.28(3)
146.1(1)
148.3(1)
151.2(1)
155.03(2)
168.83(4)
144.87(3)
129.57(5)
163.90(3)
150.44(2)
127.61(4)
1
C
ꢀ
ClO4/CH2Cl2
–
–
–
–
–
1
ClO4/MeCNB
D
NO3
(OClO3)
O2NO
NCMe
2.871(6)
2.689(6)
2.652(3)
2.694(4)
2.547(7)
–
92.2(1)
111.1(1)
106.5(1)
82.99(8)
106.7(2)
–
89.1(2)
48.9(2)
46.7(1)
47.9(1)
50.4(2)
–
90.6(1)
94.1(1)
98.9(1)
107.24(8)
102.5(2)
–
1
ꢀ
ꢀ
104.8(1)
80.9(1)
1
E
ꢀ
NO3/CHCl3
NO2/MeOHF
acG
O2NO
1
ꢀ
ONO
107.24(8)
82.2(1)
1
ꢀ
O2CCH3
OCOCF3
1
tfa (mol.1)B,H
–
105.0(2)
104.9(2)
99.19(5)
106.6(2)
107.9(1)
116.2(2)
88.6(2)
1
ꢀ
ꢀ
(mol.2)
–
–
–
1
tfs/EtOHB,I
As=ClOB4
tfaB,J
HOEt
–
–
–
–
–
–
1
ꢀ
ꢀ
(OClO3)
O2CCF3
NCMe
–
–
–
–
1
ꢀ
2.898(5)
2.706(8)
2.474(7)
2.457(4)
2.365(6)
77.9(1)
87.8(2)
98.4(2)
102.5(1)
107.3(2)
47.5(1)
91.8(3)
97.4(3)
79.1(1)
84.2(3)
135.3(1)
90.3(2)
97.3(2)
99.3(1)
107.2(3)
104.5(2)
114.3(2)
93.1(2)
1
ClO4/MeCNB,K
NCMe
HOEt
HOEt
py
1
ꢀ
EtOH
tfs/EtOHB,L
ClO4/pyB,M
OClO3
2.76(1)
ꢀ
OSO2CF3
OClO3
2.592(3)
2.498(9)
3.7091(6)
3.859(1)
115.95(1)
111.6(3)
87.82(9)
110.1(3)
1
m
0
0
˚
˚
Distances are in A, angles in degrees, M. . .M is d, E(1). . .E(2) is e, s is the dimer symmetry, E(1)–M–B is e, E(2 )–M–A is f, Ag. . .O distances less than 3 A are included.
A
Ref. [34]; Cu–N–C are 173.1(9), 157.4(9)ꢁ.
This work.
B
C
Ref. [11].
D
Ref. [3].
E
Ref. [36].
F
Ref. [33].
G
Ref. [37].
˚
Ag–O–C are 112.3(6), 112.7(6); Ag lie 0.18(2), 0.01(2) A out of the C2O2 planes.
H
I
Ag–O–C is 126.3(2).
J
˚
Ag lies 0.07(2) A out of the C2O2 plane; Ag–N is 3.176(9) A.
˚
K
L
Ag(1) is coordinated by 2 · MeCN, Ag(2) by OClO3, HOEt; Ag–N–C are 172.6(7), 151.6(8); Ag–O–Cl,C are 117.6(5), 123(1).
Ag–O–C,S are 122.8(3), 134.2(2)ꢁ.
Ag–O–Cl is 124.8(7)ꢁ (Cl lies on the mirror plane, an oxygen to either side bridging the two symmetry-related silver atoms).
M

744
Effendy et al. / Inorganica Chimica Acta 358 (2005) 735–747
parent AgClO4:dppm (1:1)2, containing the most linear
E–M–E array to be defined for MX:dpem (1:1)2 adducts
and the shortest ÆAg–P(dppm)æ and Ag. . .Ag0 distances
among them, notwithstanding a long but not insignifi-
tfa = O2CCF3 anions here are only unidentate OCOCF3
rather than chelate, with Ag–O much shorter; the angle
sums about the two three-coordinate silver atoms indi-
cate some perturbation from planarity, being 355.5ꢁ,
356.5ꢁ. The other adduct, of the weak X = tfs = O3SCF3
base, exhibits no appreciable interaction between anion
and metal; rather, the silver atoms are coordinated by
solvent ethanol (Fig. 3(c)). Here again the metal envi-
ronment is quasi-planar, the angle sum being 353.7ꢁ.
Among the array of AgX:dppm (1:1)2 dimers, Ag–P
are (broadly) shorter, where the Ag–O interactions are
weaker, with P–Ag–P straighter. Interestingly, the
Ag. . .Ag distance, presumptively indicative of any
metal. . .metal bonding interaction does not correlate
thus; it is shortest, unsurprisingly, in the unsolvated
perchlorate adduct, wherein the silver atom environ-
ment is most nearly linear, shorter than the P. . .P0 dis-
tance about it, whereas in the ethanol solvate cation, it
˚
cant perchlorate-O approach evident at 2.878(9) A.
The ꢀnakedꢁ dimer is also evinced in the previously re-
ported dichloromethane solvate [11]; interestingly the
presently obtained acetonitrile solvate, although similar
shows significant but weak interactions between the sil-
ver and both anion and solvent which have been noted
as ꢀcontactsꢁ in a cosynchronous study [10], but, as
Fig. 3(a)(ii) shows, both anion and solvent approaches
appear to constitute significant interactions.
Two new Ag oxyanion/dppm adducts are described;
in the X = tfa adduct (Fig. 3(b)), there are two independ-
ent dimers, one half of each contributing to the asym-
metric unit of the structure. Unlike the other planar
(isoelectronic) O2AB (= O2NO, O2CCH3) anions, the
2
1
122
N(1)
122'
221
222
121
O(4)
O(4')
P(2)
O(4)
Ag
Ag
112
111
1
212
211
P(1)
Cl
O(2')
O(2)
O(3)
O(1)
Cl
O(1)
C
O(3')
O(2)
216
211
P(1)
121
122
221
111
222
112
(a)
(i)
(ii)
2221
2212
221
2222
222
2211
20
212
P(2)
P(22)
O(22)
F(3)
3
F(2)
F(22)
21
0
O(3)
Ag(2)
F(1)
Ag
O(1)
P(1)
2111 P(21)
112
F(21)
F(21')
22
122
121
F(23)
2121
O(2)
O
F(23')
2122
1
2
(b)
(c)
Fig. 3. Projections of the following AgX:dppm(:S) (1:1(:x))2 dimers, normal to their P4 planes: (a) AgClO4:dppm (1:1)2 (i) in the unsolvated adduct
and (ii) in the acetonitrile solvated adduct, showing the perchlorate and solvent approaches in the latter. (b) Ag(tfa):dppm (1:1)2 (molecule 2;
molecule 1 is very similar). (c) Ag(tfs):dppm:EtOH (1:1:1)2.

Effendy et al. / Inorganica Chimica Acta 358 (2005) 735–747
745
222
F(2a)
F(3b)
F(1b)
112
O(1)
221
122
121
2
F(3a)
F(2b)
216
111
As(2)
211
Ag
As(1)
212
F(1a)
C
O(1)
O(2)
0
As(1)
112
O(3)
Cl
O(2)
111
As(2)
Ag
121
O(4)
222
221
126
(a)
(b)
22
21
N(21)
221
1111
1122
2211
222
2212
Ag(1)
1112
As(2)
2222
2221
1121
F(3)
3
212
As(22)
As(11)
N(11)
12
F(2)
O(2)
11
2
1
0
O(3)
O(24)
O22
F(1)
Ag
2122
O(1)
Cl(2)
Ag(2)
As(1)
1211
2121
As(21)
112
122
O(23)
As(12)
O(21)
121
2111
2112
O
1221
O(31)
1222
1
32
2
31
(d)
(c)
14
13
12
15
16
N(11)
222
121
221
212
122
112
211
Ag
O(11)
111
As(1)
As(2)
2
O(21)
O(23)
Cl(1)
Cl(2)
1
O(12)
O(13)
O(22)
(e)
Fig. 4. Projections of the following AgX:dpam(:S) (1:1(:x))2 dimers, normal to their As4 planes: (a) AgClO4:dpam (1:1)2. (b) Ag(tfa):dpam (1:1)2
(showing the disordered CF3 substituent). (c) Ag(tfs):dpam:EtOH (1:1:1)2 (cf. Fig. 3(c)). (d) AgClO4:dpam:MeCN:EtOH (2:2:2:1). (e)
Ag(ClO4):dpam:py (1:1:1)2.

746
Effendy et al. / Inorganica Chimica Acta 358 (2005) 735–747
is longest by a considerable margin, so much so as to ef-
fect a considerable increase in the P–C–P angle of the
ligand.
one of the perchlorate ions bridges the two four-coordi-
nate silver atoms, the other being unbound: [(py)Ag(O Æ -
ClO2 Æ O)(As-dpam-As0)2Ag(py)](ClO4). Although such
an arrangement is incompatible with inversion symme-
try, the aggregate is disposed about a crystallographic
mirror plane which passes through the CH2 groups of
the two ligands, and the chlorine and two oxygen atoms
of each perchlorate. The extended chair form of the
macrocycle is now disturbed by the bridging group, O,
A greater diversity of adducts is found among the
AgX:dpam arrays (Fig. 4); the dpam ligand being a
weaker donor than dppm, it is not surprising to find here
anion and solvent interactions with the silver atom to be
more invasive. The perchlorate adduct, AgClO4:dpam
(1:1)2 is unsolvated, with an Ag. . .anion contact indica-
tive of a weak interaction evident; despite this, Ag. . .Ag,
uniquely among these E = As arrays, is short, suggestive
of some interaction. The weakness of the anion interac-
tion is not preclusive of concomitant solvation; a novel
mixed solvate of the perchlorate has been isolated,
of the form [(MeCN)2Ag(As-dpam-As0)Ag(OClO3)
(HOEt)](ClO4), devoid of crystallographic symmetry,
one formula unit comprising the asymmetric unit of
the structure, displaying two different types of silver
environment, both four-coordinate, in one of which
the solvent/anion interactions is weak – at the second sil-
ver, the perchlorate rather than the ethanol, although
notably Ag. . .OClO3 here is shorter than in the parent
unsolvated perchlorate complex. The two As–Ag–As an-
gles here differ considerably, reflective of the different
metal environments and the strengths of the Ag. . . sol-
vent interactions. The disparity in Ag. . .O-anion/O-sol-
vent distances observed here disappears in the tfs/
EtOH solvated adduct wherein the two distances are
very similar and the metal more genuinely four-coordi-
nate. Here As–Ag–As is smaller and Ag. . .Ag and
As–C–As concomitantly larger. This complex is isomor-
phous with its dppm counterpart; comparison of the two
structures shows the differences generally to be as ex-
pected, consequent on replacement of P by As. In the
ClO4/MeCN, EtOH adduct, it is further of interest to
make comparison with the CuClO4:dppm:MeCN
(1:1:2)2 adduct, noting the differences in strength of
binding of the acetonitrile ligands between the two
(MeCN)2ME2 arrays.
˚
Ag, C lying 3.42(2), 1.080(1), ꢁ1.05(1) A out of the
As4 plane, and the planes of the ꢀaxialꢁ phenyl substitu-
ents quasi-parallel. The present ONAs2 coordination
sphere about the silver appears to be the first so defined,
also true of the N2AgAs2 and O2AgAs2 arrays above.
Finally, in the context of the above, we note the interest-
ing array in which one of the silver atoms is replaced by
mercury(II), in [Hg(P-dppm-P0)2Hg](O3SCF3)3 [38].
Acknowledgements
Support by the Australian Research Council, the
University of Camerino and Fondazione Carima are
gratefully acknowledged, also a grant from Proyek
RUT VI BPPT LIPI, Indonesia.
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