Silver(I) complexes with the mixed P/O donor ligand Ph2P(CH2)2O(CH2)2O (CH2)2PPh2 (L1) and the crystal structures of [Ag(L1)](CF3SO3), [Ag2(L1)3] (CF3SO3)2 and [Ag(L1)(NO3)]

Article abstract of DOI:10.1016/S0277-5387(01)00893-2

The Ag(I) salts AgY (Y = ClO₄, CF₃SO₃, NO₃, Cl or I) react with one molar equivalent of the diphosphinodiether ligand Ph₂P(CH₂)₂ O(CH₂)₂O(CH₂)₂PPh₂ (L¹) to give 1:1 species of stoichiometry Ag(L¹)Y. The structures of these species have been investigated in solution by ³¹P NMR spectroscopy and for [Ag(L¹)](ClO₄), [Ag(L¹)](CF₃SO₃) and [Ag(L¹)(NO₃)] in the solid state by single crystal X-ray diffraction. In particular, the ¹⁰⁷Ag-P and ¹⁰⁹Ag-P coupling constants provide a convenient method for identifying the solution speciation, especially for the occurrence of anion coordination in the nitrate and halide complexes. The conclusions from the NMR spectroscopic studies are also consistent with the solid state structures. Addition of a further equivalent of L¹ to [Ag(L¹)](CF₃SO₃) results in a very significant drop in the Ag-P coupling constants, indicative of higher P-coordination at Ag(I), now involving three P-donor atoms. This conclusion is also borne out by a crystallographic study on [Ag₂(L¹)₃] (CF₃SO₃)₂ which shows a dinuclear cation with one chelating L¹ and one bridging L¹ ligand coordinated to each metal centre, giving a distorted trigonal planar geometry.

Full text of DOI:10.1016/S0277-5387(01)00893-2

Polyhedron 20 (2001) 2741–2746
www.elsevier.com/locate/poly
Silver(I) complexes with the mixed P/O donor ligand
Ph2P(CH2)2O(CH2)2O(CH2)2PPh2 (L1) and the crystal structures of
[Ag(L1)](CF3SO3), [Ag2(L1)3](CF3SO3)2 and [Ag(L1)(NO3)]
Fiona Harrington, Melissa L. Matthews, Bhavesh Patel, Gillian Reid *
Department of Chemistry, Uni6ersity of Southampton, Highfield, Southampton, SO17 1BJ, UK
Received 12 June 2001; accepted 5 July 2001
Abstract
The Ag(I) salts AgY (Y=ClO4, CF3SO3, NO3, Cl or I) react with one molar equivalent of the diphosphinodiether ligand
Ph2P(CH2)2O(CH2)2O(CH2)2PPh2 (L1) to give 1:1 species of stoichiometry Ag(L1)Y. The structures of these species have been
investigated in solution by 31P NMR spectroscopy and for [Ag(L1)](ClO4), [Ag(L1)](CF3SO3) and [Ag(L1)(NO3)] in the solid state
by single crystal X-ray diffraction. In particular, the 107Ag–P and 109Ag–P coupling constants provide a convenient method for
identifying the solution speciation, especially for the occurrence of anion coordination in the nitrate and halide complexes. The
conclusions from the NMR spectroscopic studies are also consistent with the solid state structures. Addition of a further
equivalent of L1 to [Ag(L1)](CF3SO3) results in a very significant drop in the Ag–P coupling constants, indicative of higher
P-coordination at Ag(I), now involving three P-donor atoms. This conclusion is also borne out by a crystallographic study on
[Ag2(L1)3](CF3SO3)2 which shows a dinuclear cation with one chelating L1 and one bridging L1 ligand coordinated to each metal
centre, giving a distorted trigonal planar geometry. © 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Silver(I) complexes; Mixed P/O donor ligands; Crystal structures; NMR spectroscopy
tracarbonyl via the P atoms, affording metallocyclic
complexes which then bind alkali metal ions through
the ether oxygens [6]. They have also shown that
[Pt(H2O){Ph2P{(CH2)2O}4(CH2)2PPh2}]2+ involves co-
ordination to Pt(II) through both P atoms and one
ether oxygen, as well as the aquo ligand [7]. Very
recently, Mirkin and co-workers have demonstrated
that under appropriate conditions the phosphathia lig-
and o-C6H4{S(CH2)2PPh2}2 forms an unusual neutral
metallocyclic complex with Rh(I), via a halide-induced
ring opening reaction [8]. In the course of our recent
work we have demonstrated that Ph2P(CH2)2O(CH2)2-
O(CH2)2PPh2 (L1) reacts with AgBF4 or with AuCl(tht)
and TlPF6 to give the linear, two-coordinate [Ag(L1)]-
BF4 or [Au(L1)]PF6, respectively, both of which were
crystallographically characterised [4]. The occurrence of
two-coordinate Ag(I) species involving only phosphine
ligands is relatively rare, other examples include
[Ag{P(tol)3}2]+, [Ag(PtBu3)2]+ and [Ag{P(NMe2)3}2]+
[9–11]. This prompted us to investigate whether other
factors would lead to L1 altering its mode
1. Introduction
We have been interested for some time in the coordi-
nating properties of mixed phosphathia and phospha-
oxa ligands. These are of interest since they allow the
coordinating properties of both donor atom types to be
investigated in a single ligand and may promote un-
usual metal complexes [1–5]. Furthermore, depending
on the actual metal ion, one or other of the donor atom
types may not interact significantly. For example, we
have shown that the dinuclear [Au2{Ph2P(CH2)2-
S(CH2)2S(CH2)2PPh2}2]Cl2 adopts an unusual helical
structure through coordination via the P atoms only,
with one Cl− anion occupying the metallocyclic cavity
[1]. Also, Gray and co-workers have shown that ligands
of the form Ph2P{(CH2)2O}n(CH2)2PPh2 (n=3 or 5)
function as cis-chelating bidentate ligands to Mo te-
* Corresponding author. Tel.: +44-23-8059-3609; fax: +44-23-
8059-3781.
E-mail address: gr@soton.ac.uk (G. Reid).
0277-5387/01/$ - see front matter © 2001 Elsevier Science Ltd. All rights reserved.
PII: S0277-5387(01)00893-2

2742
F. Harrington et al. / Polyhedron 20 (2001) 2741–2746
of coordination to Ag(I), and whether we would be able
to detect this in solution through 31P NMR spectro-
scopic studies. In this paper we report our findings,
including the preparations of a series of other Ag(I)
complexes of L1 incorporating a variety of different
anions, and using different ratios of Ag:L1. Crystal
structures of specific examples are also included.
fore probed the solution coordination environment at
Ag(I) in the range of compounds incorporating differ-
ent anions by 31P NMR spectroscopy. In all cases the
31P NMR spectra exhibit a single phosphorus environ-
ment with a resonance to high frequency of free L1 (l
31P= −21.3). In most cases the room temperature
spectra reveal two doublets, consistent with coupling to
107/109Ag (both I=1/2, 49%, 51% abundant respec-
tively), although for some, the solutions had to be
cooled to observe these couplings, consistent with high
lability. The chemical shift data and couplings are given
in Table 1. In all cases the ratio of the 107Ag–P/109Ag–
P coupling constants is close to 0.87, consistent with the
relative magnetogyric ratios. The data show that for the
NO3−, Cl− and I− complexes there is a significant
reduction in the coupling constants (cf. the BF4− salt),
strongly suggesting some interaction of these relatively
strongly coordinating anions with the Ag(I) centre,
increasing the formal coordination number at Ag(I). In
contrast, the coupling constants for the ClO4− and the
1:1 Ag:L1 CF3SO3− salts show virtually no change,
consistent with retention of the linear P2-donor set seen
for the BF4− salt. The resonance for (AgI)2(L1) is
significantly to low frequency of those for the 1:1 Ag:L1
species, but clearly shows coupling to 107/109Ag at low
temperature. Addition of a further molar equivalent of
L1 to [Ag(L1)](CF3SO3) leads to a dramatic reduction in
J107/109Ag–P, strongly suggesting generation of a higher
coordination number at Ag(I). In fact, the coupling
constants for [Ag2(L1)3](CF3SO3)2 of 332 and 380 Hz
are intermediate between those seen for P2 coordination
from L1 on Ag(I) (523, 601 Hz—see above) and P4
coordination at Ag(I), e.g. in tetrahedral [Ag(dppe)2]+,
1J(107Ag–P)=231, 1J(109Ag–P)=266 Hz [14]. These
data suggest that [Ag2(L1)3]2+ probably involves P3
coordination at Ag(I). It is notable that 31P NMR
spectroscopy shows that addition of a further molar
equivalent of L1 to [Ag(L1)(NO3)] leads to dissociation
2. Results and discussion
The silver(I) complexes were prepared in good yield
by treatment of the appropriate silver salt with one (or
two for [Ag2(L1)3](CF3SO3)2) molar equivalent(s) of L1
in CH2Cl2 at 0 °C (or reflux for the Cl and I deriva-
tives) in foil-wrapped flasks to protect the solutions
from bright light, followed by precipitation with diethyl
ether. Reaction of Ag(CF3SO3) with two molar equiva-
lents of L1 repeatedly yielded the 2:3 Ag:L1 complex,
and we saw no evidence for the formation of
[Ag(L1)2](CF3SO3)2 despite using excess L1, whereas
reaction of L1 with two molar equivalents of AgI
afforded the dinuclear species (AgI)2(L1). The electro-
spray mass spectra of the 1:1 Ag:L1 salts each show
peaks with the correct isotopic distribution for
[Ag(L1)]+ (m/z=593, 595), in addition Ag(L1)I shows
peaks with the correct isotopic distribution for
[Ag2(L1)2I]+. The mass spectrum of [Ag2(L1)3]-
(CF3SO3)2 shows peaks consistent with [Ag(L1)2]+ (m/
z=1079, 1081) and [Ag(L1)]+ (m/z=593, 595). These
data, together with elemental microanalyses and 1H
NMR spectroscopy, confirm the stoichiometries of the
products as Ag(L1)X (X=ClO4, CF3SO3, NO3, Cl or
I), [Ag2(L1)3](CF3SO3)2 and [(AgI)2(L1)].
We have shown previously that J(107Ag–P) and
J(109Ag–P) for [Ag(L1)]BF4 are 523 and 601 Hz, re-
spectively and a crystallographic analysis of this salt
revealed two-coordinate Ag(I)—see above [4]. It is
known that the magnitude of the Ag–P coupling con-
stants in silver phosphine complexes varies with coordi-
nation number at silver, becoming smaller as the
coordination number increases [12,13]. We have there-
of the ligating nitrate and formation of [Ag2(L1)3]2+
,
the nitrate now functioning as counterion. In order to
investigate whether these solution effects were mirrored
in the solid state, crystallographic analyses were under-
taken on [Ag(L1)](ClO4), [Ag(L1)](CF3SO3), [Ag2(L1)3]-
(CF3SO3)2 and [Ag(L1)(NO3)].
Table 1
[Ag(L1)](ClO4) (monoclinic, C2/c, Z=4, a=
31P{1H} NMR data a
,
15.8420(2), b=13.2335(3), c=15.7553(3) A, i=
Compound
l
31P (ppm)
1J107/109Ag–P (Hz)
118.012(2)°) is isostructural with [Ag(L1)]BF4, [4] with
crystallographic two-fold symmetry and linear Ag(I)
coordinated to the two P-donor atoms of L1,
Ag(L1)BF4
Ag(L1)CF3SO3
Ag(L1)ClO4
Ag(L1)NO3
Ag(L1)Cl
−3.4
−1.4
−0.7
−1.9
−5.5
−5.4
−22.9
−5.4
523, 601
511, 582
522, 604
497, 568
438, 505
410, 473
458, 536
332, 380
,
d(AgꢀP)=2.405(1)
A
and ÚP(1)ꢀAg(1)ꢀP(1*)=
165.16(7)°. The crystal structure of [Ag(L1)](CF3SO3),
although not isostructural, shows (Fig. 1, Table 2) a
very similar geometry at Ag(I) which coordinates to
both P atoms of L1 giving an approximately linear
arrangement with no interaction between the triflate
anion and the silver ion, AgꢀP(1)=2.4070(9),
Ag(L1)I
(AgI)2(L1)
Ag2(L1)3(CF3SO3)2
a Spectra recorded in CH2Cl2/CDCl3.

F. Harrington et al. / Polyhedron 20 (2001) 2741–2746
2743
Table 3
1
,
Selected bond lengths (A) and bond angles (°) for [Ag(L )(NO3)]
Bond lengths
Ag(1)ꢀP(1)
Ag(1)ꢀP(2)
Ag(1)ꢀO(3)
Ag(1)ꢀO(4)
2.412(2)
2.616(2)
2.675(7)
2.496(9)
Bond angles
P(1)ꢀAg(1)ꢀP(2)
P(1)ꢀAg(1)ꢀO(3)
P(1)ꢀAg(1)ꢀO(4)
P(2)ꢀAg(1)ꢀO(3)
P(2)ꢀAg(1)ꢀO(4)
O(3)ꢀAg(1)ꢀO(4)
139.2(1)
106.9(2)
115.9(2)
110.2(1)
101.2(1)
49.2(2)
Fig. 1. View of the structure of the Ag-containing species in
[Ag(L1)](CF3SO3). CH2Cl2 with numbering scheme adopted. Ellip-
soids are drawn at 40% probability. H atoms are omitted for clarity.
tions to two O atoms from an asymmetrically bound
bidentate NO3− ligand, AgꢀO=2.496(9), 2.675(7) A.
,
The overall coordination geometry is distorted psuedo-
tetrahedral, with ÚP(1)ꢀAg(1)ꢀP(2)=139.2(1)°. The
structure of [Ag2(L1)3](CF3SO3)2 shows that the cation
is centrosymmetric (Fig. 3, Table 4) with each of the
two Ag atoms coordinated to one chelating L1 via the
two P donors, and to one P donor atom from a
bridging L1. Thus each Ag(I) ion is in a distorted
trigonal planar environment of three P atoms, with no
Ag–O interactions. The angles around Ag(I) lie in the
range 114.10(4)–125.84(4)°. The AgꢀP bond lengths
Table 2
Selected bond lengths (A) and bond angles (°) for [Ag(L1)]-
(CF3SO3)·CH2Cl2
,
Bond lengths
Ag(1)ꢀP(1)
Ag(1)ꢀP(2)
2.4070(9)
2.4172(9)
Bond angles
P(1)ꢀAg(1)ꢀP(2)
167.55(3)
,
(2.4494(12), 2.4551(12), 2.4729(12) A) are slightly
longer than those in the linear two-coordinate species
[Ag(L1)]+, consistent with the increase in coordination
number.
,
AgꢀP(2)=2.4172(9) A, ÚP(1)ꢀAgꢀP(2)=167.55(3)°.
In contrast, the crystal structure of [Ag(L1)(NO3)]
shows (Fig. 2, Table 3) the silver centre coordinated to
the two P atoms from L1, with additional weak interac-
Thus, the solid state structures of these complexes are
entirely consistent with the conclusions from the 31P
Fig. 2. View of the structure of Ag(L1)(NO3) with numbering scheme adopted. Ellipsoids are drawn at 40% probability. H atoms are omitted for
clarity.

2744
F. Harrington et al. / Polyhedron 20 (2001) 2741–2746
Fig. 3. View of the structure of the Ag-containing species in [Ag2(L1)3](CF3SO3)2 with numbering scheme adopted. Ellipsoids are drawn at 40%
probability. H atoms and phenyl rings are omitted for clarity. Atoms marked with a prime are related by a crystallographic inversion centre.
form. 1H NMR spectra were recorded in CDCl3 using a
Bruker AM300 spectrometer. 31P{1H} NMR spectra
were recorded in CH2Cl2 containing approximately 10–
15% CDCl3 using a Bruker AM360 or DPX400 spec-
trometer operating at 145.8 or 162.0 MHz, respectively
and are referenced to 85% H3PO4 (l=0). Microanaly-
ses were undertaken by the University of Strathclyde
microanalytical service. L1 was prepared as described
previously [4].
NMR spectra described above. It is somewhat surpris-
ing that there is no interaction between the ether oxy-
gen atoms and the silver(I) ion in any of these species,
but that NO-3 does interact significantly despite the low
affinity of Ag(I) for O-donor ligands.
These results demonstrate that L1 is a very versatile
ligand to silver(I), readily altering its mode of coordina-
tion and conformation to accommodate changes at the
metal centre. Furthermore, the structures identified for
the complexes in the solid state are consistent with the
conclusions from the solution NMR studies, with the
107Ag–31P and 109Ag–31P coupling constants changing
in a predictable way with changes in the coordination
number and environment at Ag(I).
Table 4
,
Selected bond lengths (A) and bond angles (°) for
[Ag2(L1)3](CF3SO3)2
Bond lengths
Ag(1)ꢀP(1)
Ag(1)ꢀP(2)
Ag(1)ꢀP(3)
2.4494(12)
2.4551(12)
2.4729(12)
3. Experimental
Bond angles
Infrared spectra were recorded as KBr or CsI discs
using a Perkin–Elmer 1710 spectrometer over the range
4000–220 cm−1. Mass spectra were run by positive ion
electrospray (MeCN solution) using a VG Biotech plat-
P(1)ꢀAg(1)ꢀP(2)
P(1)ꢀAg(1)ꢀP(3)
P(2)ꢀAg(1)ꢀP(3)
125.84(4)
114.10(4)
119.93(4)

F. Harrington et al. / Polyhedron 20 (2001) 2741–2746
2745
3.1. Preparations
spectrum (MeCN): found m/z=1315, 593, 595. Calc.
for [109Ag2(L1)2I]+ 1317, [107Ag(L1)]+ 593, [109Ag(L1)]+
Ag(L1)(CF3SO3): To a degassed solution of L1 (0.100
g, 0.206 mmol) in CH2Cl2 (20 cm3) at 0 °C was added
Ag(CF3SO3) (0.053 g, 0.206 mmol). The resulting solu-
tion was stirred for approximately 3 h in a foil-wrapped
flask. The solution was then concentrated in vacuo to
approximately 5 cm3 and hexane (ca. 30 cm3) was
added to afford a white solid, which was filtered and
dried in vacuo. Yield 72%, 0.110 g. Anal. Found: C,
50.1; H, 4.3. Calc. for C31H32AgF3O5P2S: C, 50.1; H,
4.3%. Electrospray mass spectrum (MeCN): found m/
z=595, 593. Calc. for [109Ag(L1)]+ 595, [107Ag(L1)]+
595. H NMR: l 7.3–7.7 (m, Ph, 20H), 3.8 (m, CH2O,
1
4H), 3.6 (s, CH2O, 4H), 2.6 (m, CH2P, 4H). IR (cm−1):
3069 w, 2960 w, 2935 w, 2870 w, 1590 w, 1484 m, 1431
m, 1359 m, 1312 w, 1187 w, 1100 s, 1036 w, 989 m, 890
m, 850 w, 744 m, 692 m, 619 w, 540 w, 507 m. \m
(CH2Cl2, 10−3 mol dm−3)=1.9 ohm−1 cm2 mol−1
.
[(AgI)2(L1)]: Method as above, with refluxing CH2Cl2
and using two molar equivalents of AgI. Yield 41%.
Anal. Found: C, 38.0; H, 3.5. Calc. for
C30H32Ag2I2O2P2: C, 37.7; H, 3.4%. Electrospray mass
spectrum (MeCN): found m/z=593, 595. Calc. for
1
1
593. H NMR: l 7.3–7.6 (m, Ph, 20H), 3.6–3.8 (m,
[
107Ag(L1)]+ 593, [109Ag(L1)]+ 595. H NMR: l 7.3–7.7
CH2O, 8H), 2.7 (m, CH2P, 4H). IR (cm−1): 3059 w,
2961 w, 2925 w, 2866 w, 1560 w, 1484 m, 1439 m, 1349
m, 1271 s, 1221 m, 1147 m, 1122 m, 1097 m, 1023 s, 904
w, 795 m, 750 m, 691 s, 667 m, 637 s, 513 s, 463 w, 433
w, 349 w.
(m, Ph, 20H), 3.8 (m, CH2O, 4H), 3.6 (s, CH2O, 4H),
2.6 (m, CH2P, 4H). IR (cm−1): 3069 w, 2945 w, 2859 w,
1572 w, 1482 m, 1435 m, 1357 m, 1308 w, 1260 m, 1185
w, 1158 w, 1096 s, 1025 w, 996 m, 975 w, 788 m, 741 m,
694m, 618 w, 512 m, 482 w. \m (CH2Cl2, 10−3
Ag(L1)(NO3): Method as above giving a white solid.
Yield 43%. Anal. Found: C, 54.9; H, 4.7. Calc. for
C30H32AgNO5P2: C, 54.9; H, 4.9%. Electrospray mass
mol dm−3)=1.6 ohm−1 cm2 mol−1
.
[Ag2(L1)3](CF3SO3)2: Method as above but using two
molar equivalents of L1. Yield 23%. Anal. Found: C,
56.7; H, 5.1. Calc. for C92H96Ag2F6O12P6S2: C, 56.0; H,
4.9%. Electrospray mass spectrum (MeCN): found m/
z=1079, 1081, 593, 595. Calc. for [107Ag(L1)2]+ 1079,
spectrum (MeCN): found m/z=595, 593. Calc. for
1
[
109Ag(L1)]+ 595, [107Ag(L1)]+ 593. H NMR: l 7.3–7.7
(m, Ph, 20H), 3.5–3.8 (m, CH2O, 8H), 2.6 (m, CH2P,
4H). IR (cm−1): 3051 w, 2955 w, 2959 w, 1484 m, 1435
m, 1384 s, 1297 s, 1187 w, 1130 m, 1100 s, 1034 w, 998
m, 894 w, 821 w, 741 m, 694 m, 517 m, 473 w, 438 w.
Ag(L1)(ClO4): Method as above, giving a white solid.
Yield 42%. Anal. Found: C, 50.6; H, 4.7. Calc. for
C30H32AgClO6P2·1/2CH2Cl2: C, 49.8; H, 4.5%. Electro-
spray mass spectrum (MeCN): found m/z=595, 593;
[
109Ag(L1)2]+ 1081, [107Ag(L1)]+ 593, [109Ag(L1)]+ 595.
1H NMR: l 7.3–7.6 (m, Ph, 20H), 3.5–3.7 (m, CH2O,
8H), 2.6 (br, CH2P, 4H). IR (cm−1): 3062 w, 2950 w,
2930 w, 2874 w, 1484 m, 1437 m, 1403 m, 1364 m, 1266
s, 1224 m, 1148 m, 1100 s, 1033 m, 999 m, 911 w, 750
s, 697 s, 638 s, 518 s, 524 w, 486 w.
Calc. for [109Ag(L1)]+ 595, [107Ag(L1)]+ 593. H NMR:
3.2. X-ray crystallography
1
l 7.4–8.0 (m, Ph, 20H), 3.7–4.0 (m, CH2O, 4H), 3.5
(m, CH2O, 2H), 2.8 (m, CH2O, 2H), 2.6 (m, CH2P,
4H). IR (cm−1): 3046 w, 2956 w, 2907 w, 2862 w, 1560
w, 1473 m, 1463 w, 1438 s, 1406 w, 1367 m, 1346 m,
1306 w, 1285 m, 1237 w, 1221 m, 1185 w, 1164m, 1097
vs br, 995 s, 909 m, 884 m, 792 m, 759 s, 748 s, 710 m,
694 s, 623 s, 548 w, 523 m, 510 m, 463 m, 419 w, 362
w.
Details of the crystallographic data collection and
refinement parameters are given in Table 5. The crystals
were grown by vapour diffusion of diethyl ether into
solutions of the complexes in CH2Cl2 at approximately
−15 °C. Data collection used a Rigaku AFC7S four-
circle diffractometer or an Enraf–Nonius Kappa CCD
diffractometer operating at T=150 K and using
graphite-monochromated Mo Ka X-radiation (u=
Ag(L1)Cl: Method as above, except the CH2Cl2 solu-
tion was refluxed. Yield 54%. Anal. Found: C, 55.2; H,
5.5. Calc. for C30H32AgClO2P2·1/2CH2Cl2: C, 54.5; H,
4.9%. Electrospray mass spectrum (MeCN): found m/
,
0.71073 A). Structure solution and refinement were
routine, except for some disorder in some of the C
atoms associated with the phenyl groups in
[Ag(L1)(NO3)] which was modelled satisfactorily using
partial occupancies [15–17]. Selected bond lengths and
angles are given in Tables 2–4.
z=595, 593. Calc. for
[
[
107Ag(L1)]+ m/z=593,
1
109Ag(L1)]+ m/z=595. H NMR: l 7.4–7.7 (m, Ph,
20H), 3.8 (m, CH2O, 4H), 3.7 (s, CH2O, 4H), 2.6 (m,
CH2P, 4H). IR (cm−1): 3061 w, 2970 w, 2864 w, 1540
w, 1489 m, 1441 m, 1359 m, 1262 m, 1190 w, 1103 s,
1036 m, 809 m, 751 m, 698 m, 621 w, 545 w, 515 m, 486
w, 445 w, 410 w. \m (CH2Cl2, 10−3 mol dm−3)=1.7
4. Supplementary material
ohm−1 cm2 mol−1
.
Cystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC Nos. 164925–164928. Copies of
this information may be obtained free of charge from
Ag(L1)I: Method as above, with refluxing CH2Cl2.
Yield 84%. Anal. Found: C, 50.0; H, 4.5. Calc. for
C30H32AgIO2P2: C, 50.3; H, 4.6%. Electrospray mass

2746
F. Harrington et al. / Polyhedron 20 (2001) 2741–2746
Table 5
Crystallographic data and structure refinement parameters
Complex
[Ag(L1)](CF3SO3).CH2Cl2
C32H34AgCl2F3O5P2S
828.39
[Ag2(L1)3](CF3SO3)2
C92H96Ag2F6O12P6S2
1973.45
[Ag(L1)(NO3)]
C30H32AgNO5P2
656.40
monoclinic
C2/c
Empirical formula
Formula weight
Crystal system
Space group
triclinic
triclinic
(
(
P1
P1
Unit cell dimensions
,
a (A)
10.0928(1)
10.4575(1)
16.5622(2)
90.5877(5)
90.8655(5)
100.5412(5)
1718.22(3)
2
11.0275(1)
12.5004(2)
16.9448(2)
80.7110(8)
81.7090(8)
76.0320(5)
2223.47(5)
1
25.87(7)
9.20(2)
24.74(4)
90
101.1(2)
90
5777.8(2)
8
8.46
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
V (A )
3
,
Z
v (Mo Ka) (cm−1
Unique observed reflections
)
9.49
7022
6.67
10186
5427
Reflections observed [Io\n|(Io)]
Parameters
5031, n=3
415
7028, n=3
541
3725, n=2
437
R
Rw
0.039
0.048
0.058
0.067
0.050
0.070
R=ꢀ (ꢁFobsꢁi−ꢁFcalcꢁi)/ꢀ ꢁFobsꢁi; Rw=[ꢀ wi(ꢁFobsꢁi−ꢁFcalcꢁi)2/ꢀ wiꢁFobsꢁi ].
2
[5] C.L. Doel, A.M. Gibson, G. Reid, C.S. Frampton, Polyhedron
14 (1995) 3139.
[6] A. Varshney, G.M. Gray, Inorg. Chem. 30 (1991) 1748.
[7] A. Varshney, M.L. Webster, G.M. Gray, Inorg. Chem. 31 (1882)
2580.
The Director, CCDC, 12 Union Road, Cambridge,
CB2 1EZ, UK (fax: +44-1223-336033; e-mail: de-
posit@ccdc.cam.ac.uk or www: http://www.ccdc.cam.
ac.uk).
[8] F.M. Dixon, A.H. Eisenberg, J.R. Farrell, C.A. Mirkin, L.M.
Liable-Sands, A.L. Rheingold, Inorg. Chem. 39 (2000) 3432.
[9] E.L. Meutterties, C.W. Alegranti, J. Am. Chem. Soc. 94 (1972)
6386.
Acknowledgements
[10] R.G. Goel, P. Pilon, Inorg. Chem. 17 (1978) 2876.
[11] S.M. Socol, R.A. Jacobson, J.G. Verkade, Inorg. Chem. 23
(1984) 88.
[12] R. Stein, C. Knobler, Inorg. Chem. 16 (1977) 242.
[13] P.F. Barron, J.C. Dyason, P.C. Healy, L.M. Engelhardt, B.W.
Skelton, A.H. White, J. Chem. Soc., Dalton Trans. (1986) 1965.
[14] S.J. Berners Price, C. Brevard, A. Pagelot, P.J. Sadler, Inorg.
Chem. 24 (1985) 4278.
We thank the EPSRC for support and Professor
M.B. Hursthouse for access to the Kappa CCD
diffractometer.
References
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