Synthesis and structural characterization of adducts of silver(I) carboxylate salts AgX (X = CF3COO, CH3COO) with ER3 (E = P, As; R = Ph, cy, o-tolyl) and oligodentate aromatic bases derivative of 2,2′-bipyridyl, L, AgX:PR3:L (1:1:1)

Article abstract of DOI:10.1016/j.ica.2006.07.015

Twenty-one adducts of the form AgX:ER₃:L (1:1:1) (X = CF₃COO ('tfa'), CH₃COO ('ac'), E = P, As; R = Ph, cy, o-tolyl; L = 2,2′-bipyridyl ('bpy')-based ligand) have been synthesized and characterized by analytical, spectroscopic (IR, far-IR, ¹H, ¹⁹F and ³¹P NMR) and single crystal X-ray diffraction studies. The resulting complexes are predominantly of the form [(R₃E)AgL]⁺X^-, with a trigonal EAgN₂ coordination environment, the planarity of which may be perturbed by the approach of anion or solvent. The carboxylate anions have been found to be uni-, or semi-bidentate, or also completely ionic, as in the complexes [Ag(PPh₃)(bpy)(H₂O)](tfa) and [Ag(PPh₃)(dpk · H₂O)](tfa) ('dpk · H₂O' = bis(2-pyridyl)ketone (hydrated)). The complexes Agac:PPh₃:dpa (1:1:1) and Agac:P(o-tol)₃:dpa:MeCN (1:1:1:1) are dinuclear, with bridging unidentate acetate and terminal unidentate dpa ('dpa' = bis(2-pyridyl)amine).

Full text of DOI:10.1016/j.ica.2006.07.015

Inorganica Chimica Acta 360 (2007) 1451–1465
www.elsevier.com/locate/ica
Synthesis and structural characterization of adducts of
silver(I) carboxylate salts AgX (X = CF3COO, CH3COO) with
ER3 (E = P, As; R = Ph, cy, o-tolyl) and oligodentate aromatic
bases derivative of 2,20-bipyridyl, L, AgX:PR3:L (1:1:1)
c
c,
c
Effendy a,b, Fabio Marchetti , Claudio Pettinari *, Riccardo Pettinari ,
a
a
Brian W. Skelton , Allan H. White
a
Chemistry M313, School of Biomedical, Biomolecular and Chemical Sciences, The University of Western Australia, Crawley, WA 6009, Australia
b
Jurusan Pendidikan Kimia, FMIPA Universitas Negeri Malang, Jalan Surabaya 6, Malang 65145, Indonesia
c
`
Dipartimento di Scienze Chimiche, Universita degli Studi di Camerino, via S. Agostino 1, 62032 Camerino MC, Italy
Received 29 May 2006; accepted 6 July 2006
Available online 21 July 2006
Abstract
Twenty-one adducts of the form AgX:ER3:L (1:1:1) (X = CF3COO (‘tfa’), CH3COO (‘ac’), E = P, As; R = Ph, cy, o-tolyl; L = 2,20-
bipyridyl (‘bpy’)-based ligand) have been synthesized and characterized by analytical, spectroscopic (IR, far-IR, 1H, 19F and 31P NMR)
and single crystal X-ray diffraction studies. The resulting complexes are predominantly of the form [(R3E)AgL]+Xꢀ, with a trigonal
EAgN2 coordination environment, the planarity of which may be perturbed by the approach of anion or solvent. The carboxylate anions
have been found to be uni-, or semi-bidentate, or also completely ionic, as in the complexes [Ag(PPh3)(bpy)(H2O)](tfa) and
[Ag(PPh3)(dpk Æ H2O)](tfa) (‘dpk Æ H2O’ = bis(2-pyridyl)ketone (hydrated)). The complexes Agac:PPh3:dpa (1:1:1) and Agac:P(o-tol)3:
dpa:MeCN (1:1:1:1) are dinuclear, with bridging unidentate acetate and terminal unidentate dpa (‘dpa’ = bis(2-pyridyl)amine).
ꢀ 2006 Published by Elsevier B.V.
Keywords: Silver carboxylates; Phosphine; Aromatic N-bases; Single crystal X-ray studies; NMR
1. Introduction
while coordination polymers and networks of Ag(I) with
binaphthylbis(amidopyridyl) ligands contain trifluoroace-
tate groups coordinated to silver and involved in hydro-
gen-bonding with the N–H groups of the donors [6]. In
the preceding pair of papers [7,8], we have described a
number of quasi-systematic studies of arrays of complexes
of silver(I) oxyanion salts, with oxyanions of increasing
basicity – perchlorate [7] and nitrate [8] – with mixed group
15 ligand arrays of the form unidentate ER3 (E = P, As,
Sb; R various) and oligodentate nitrogen-donor aromatic
ligands L. We now extend the array to encompass the more
basic carboxylate anions acetate (‘ac’) and trifluoroacetate
(‘tfa’) in combination with various ER3 arrays for E = P,
As; R = Ph, cy (=cyclohexyl), o-tol (=o-tolyl), and ligands
L = 2,20-bipyridyl (‘bpy’), 1,10-phenanthroline (‘phen’),
2,9-dimethyl,1,10-phenanthroline (‘dmp’), 2,20-biquinolyl
Silver carboxylate derivatives have received attention
because of a variety of potential applications. Thus, recent
papers report on the use of silver trimethylacetate phos-
phine derivatives as CVD molecular precursors [1–3], alter-
natives to fluorinated b-diketonate silver complexes [4],
because of diminished sensitivity to light and moisture,
higher volatility and thermal stability. Other studies of sil-
ver fluorinated carboxylate complexes with 4,40-bipyridine
show the formation of supramolecular assemblies of
Ag(I) polyhedra containing embedded acetylenediyne [5],
*
Corresponding author. Tel.: +39 0737 402234; fax: +39 0737 637345.
E-mail address: claudio.pettinari@unicam.it (C. Pettinari).
0020-1693/$ - see front matter ꢀ 2006 Published by Elsevier B.V.
doi:10.1016/j.ica.2006.07.015

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Effendy et al. / Inorganica Chimica Acta 360 (2007) 1451–1465
(‘bq’), bis(2-pyridyl)amine (‘dpa’), bis(2-pyridyl)ketone
(‘dpk’) (as its hydrated form ‘dpk Æ H2O’), the dominant
stoichiometry being AgX:ER3:L (1:1:1); the results are pre-
sented hereunder.
PPh3 (0.262 g, 1.0 mmol), and phen (0.180 g, 1.0 mmol);
m.p. 186–186 ꢁC. Anal. Calc. for C32H23AgF3N2O2P: C,
57.94; H, 3.49; N, 4.22. Found: C, 57.70; H, 3.62; N,
4.21%. Km (CH3CN, 10ꢀ4 M): 109 Xꢀ1 cm2 molꢀ1. Km
(CH2Cl2, 10ꢀ4 M): 27 Xꢀ1 cm2 molꢀ1. IR (KBr, cmꢀ1):
. . . . . .
1619m, 1589m, 1569m, 1513s m(C C, C N), 1687vs,
• •
2. Experimental
1435s m(CF3COO). IR (nujol, cmꢀ1): 525vs, 504s, 491s,
445m, 431m, 417m m(PPh3), 267m. 1H NMR (CDCl3,
293 K): d, 7.48m (15H, PC18H15), 7.75dd, 7.89s, 8.37dd,
9.10dd (8H, CHphen). 19F NMR (CDCl3, 223 K): d,
ꢀ74.7s. 31P NMR (CDCl3, 223 K): d, 13.5dd
Experimental procedures follow those recorded in an
accompanying paper [9]; in a number of cases, following
those precedents, crystals were readily obtained from a
few mL of MeCN solutions of the reagents on a millimolar
scale by slow cooling and/or evaporation in ambience. In a
few cases, probably consequent on solubility consider-
ations, methanol proved more congenial.
1
(1J(31P–109Ag): 701.9 Hz; J(31P–107Ag): 620.2 Hz), 10.8d
br (1J(31P–107/109Ag): 463.6 Hz). The compound was mod-
:
elled from the X-ray study as 3Æ MeOH.
2.1. Syntheses
2.1.4. Synthesis of Agac:PPh3:phen:MeOH
(1:1:1:2) Æ MeOH (4 Æ 2MeOH)
2.1.1. Synthesis of Agtfa:PPh3:bpy (1:1:1) Æ MeOH
(1 Æ MeOH)
Compound 4 (0.545 g, yield: 85%) has been prepared
following a procedure similar to that reported for 3 by
using a methanol solution of Agac (0.167 g, 1.0 mmol),
PPh3 (0.262 g, 1.0 mmol), and phen (0.180 g, 1.0 mmol);
m.p. 116–118 ꢁC. Anal. Calc. for C33H30AgN2O3P (mono-
solvate): C, 61.86; H, 4.72; N, 4.38. Found: C, 61.41; H,
A solution containing Agtfa (0.221 g, 1.0 mmol), PPh3
(0.262 g, 1.0 mmol), and bpy (0.156 g, 1.0 mmol) in 5 mL
of methanol was stirred with warming for 1 h and then
cooled at room temperature. A colourless crystalline precip-
itate slowly formed, which was filtered off, washed with
methanol (5 mL), dried under reduced pressure and shown
to be compound 1 (0.588 g, yield: 92%); m.p. 101–103 ꢁC.
Anal. Calc. for C30H23AgF3N2O2P: C, 56.36; H, 3.63; N,
4.38. Found: C, 56.15; H, 3.76; N, 4.42%. Km (CH3CN,
4.48; N, 4.36. Km (CH3CN, 10ꢀ4 M): 110 Xꢀ1 cm2 molꢀ1
Km (CH2Cl2, 10ꢀ4 M): 30 Xꢀ1 cm2 molꢀ1
IR (KBr,
cmꢀ1): 3350br m(CH3O–H), 1651m d (CH3O–H), 1617m,
. . . . . .
.
.
1507m m(C C, C N), 1561vs, 1407s m(CH3COO). IR
•
•
(nujol, cmꢀ1): 512s, 502s, 493s, 4437m, 4329m, 420m
m(PPh3), 281w, 266m, 246m, 228m. 1H NMR (CDCl3,
293 K): d, 1.88s (3H, CH3COO), 2.04s (3H, CH3OH),
3.48s (1H, CH3OH), 7.45m (15H, PC18H15), 7.67dd,
7.84s, 8.30dd, 9.15dd (8H, CHphen). 31P NMR (CDCl3,
293 K): d, 12.4br. 31P NMR (CDCl3, 223 K): d, 12.7br,
8.1d (1J(31P–109/107Ag): 449.8 Hz).
10ꢀ4 M): 115 Xꢀ1 cm2 molꢀ1
29 Xꢀ1 cm2 molꢀ1 IR (KBr, cmꢀ1): 1580m, 1558m
. . . . . .
.
Km (CH2Cl2, 10ꢀ4 M):
.
m(C C, C N), 1675vs, 1435s m(CF3COO). IR (nujol,
•
•
cmꢀ1): 523s, 505s, 494s, 445m, 434m, 417m m(PPh3), 399w,
262m. 1H NMR (CDCl3, 293 K): d, 7.40m (15H, PC18H15),
7.54m, 7.91dt, 8.20dd, 8.70m (8H, CHbpy). 19F NMR
(CDCl3, 223 K): d, ꢀ74.7s. 31P NMR (CDCl3, 223 K): d,
13.6dd (1J(31P–109Ag): 699.4 Hz; 1J(31P–107Ag): 620.0 Hz).
2.1.5. Synthesis of Agtfa:PPh3:dmp (1:1:1) (5)
Compound 5 (0.621 g, yield: 90%) has been prepared
following a procedure similar to that reported for 1 by
using a methanol/ethanol solution of Agtfa (0.221 g,
1.0 mmol), PPh3 (0.262 g, 1.0 mmol), and dmp (0.208 g,
1.0 mmol); m.p. 205–207 ꢁC. Anal. Calc. for C34H27AgF3-
N2O2P: C, 59.12; H, 3.94; N, 4.06. Found: C, 59.34; H,
2.1.2. Synthesis of Agtfa:PPh3:bpy:H2O (1:1:1:1) (2)
Compound 2 (0.578 g, yield: 88%) has been prepared
following a procedure similar to that reported for 1 by
using an acetonitrile solution of Agtfa (0.221 g, 1.0 mmol),
PPh3 (0.262 g, 1.0 mmol), and bpy (0.156 g, 1.0 mmol);
m.p. >97 ꢁC (dec.). Anal. Calc. for C30H25AgF3N2O3P:
C, 54.81; H, 3.83; N, 4.26. Found: C, 54.85; H, 4.01; N,
4.20%. IR (KBr, cmꢀ1): 3280br m(H2O), 1684m d (H2O),
4.00; N, 4.12; Km (CH3CN, 10ꢀ4 M): 119 Xꢀ1 cm2 molꢀ1
Km (CH2Cl2, 10ꢀ4 M): 40 Xꢀ1 cm2 molꢀ1
IR (KBr,
. . . . . .
.
.
cmꢀ1): 1619m, 1555m, 1499s m(C C, C N), 1665vs,
•
•
1589s m(CF3COO). IR (nujol, cmꢀ1): 520s, 506vs, 490s,
. . .
. . .
1594s, 1580m m(C C, C N), 1661s, 1465s m(CF3COO).
•
•
1
IR (nujol, cmꢀ1): 524s, 505s, 493s, 442m, 424m, 414m
432m br m(PPh3), 317w, 272m, 248m H NMR (CDCl3,
1
m(PPh3), 394w, 265m. H NMR (CDCl3, 293 K): d, 7.43m
293 K): d, 2.85s (6H, CH3dmp), 7.36m, 7.47m (15H,
PC18H15), 7.62d, 7.83s, 8.29d (6H, CHdmp). 19F NMR
(CDCl3, 223 K): d, ꢀ74.5s. 31P NMR (CDCl3, 223 K): d,
(15H, PC18H15), 7.56m, 7.987dt, 8.19dd, 8.58m (8H,
CHbpy). 19F NMR (CDCl3, 223 K): d, ꢀ75.5s. 31P NMR
(CDCl3, 223 K): d, 14.8dd (1J(31P–109Ag): 702.1 Hz;
1J(31P–107Ag): 621.4 Hz).
1
10.8dd (1J(31P–109Ag): 516.3 Hz; J(31P–107Ag): 454.0 Hz),
1
13.1dd (1J(31P–109Ag): 686.0 Hz; J(31P–107Ag): 599.4 Hz).
2.1.3. Synthesis of Agtfa:PPh3:phen (1:1:1) (3)
2.1.6. Synthesis of Agac:PPh3:dmp (1:1:1:1) Æ MeOH
(6 Æ MeOH)
Compound 6 (0.615 g, yield: 92%) has been prepared fol-
lowing a procedure similar to that reported for 1 by using a
Compound 3 (0.629 g, yield: 95%) has been prepared
following a procedure similar to that reported for 1 by
using a methanol solution of Agtfa (0.221 g, 1.0 mmol),

Effendy et al. / Inorganica Chimica Acta 360 (2007) 1451–1465
1453
methanol solution of Agac (0.167 g, 1.0 mmol), PPh3
(0.262 g, 1.0 mmol), and dmp (0.208 g, 1.0 mmol); m.p.
233–235 ꢁC. Anal. Calc. for C35H34AgN2O3P: C, 62.79; H,
5.12; N, 4.18. Found: C, 62.78; H, 4.95; N, 4.40%. Km
using an acetonitrile solution of Agac (0.167 g, 1.0 mmol),
PPh3 (0.262 g, 1.0 mmol), and dpa (0.171 g, 1.0 mmol);
m.p. 134–136 ꢁC. Anal. Calc. for C30H27AgN3O2P: C,
60.01; H, 4.53; N, 7.00. Found: C, 60.29; H, 4.71; N,
7.18%. Km (CH3CN, 10ꢀ4 M): 10 Xꢀ1 cm2 molꢀ1. Km
(CH3CN, 10ꢀ4 M): 106 Xꢀ1 cm2 molꢀ1
.
Km (CH2Cl2,
10ꢀ4 M): 41 Xꢀ1 cm2 molꢀ1. IR (KBr, cmꢀ1): 3240br
. . . . . .
(CH2Cl2, 10ꢀ4 M): 1 Xꢀ1 cm2 molꢀ1. IR (KBr, cmꢀ1):
. . .
N), 1548vs, 1439s m(CH3COO). IR (nujol, cmꢀ1):
m(CH3O–H), 1617m, 1586m m(C C, C N), 1564vs,
3244m, 3165m m(N–Hdpa), 1605s, 1594s, 1566m m(C C,
•
•
•
1499s m(CH3COO). IR (nujol, cmꢀ1): 517vs, 506vs, 495vs,
435m, 422m m(PPh3), 549s, 396m, 330w, 310m, 274w,
263w, 251m. 1H NMR (CDCl3, 293 K): d, 1.97s (3H,
CH3COO), 2.81s (6H, CH3dmp), 3.33s (3H, CH3OH),
3.95s (1H, CH3OH), 7.25m, 7.42m (15H, PC18H15), 7.51d,
7.72s, 8.217d (6H, CHdmp). 31P NMR (CDCl3, 223 K): d,
C
. . .
•
516s, 506vs, 494s, 436m, 424m, 417m, 408m m(PPh3),
1
332w, 317w, 259m, 218m. H NMR (CDCl3, 293 K): d,
2.14s (3H, CH3COO), 7.42m (15H, PC18H15), 6.81dt,
7.55dt, 7.65dd, 8.18dd (8H, CHdpa), 8.55br (1H, NHdpa).
31P NMR (CDCl3, 223 K): d, 13.8d br (1J(31P–109/107Ag):
653.1 Hz).
1
9.5dd (1J(31P–109Ag): 643.4 Hz; J(31P–107Ag): 559.1 Hz),
1
9.8dd (1J(31P–109Ag): 343.0 Hz; J(31P–107Ag): 279.8 Hz).
2.1.10. Synthesis of Agtfa:PPh3:dpk Æ H2O (1:1:1) Æ MeCN
(10 Æ MeCN)
2.1.7. Synthesis of Agtfa:PPh3:bq (1:1:1) (7)
Compound 7 (0.635 g, yield: 86%) has been prepared
following a procedure similar to that reported for 1 by
using an acetonitrile solution of Agtfa (0.221 g, 1.0 mmol),
PPh3 (0.262 g, 1.0 mmol), and bq (0.256 g, 1.0 mmol); m.p.
215–217 ꢁC. Anal. Calc. for C38H27AgF3N2O2P: C, 61.78;
H, 3.69; N, 3.79. Found: C, 61.92; H, 3.80; N, 3.84%. Km
Compound 10 (0.558 g, yield: 85%) has been prepared
following a procedure similar to that reported for 1 by
using an acetonitrile solution of Agtfa (0.221 g, 1.0 mmol),
PPh3 (0.262 g, 1.0 mmol), and dpk (0.184 g, 1.0 mmol);
m.p. 87–89 ꢁC. Anal. Calc. for C33H28AgF3NO4P: C,
56.75; H, 4.04; N, 2.01. Found: C, 56.81; H, 3.95; N,
1.94%. Km (CH3CN, 10ꢀ4 M): 125 Xꢀ1 cm2 molꢀ1. Km
(CH2Cl2, 10ꢀ4 M): 44 Xꢀ1 cm2 molꢀ1. IR (KBr, cmꢀ1):
(CH3CN, 10ꢀ4 M): 108 Xꢀ1 cm2 molꢀ1
10ꢀ4 M): 38 Xꢀ1 cm2 molꢀ1. IR (KBr, cmꢀ1): 1619m,
. . . . . .
. Km (CH2Cl2,
. . .
. . .
1552m, 1502s m(C C, C N), 1659vs, 1594s m(CF3COO).
3150br m(O–Hdpk), 1583s, 1572m m(C C,
C
N),
•
•
•
•
IR (nujol, cmꢀ1): 520vs, 505vs, 493vs, 440m, 427m m(PPh3),
394m, 270s. 1H NMR (CDCl3, 293 K): d, 7.45m (15H,
PC18H15), 7.60dt, 7.67dt, 7.79dd, 8.28d, 8.38dd, 8.46d
(12H, CHbq). 19F NMR (CDCl3, 223 K): d, ꢀ74.3s. 31P
NMR (CDCl3, 293 K): d, 10.2br, 14.6br. 31P NMR
(CDCl3, 223 K): d, 8.9dd (1J(31P–109Ag): 423.9 Hz;
1J(31P–107Ag): 350.8 Hz), 9.7dd (1J(31P–109Ag): 519.0 Hz;
1J(31P–107Ag): 449.6 Hz), 12.1dd (1J(31P–109Ag): 685.8 Hz;
1J(31P–107Ag): 594.2 Hz).
1678vs, 1434s m(CF3COO). IR (nujol, cmꢀ1): 525vs, 507s,
494s, 441m, 425m, 416m, 406w m(PPh3), 386w, 376w,
352w, 278w, 263m, 246w, 227w. 1H NMR (CDCl3,
293 K): d, 2.02s (3H, CH3CN), 7.47m (15H, PC18H15),
7.26dt, 7.78dt, 8.09dd, 8.32dd (8H, CHdpk), 9.90br (2H,
O–Hdpk). 19F NMR (CDCl3, 223 K): d, ꢀ76.1s. 31P
NMR (CDCl3, 223 K): d, 18.2dd (1J(31P–109Ag):
1
747.1 Hz; J(31P–107Ag): 646.9 Hz).
2.1.11. Synthesis of Atfa:Pcy3:bpy (1:1:1) (11)
2.1.8. Synthesis of Agtfa:PPh3:dpa (1:1:1) (8)
Compound 11 (0.571 g, yield: 87%) has been prepared
following a procedure similar to that reported for 1 by
using an ethanol solution of Agtfa (0.221 g, 1.0 mmol),
Pcy3 (0.280 g, 1.0 mmol), and bpy (0.156 g, 1.0 mmol);
m.p. 170–172 ꢁC. Anal. Calc. for C30H41AgF3N2O2P: C,
54.80; H, 6.29; N, 4.26. Found: C, 54.94; H, 6.25; N,
4.47%. Km (CH3CN, 10ꢀ4 M): 104 Xꢀ1 cm2 molꢀ1. Km
(CH2Cl2, 10ꢀ4 M): 14 Xꢀ1 cm2 molꢀ1. IR (KBr, cmꢀ1):
Compound 8 (0.602 g, yield: 92%) has been prepared fol-
lowing a procedure similar to that reported for 1 by using an
acetonitrile solution of Agtfa (0.221 g, 1.0 mmol), PPh3
(0.262 g, 1.0 mmol), and dpa (0.171 g, 1.0 mmol); m.p.
164–166 ꢁC. Anal. Calc. for C30H24AgF3N3O2P: C, 55.01;
H, 3.70; N, 6.42. Found: C, 55.28; H, 3.86; N, 6.65%. Km
(CH3CN, 10ꢀ4 M): 101 Xꢀ1 cm2 molꢀ1
10ꢀ4 M): 3 Xꢀ1 cm2 molꢀ1. IR (KBr, cmꢀ1): 3322m, 3204m
. . . . . .
. Km (CH2Cl2,
. . .
. . .
1618m, 1590m, 1574w m(C C, C N), 1680vs, 1461s
•
•
m(N–Hdpa), 1647s, 1575s, 1547m 1530s m(C C, C N),
m(CF3COO). IR (nujol, cmꢀ1): 543s, 515s, 472m, 460m,
410s m(Pcy3), 389w, 267s. 1H NMR (CDCl3, 293 K): d,
1.28m, 1.88m (33H, PC18H33), 7.42dd, 7.93dt, 8.39dd,
8.71dd (8H, CHbpy). 19F NMR (CDCl3, 223 K): d,
ꢀ74.9s. 31P NMR (CDCl3, 223 K): d, 46.1dd
•
•
1667vs, 1592s m(CF3COO). IR (nujol, cmꢀ1): 521s, 503m,
1
493s, 434m, 425m, 403m m(PPh3), 328m, 267m. H NMR
(CDCl3, 293 K): d, 7.45m (15H, PC18H15), 6.82dt, 7.63dt,
7.72dd, 8.07dd (8H, CHdpa), 9.95br (1H, NHdpa). 19F
NMR (CDCl3, 223 K): d, ꢀ75.1s. 31P NMR (CDCl3,
223 K): d, 10.6d br (1J(31P–109/07Ag): 474.8 Hz), 17.1dd
(1J(31P–109Ag): 732.5 Hz; 1J(31P–107Ag): 637.2 Hz).
1
(1J(31P–109Ag): 719.1 Hz; J(31P–107Ag): 622.4 Hz).
2.1.12. Synthesis of Agtfa:Pcy3:dmp (1:1:1) (12)
Compound 12 (0.653 g, yield: 92%) has been prepared
following a procedure similar to that reported for 1 by
using an ethanol solution of Agtfa (0.221 g, 1.0 mmol),
Pcy3 (0.280 g, 1.0 mmol), and dmp (0.208 g, 1.0 mmol);
2.1.9. Synthesis of Agac:PPh3:dpa (1:1:1)(2) (9)
Compound 9 (0.504 g, yield: 84%) has been prepared
following a procedure similar to that reported for 1 by

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Effendy et al. / Inorganica Chimica Acta 360 (2007) 1451–1465
m.p. 203–205 ꢁC. Anal. Calc. for C34H45AgF3N2O2P: C,
57.55; H, 6.39; N, 3.95. Found: C, 57.24; H, 6.30; N,
4.04%. Km (CH3CN, 10ꢀ4 M): 107 Xꢀ1 cm2 molꢀ1. Km
(CH2Cl2, 10ꢀ4 M): 18 Xꢀ1 cm2 molꢀ1. IR (KBr, cmꢀ1):
m.p. 122–124 ꢁC. Anal. Calc. for C30H41AgAsN2O2F3: C,
51.37; H, 5.89; N, 3.99. Found: C, 51.53; H, 5.82; N,
4.12%. Km (CH3CN, 10ꢀ4 M): 124 Xꢀ1 cm2 molꢀ1. Km
(CH2Cl2, 10ꢀ4 M): 38 Xꢀ1 cm2 molꢀ1
.
. . .
. . .
1622m, 1591m, 1558m, 1505s m(C C, C N), 1689vs,
•
•
1446s m(CF3COO). IR (nujol, cmꢀ1): 547s, 513s, 492m,
439m, 434m m(Pcy3), 398m, 384m, 377m, 352w, 314m,
2.1.16. Synthesis of Agtfa:Ascy3:dpa (1:1:1) (16)
Compound 16 (0.602 g, yield: 84%) has been prepared
following a procedure similar to that reported for 1 by
using an ethanol solution of Agtfa (0.221 g, 1.0 mmol),
Ascy3 (0.324 g, 1.0 mmol), and dpa (0.171 g, 1.0 mmol);
m.p. 142–145 ꢁC. Anal. Calc. for C30H42AgAsF3N3O2: C,
50.29; H, 5.91; N, 5.86. Found: C, 50.23; H, 5.84; N,
5.96%. Km (CH3CN, 10ꢀ4 M): 119 Xꢀ1 cm2 molꢀ1. Km
1
280w, 265s, 248w. H NMR (CDCl3, 293 K): d, 1.30m,
1.85m (33H, PC18H33), 2.94s (6H, CH3dmp), 7.79d,
7.93dt, 7.94s, 8.43d (6H, CHdmp). 19F NMR (CDCl3,
223 K): d, ꢀ74.8s. 31P NMR (CDCl3, 223 K): d, 31.1dd
1
(1J(31P–109Ag): 517.6 Hz; J(31P–107Ag): 447.9 Hz), 31.4dd
1
(1J(31P–109Ag): 518.7 Hz; J(31P–107Ag): 448.0 Hz), 38.2dd
1
(1J(31P–109Ag): 701.8 Hz; J(31P–107Ag): 618.9 Hz).
(CH2Cl2, 10ꢀ4 M): 34 Xꢀ1 cm2 molꢀ1
.
2.1.13. Synthesis of Agtfa:Pcy3:bq (1:1:1) (13)
2.1.17. Synthesis of Agac:P(o-tol)3:bpy (1:1:1) Æ H2O
(17 Æ H2O)
Compound 13 (0.712 g, yield: 94%) has been prepared
following a procedure similar to that reported for 1 by
using an ethanol solution of Agtfa (0.221 g, 1.0 mmol),
Pcy3 (0.280 g, 1.0 mmol), and bq (0.256 g, 1.0 mmol);
m.p. 192–194 ꢁC. Anal. Calc. for C38H45AgF3N2O2P: C,
60.24; H, 5.99; N, 3.70. Found: C, 60.42; H, 5.82; N,
3.87%. Km (CH3CN, 10ꢀ4 M): 112 Xꢀ1 cm2 molꢀ1. Km
(CH2Cl2, 10ꢀ4 M): 26 Xꢀ1 cm2 molꢀ1. IR (KBr, cmꢀ1):
Compound 17 (0.613 g, yield: 95%) has been prepared
following a procedure similar to that reported for 1 by
using an acetonitrile/water solution of Agac (0.167 g,
1.0 mmol), P(o-tol)3 (0.304 g, 1.0 mmol), and bpy
(0.156 g, 1.0 mmol); m.p. 130–132 ꢁC. Anal. Calc. for
C33H34AgN2O3P: C, 61.41; H, 5.31; N, 4.34. Found: C,
61.45; H, 5.23; N, 4.36%. Km (CH3CN, 10ꢀ4 M):
1617m, 1589m, 1534m, 1501s m(C C, C N), 1680s,
6 Xꢀ1 cm2 molꢀ1. Km (CH2Cl2, 10ꢀ4 M): 2 Xꢀ1 cm2 molꢀ1
. . . . . .
.
. . .
. . .
•
•
1459s m(CF3COO). IR (nujol, cmꢀ1): 512s, 483s, 449m,
441m, 420m m(Pcy3), 398m, 385w, 352w, 327w, 303w,
IR (KBr, cmꢀ1): 1589s, 1573s m(C C, C N), 1561vs,
•
•
1401s m(CH3COO). IR (nujol, cmꢀ1): 564m, 557m, 520m,
463vs, 418w, 403m m(P(o-tol)3), 278m, 268s, 255w, 247w,
1
279m, 264s, 247s, 231w, 224m. H NMR (CDCl3, 293 K):
1
d, 1.28m, 1.86m (33H, PC18H33), 7.60dt, 7.77dt, 7.90dd,
8.28d, 8.41d, 8.80d (12H, CHbq). 19F NMR (CDCl3,
223 K): d, ꢀ74.7s. 31P NMR (CDCl3, 223 K): d, 31.3dd
227m. H NMR (CDCl3, 293 K): d, 1.84s (3H, CH3COO),
2.08s (2H, H2O), 2.56s (9H, P(C6H4-ortho-CH3)3), 6.82dt,
7.40m (12H, P(C6H4-ortho-CH3)3), 7.18dt, 7.84dt, 8.38dd,
8.69d (8H, CHbpy). 31P NMR (CDCl3, 223 K): d, ꢀ17.6d
br (1J(31P–109/107Ag): 700.6 Hz).
1
(1J(31P–109Ag): 701.8 Hz; J(31P–107Ag): 618.9 Hz), 38.9dd
1
(1J(31P–109Ag): 516.4 Hz; J(31P–107Ag): 449.2 Hz).
2.1.14. Synthesis of Agtfa:Pcy3:dpa (1:1:1) (14)
2.1.18. Synthesis of Agtfa:P(o-tol)3:phen:H2O
(1:1:1) Æ H2O (18 Æ H2O)
Compound 14 (0.618 g, yield: 92%) has been prepared
following a procedure similar to that reported for 1 by
using an acetonitrile solution of Agtfa (0.221 g, 1.0 mmol),
Pcy3 (0.280 g, 1.0 mmol), and dpa (0.171 g, 1.0 mmol); m.p.
173–175 ꢁC. Anal. Calc. for C30H42AgF3N3O2P: C, 53.58;
H, 6.29; N, 6.25. Found: C, 53.81; H, 6.34; N, 6.33%. Km
Compound 18 (0.665 g, yield: 92%) has been prepared
following a procedure similar to that reported for 1 by
using an acetonitrile/water solution of Agtfa (0.221 g,
1.0 mmol), P(o-tol)3 (0.304 g, 1.0 mmol), and phen
(0.180 g, 1.0 mmol); m.p. 127–219 ꢁC. Anal. Calc. for
C35H31AgF3N2O3P: C, 58.11; H, 4.32; N, 3.87. Found:
C, 57.92; H, 4.34; N, 3.56%. Km (CH3CN, 10ꢀ4 M):
(CH3CN, 10ꢀ4 M): 101 Xꢀ1 cm2 molꢀ1
. Km (CH2Cl2,
10ꢀ4 M): 1 Xꢀ1 cm2 molꢀ1
.
IR (KBr, cmꢀ1): 3328m,
3204m, 3137m m(N–Hdpa), 1592m, 1578s, 1533m m(C C,
12 Xꢀ1 cm2 molꢀ1
molꢀ1. IR (KBr, cmꢀ1): 1617m, 1587m, 1567m, 1508s
. . . . . .
.
Km (CH2Cl2, 10ꢀ4 M): 2 Xꢀ1 cm2
. . .
N), 1684vs, 1474s m(CF3COO). IR (nujol, cmꢀ1):
•
. . .
C
•
527vs, 515vs, 472m, 462m, 413s m(Pcy3), 390w, 326m,
m(C C, C N), 1671vs, 1459s m(CF3COO). IR (nujol,
• •
1
280w, 267m, 247w, 229w. H NMR (CDCl3, 293 K): d,
cmꢀ1): 559m br, 518m, 460s, 414m, 402m m(P(o-tol)3),
278m, 264m, 254s, 247m, 227m. 1H NMR (CDCl3,
293 K): d, 2.12s (2H, H2O), 2.58s (9H, P(C6H4-ortho-
CH3)3), 6.97t, 7.23t, 7.45m (12H, P(C6H4-ortho-CH3)3),
7.86dd, 7.99s, 8.53dd, 8.83dd (8H, CHbpy). 19F NMR
(CDCl3, 223 K): d, ꢀ75.3s. 31P NMR (CDCl3, 223 K): d,
ꢀ18.0d br (1J(31P–109/107Ag): 678.7 Hz).
1.27m, 1.86m (33H, PC18H33), 6.86dt, 7.63dt, 7.67dd,
8.14dd (8H, CHdpa), 8.55br (1H, NHdpa). 19F NMR
(CDCl3, 223 K): d, ꢀ75.2s. 31P NMR (CDCl3, 223 K): d,
1
44.2dd (1J(31P–109Ag): 720.2 Hz; J(31P–107Ag): 625.7 Hz).
2.1.15. Synthesis of Agtfa:Ascy3:bpy (1:1:1) (15)
Compound 15 (0.547 g, yield: 78%) has been prepared
following a procedure similar to that reported for 1 by
using an acetonitrile solution of Agtfa (0.221 g, 1.0 mmol),
Ascy3 (0.324 g, 1.0 mmol), and bpy (0.156 g, 1.0 mmol);
2.1.19. Synthesis of Agtfa:P(o-tol)3:bq (1:1:1) (19)
Compound 19 (0.687 g, yield: 88%) has been prepared
following a procedure similar to that reported for 1 by

Effendy et al. / Inorganica Chimica Acta 360 (2007) 1451–1465
1455
using an acetonitrile solution of Agtfa (0.221 g, 1.0 mmol),
2.2. Structure determinations
P(o-tol)3 (0.304 g, 1.0 mmol), and bq (0.256 g, 1.0 mmol);
m.p. 221–223 ꢁC. Anal. Calc. for C41H33AgF3N2O2P: C,
63.01; H, 4.26; N, 3.58. Found: C, 62.92; H, 4.35; N,
3.54%. Km (CH3CN, 10ꢀ4 M): 105 Xꢀ1 cm2 molꢀ1. Km
(CH2Cl2, 10ꢀ4 M): 26 Xꢀ1 cm2 molꢀ1. IR (KBr, cmꢀ1):
General procedures are described in an accompanying
paper [9]; specific details are as follows. Data for 2, 7,
10 and 15 were measured at ca. 298 K using a single-
counter instrument (Gaussian absorption corrections,
2h/h scan mode, I > 3r(I) ‘observed’). CCDC Nos.
602570–602590.
. . .
. . .
1617m, 1591s, 1564m, 1552m, 1502s m(C C, C N),
•
•
1670vs, 1452s m(CF3COO). IR (nujol, cmꢀ1): 565m,
550m, 531s, 519m, 509m, 479vs, 465vs, 433w m(P(o-tol)3),
1
395w, 278m, 268s, 255m, 247m, 225m. H NMR (CDCl3,
2.2.1. Crystal/refinement data
2.2.1.1. Agtfa:PPh3:bpy (1:1:1) Æ MeOH (1). C31H27AgF3-
293 K): d, 2.47s (9H, P(C6H4-ortho-CH3)3), 6.95dt, 7.20t,
7.42m (12H, P(C6H4-ortho-CH3)3), 7.61dt, 7.68dt,
7.91dd, 8.08dd, 8.45d, 8.80dd (12H, CHbq). 19F NMR
(CDCl3, 223 K): d, ꢀ74.7s. 31P NMR (CDCl3, 223 K): d,
ꢀ8.8br.
1
ꢀ
N2O3P, M = 671.4. Triclinic, space group P1 (Ci , No. 2),
˚
˚
˚
c = 16.114(1) A,
a = 9.0126(6) A,
b = 10.5085(7) A,
a = 93.397(1)ꢁ, b = 97.819(1)ꢁ, c = 92.064(1)ꢁ, V =
3
1508 A . Dcalc (Z = 2) = 1.479 g cmꢀ3. lMo = 7.7 cmꢀ1
;
˚
specimen:
2hmax = 58ꢁ;
No = 6143; R = 0.026, Rw = 0.036.
0.30 · 0.18 · 0.12 mm;
Nt = 17478; N = 7338
‘Tmin/max’ = 0.81.
(Rint = 0.014),
2.1.20. Synthesis of Agtfa:P(o-tol)3:dpa (1:1:1) (20)
Compound 20 (0.585 g, yield: 84%) has been prepared
following a procedure similar to that reported for 1 by
using an acetonitrile solution of Agtfa (0.221 g, 1.0 mmol),
P(o-tol)3 (0.304 g, 1.0 mmol), and dpa (0.171 g, 1.0 mmol);
m.p. 170–171 ꢁC. Anal. Calc. for C33H30AgF3N3O2P: C,
56.91; H, 4.34; N, 6.03. Found: C, 56.86; H, 4.43; N,
6.28%. Km (CH3CN, 10ꢀ4 M): 113 Xꢀ1 cm2 molꢀ1. Km
(CH2Cl2, 10ꢀ4 M): 1 Xꢀ1 cm2 molꢀ1. IR (KBr, cmꢀ1):
3333m, 3210m, 3142m m(N–Hdpa), 1594s, 1578s, 1551m,
Variata. The CF3 group was modelled as rotationally
disordered over two sets of sites set at equal occupancy
after trial refinement.
2.2.1.2. Agtfa:PPh3:bpy:H2O (1:1:1:1) (2). C30H25AgF3-
ꢀ
N3O3P, M = 657.4. Triclinic, space group P1,
˚
˚
˚
a = 15.270(2) A, b = 10.694(1) A, c = 8.9651(8) A, a =
3
˚
93.804(8)ꢁ, b = 92.33(1)ꢁ, c = 106.58(1)ꢁ, V = 1397 A .
1533s m(C C, C N), 1678vs, 1474s m(CF3COO). IR
Dcalc (Z = 2) = 1.562 g cmꢀ3. lMo = 8.3 cmꢀ1; specimen:
0.28 · 0.44 · 0.40 mm; ‘Tmin/max’ = 0.90. 2hmax = 50ꢁ;
N = 4910, No = 4153; R = 0.028, Rw = 0.032. (x,y,z,
. . .
. . .
•
•
(nujol, cmꢀ1): 563s, 520s, 509m, 463vs, 443w, 418w, 404m
m(P(o-tol)3), 326m, 303w, 278m, 268s, 254m, 247m, 227m.
1H NMR (CDCl3, 293 K): d, 2.51s (9H, P(C6H4-ortho-
CH3)3), 6.84dt, 7.24t, 7.40m (12H, P(C6H4-ortho-CH3)3),
6.75dt, 7.64dt, 7.68dd, 7.93dd (8H, CHdpa), 9.57br (1H,
NHdpa). 19F NMR (CDCl3, 223 K): d, ꢀ75.2s. 31P NMR
(CDCl3, 223 K): d, ꢀ17.5d (1J(31P–109/107Ag): 687.3 Hz).
The compound was modelled from the X-ray study as
20ƽMeCN.
Uiso)H refined.
:
:
-
2.2.1.3. Agtfa:PPh3:phen (1:1:1) Æ MeOH (3 Æ
MeOH). C32H23AgF3N2O2P Æ 0.75CH4O, M = 687.4. Tri-
ꢀ
˚
˚
clinic, space group P1, a = 8.772(3) A, b = 10.451(4) A,
˚
c = 17.042(6) A, a = 85.202(6)ꢁ, b = 87.561(6)ꢁ, c =
84.357(6)ꢁ, V = 1548 A . Dcalc (Z = 2) = 1.474 g cmꢀ3
.
3
˚
l
Mo = 7.6 cmꢀ1; specimen: 0.35 · 0.20 · 0.15 mm; ‘Tmin/
2.1.21. Synthesis of Agac:P(o-tol)3:dpa (1:1:1)(2) (21)
Compound 21 (0.565 g, yield: 88%) has been prepared
following a procedure similar to that reported for 1 by
using an acetonitrile solution of Agac (0.167 g, 1.0 mmol),
P(o-tol)3 (0.304 g, 1.0 mmol), and dpa (0.171 g,
1.0 mmol); m.p. 155–157 ꢁC. Anal. Calc. for C33H33Ag-
N3O2P: C, 61.69; H, 5.18; N, 6.54. Found: C, 61.42; H,
max’ = 0.66. 2hmax = 58ꢁ; Nt = 17551, N = 7548 (Rint
0.040), No = 3566; R = 0.057, Rw = 0.062.
=
Variata. The fluorine atoms were modelled as disordered
over two sets of sites, occupancies set at 0.5 after trial
refinement; difference map residues were modelled as sol-
vent methanol, site occupancy 0.75.
5.30; N, 6.75%. Km (CH3CN, 10ꢀ4 M): 7 Xꢀ1 cm2 molꢀ1
Km (CH2Cl2, 10ꢀ4 M): 1 Xꢀ1 cm2 molꢀ1
IR (KBr,
cmꢀ1): 3249m, 3165m m(N–Hdpa), 1605s, 1588s, 1532s
. . . . . .
.
.
2.2.1.4. Agac:PPh3:phen (1:1:1) Æ 2MeOH (4 Æ 2MeOH).
ꢀ
C34H34AgN2O4P, M = 673.5. Triclinic, space group P1,
˚
˚
˚
m(C C, C N), 1564vs, 1465s m(CH3COO). IR (nujol,
a = 8.7309(6) A, b = 10.6579(7) A, c = 16.892(1) A, a =
•
•
3
cmꢀ1): 562s, 523s, 516m, 460vs, 443m, 413m, 407sh
m(P(o-tol)3), 384w, 351w, 332m, 303w, 279m, 269m,
254w, 247m, 224m. 1H NMR (CDCl3, 293 K): d, 2.09s
(3H, CH3COO), 2.54s (9H, P(C6H4-ortho-CH3)3),
6.85dt, 7.16t, 7.42m (12H, P(C6H4-ortho-CH3)3), 6.76dt,
7.62m, 8.14dd (8H, CHdpa), 8.35br (1H, NHdpa). 31P
NMR (CDCl3, 223 K): d, 18.1d br (1J(31P–109/107Ag):
667.7 Hz). The compound was modelled from the X-ray
study as 21Æ2MeCN.
100.500(2)ꢁ, b = 93.087(2)ꢁ, c = 93.049(2)ꢁ, V = 1540 A .
˚
Dcalc (Z = 2) = 1.452 g cmꢀ3. lMo = 7.5 cmꢀ1; specimen:
0.25 · 0.20 · 0.15 mm; ‘Tmin/max’ = 0.81. 2hmax = 70ꢁ;
Nt = 27823, N = 13401 (Rint = 0.045), No = 11091; R =
0.053, Rw = 0.085.
Variata. The second solvent molecule was modelled as
disordered over two sets of sites, occupancies set at 0.5
after trial refinement, associated hydrogen atoms not
located.

1456
Effendy et al. / Inorganica Chimica Acta 360 (2007) 1451–1465
2.2.1.5. Agtfa:PPh3:dmp (1:1:1) (5). C34H27AgF3N2O2P,
M = 691.4. Orthorhombic, space group P212121 (D42, No.
(Z = 4) = 1.415 g cmꢀ3
0.21 · 0.04 · 0.15 mm; ‘Tmin/max’ = 0.84. 2hmax 58ꢁ;
Nt = 34390, N = 7767 (Rint = 0.036), No = 2763;
R = 0.049, Rw = 0.040.
.
l
Mo = 7.5 cmꢀ1
;
specimen:
˚
˚
˚
19), a = 9.5707(9) A, b = 15.1540(15) A, c = 21.003(2) A,
3
V = 3046 A . Dcalc (Z = 4) = 1.507 g cmꢀ3
.
lMo = 7.7
˚
cmꢀ1; specimen: 0.30 · 0.27 · 0.20 mm; ‘Tmin/max’ = 0.76.
2hmax = 58ꢁ;
Nt = 32535, N = 4378 (Rint = 0.025),
2.2.1.12. Agtfa:Pcy3:dmp (1:1:1) (12). C34H45AgF3-
ꢀ
No = 3514; R = 0.029, Rw = 0.035. xobs = 0.03(3).
N2O2P, M = 709.6. Triclinic, space group P1,
˚
˚
˚
a = 9.417(1) A, b = 10.158(1) A, c = 19.637(2) A, a =
3
˚
91.388(2)ꢁ, b = 95.643(2)ꢁ, c = 116.055(2)ꢁ, V = 1675 A .
2.2.1.6. Agac:PPh3:dmp (1:1:1) Æ MeOH (6 Æ MeOH).
C35H34AgN2O3P, M = 669.5. Monoclinic, space group
Dcalc (Z = 2) = 1.407 gcmꢀ3. lMo = 7.0 cmꢀ1; specimen:
5
˚
0.27 · 0.17 · 0.08 mm; ‘Tmin/max’ = 0.80. 2hmax = 58ꢁ;
P21/n (C2h, No. 14 (variant)), a = 9.1859(7) A, b = 21.015
3
˚
˚
˚
Nt = 19468;
N = 8160
(Rint = 0.022),
No = 6172;
(2) A, c = 16.274(1) A, b = 101.397(2)ꢁ, V = 3080 A . Dcalc
(Z = 4) = 1.444 g cmꢀ3. lMo = 7.4 cmꢀ1; specimen: 0.35 ·
0.20 · 0.13 mm; ‘Tmin/max’ = 0.88. 2hmax = 75ꢁ; Nt =
62693, N = 16144 (Rint = 0.027), No = 12964; R = 0.026,
R = 0.035, Rw = 0.044.
2.2.1.13. Agtfa:Pcy3:bq (1:1:1) (13). C38H45AgF3N2O2P,
ꢀ
˚
Rw = 0.033. (x,y,z,Uiso)H refined (MeOH excepted).
M = 757.6. Triclinic, space group P1, a = 9.829(1) A,
˚
˚
b = 10.670(1) A, c = 19.047(2) A, a = 79.496(2)ꢁ, b =
3
˚
2.2.1.7. Agtfa:PPh3:bq (1:1:1) (7). C38H27AgF3N2O2P,
M = 739.5. Monoclinic, space group P21/c (C52h, No. 14),
81.478(2)ꢁ, c = 64.812(2)ꢁ, V = 1772 A . Dcalc (Z = 2)
= 1.420 g cmꢀ3
.
l
Mo = 6.7 cmꢀ1
;
specimen:
0.30 ·
˚
˚
˚
a = 18.974(2) A,
b = 10.323(1) A,
c = 18.627(3) A,
0.12 · 0.03 mm; ‘Tmin/max’ = 0.79. 2hmax = 58ꢁ; Nt =
18946; N = 8573 (Rint = 0.025), No = 4766; R = 0.042,
Rw = 0.038.
b = 116.30(1)ꢁ, V = 3271 A . Dcalc (Z = 4) = 1.501 g cmꢀ3
.
’
3
˚
l
Mo = 7.2 cmꢀ1; specimen: 0.33 · 0.19 · 0.39 mm; ‘Tmin/max
= 0.86. 2hmax = 50ꢁ; N = 5751, No = 3173; R = 0.046,
Rw = 0.044. (x,y,z,Uiso H refined.
)
2.2.1.14. Agtfa:Pcy3:dpa (1:1:1) (14). C30H42AgF3N3O2P,
M = 672.5.
Monoclinic,
space
group
P21/n,
˚
˚
˚
2.2.1.8. Agtfa:PPh3:dpa (1:1:1) (8). C30H24AgF3N3O2P,
M = 654.4. Monoclinic, space group P21/c, a =
a = 9.4940(1) A, b = 20.294(1) A, c = 15.759(2) A, b =
90.932(1)ꢁ, V = 3036 A . Dcalc (Z = 4) = 1.471 g cmꢀ3
.
3
˚
Mo = 7.7 cmꢀ1
;
specimen:
0.65 · 0.60 · 0.25 mm;
˚
˚
˚
9.1934(7) A, b = 19.691(2) A, c = 15.514(1) A, b =
l
101.517(1)ꢁ, V = 2752 A . Dcalc (Z = 4) = 1.579 g cmꢀ3
.
3
˚
‘Tmin/max’ = 0.84. 2hmax = 58ꢁ; Nt = 34475; N = 7581
(Rint = 0.016), No = 7125; R = 0.043, Rw = 0.10.
Variata. Oxygen and fluorine components of the anion
were modelled as disordered over pairs of sites, occupan-
cies refining to 0.86(1) and complement.
l
Mo = 8.4 cmꢀ1; specimen: 0.70 · 0.50 · 0.40 mm; ‘Tmin/
max’ = 0.83. 2hmax = 58ꢁ; Nt = 31144, N = 6830 (Rint
=
)
0.016), No = 6183; R = 0.027, Rw = 0.041. (x,y,z,Uiso H
refined.
2.2.1.9. Agac:PPh3:dpa (1:1:1)(2) (9). C60H54Ag2N6O4P2,
M = 1200.8. Monoclinic, space group P21/n, a =
2.2.1.15. Agtfa:Ascy3:bpy (1:1:1) (15). C30H41AgAs-
N2O2F3, M = 701.5. Monoclinic, space group P21/n,
˚
˚
˚
10.7911(8) A, b = 8.9787(6) A, c = 28.135(2) A, b =
˚
˚
˚
a = 9.473(2) A, b = 21.178(6) A, c = 15.718(2) A, b =
3
˚
90.19(1)ꢁ, V = 3153 A . Dcalc (Z = 4) = 1.478 g cmꢀ3. lMo
3
96.724(1)ꢁ, V = 2707 A . Dcalc (Z = 2 dimers) =
˚
1.473 g cmꢀ3
. l ; specimen: 0.28 · 0.20 ·
Mo = 8.4 cmꢀ1
= 17.3 cmꢀ1; specimen: 0.52 · 0.36 · 0.38 mm; ‘Tmin/max
’
0.14 mm; ‘Tmin/max’ = 0.88. 2hmax = 58ꢁ; Nt = 29541,
N = 6861
= 0.90. 2hmax = 50ꢁ; N = 5256, No = 3664; R = 0.036,
Rw = 0.037.
(Rint = 0.019),
No = 6377;
R = 0.029,
Rw = 0.065.
2.2.1.16. Agtfa:Ascy3:dpa (1:1:1) (16). C30H42AgAs-
F3N3O2, M = 716.5. Monoclinic, space group P21/n, a =
2.2.1.10. Agtfa:PPh3:dpk Æ H2O (1:1:1) Æ MeCN (10 Æ
MeCN). C31H25AgF3N2O4P Æ C2H3N, M = 726.5. Tri-
˚
˚
˚
9.506(2) A, b = 20.519(4) A, c = 15.833(3) A, b = 90.589
˚
˚
ꢀ
3
(3)ꢁ, V = 3088 A . Dcalc (Z = 4) = 1.541 g cmꢀ3. lMo
=
clinic, space group P1, a = 13.910(1) A, b = 12.042(3) A,
˚
˚
17.7 cmꢀ1
= 0.83. 2hmax = 58ꢁ; Nt = 35878; N = 7801 (Rint = 0.032),
No = 6241; R = 0.028, Rw = 0.033. (x,y,z,Uiso H refined.
; specimen: 0.22 · 0.15 · 0.11 mm; ‘Tmin/max’
c = 10.573(2) A, a = 105.65(2)ꢁ, b = 90.04(1)ꢁ, c = 111.04
3
(2)ꢁ, V = 1582 A . Dcalc (Z = 2) = 1.525 g cmꢀ3. lMo
=
˚
7.5 cmꢀ1
= 0.43. 2hmax = 50ꢁ; N = 5618, No = 4728; R = 0.035,
Rw = 0.041. (x,y,z,Uiso H refined (MeCN excepted).
; specimen: 0.82 · 0.42 · 0.28 mm; ‘Tmin/max’
)
)
2.2.1.17. Agac:P(o-tol)3:bpy (1:1:1) Æ H2O (17 Æ H2O).
ꢀ
C33H34AgN2O3P, M = 645.5. Triclinic, space group P1,
2.2.1.11. Agtfa:Pcy3:bpy (1:1:1) (11). C30H41AgF3N2O2P,
M = 657.5. Monoclinic, space group P21/n (C52h, No. 14
˚
˚
˚
a = 9.2929(9) A, b = 10.537(1) A, c = 15.816(2) A, a =
3
˚
87.955(1)ꢁ, b = 88.471(1)ꢁ, c = 76.600(1)ꢁ, V = 1505 A .
Dcalc (Z = 2) = 1.424 g cmꢀ3. lMo = 7.6 cmꢀ1; specimen:
˚
˚
3
(variant)),
15.586(3) A,
a = 9.438(2) A,
b = 20.984(3) A,
c =
Dcalc
˚
˚
0.38 · 0.21 · 0.22 mm; ‘Tmin/max’ = 0.93. 2hmax = 58ꢁ;
b = 90.029(4)ꢁ,
V = 3087 A .

Effendy et al. / Inorganica Chimica Acta 360 (2007) 1451–1465
1457
S
Nt = 14525; N = 7220 (Rint = 0.020), No = 6276;
R = 0.030, Rw = 0.040.
AgX þ ER3 þ L ! AgX : ER3 : L ð1 : 1 : 1Þ
ð1Þ
(X = tfa or ac; E = P or As; R = Ph, cy or o-tolyl; L = bpy,
phen, dmp, bq, dpa or dpk; S = acetonitrile or ethanol).
All the compounds, air-stable, colourless materials, are
insoluble in diethyl ether and alcohols but soluble in chlo-
rinated solvents, acetone, acetonitrile and DMSO. The
conductivity measurements are in accordance with the
ionic formulation found in the solid state for the deriva-
tives 2 and 10. In addition the compounds 1, 3–7, 11–13,
15 and 17–19, containing weakly coordinated tfa or ac spe-
cies, undergo complete ionic dissociation, not only in ace-
tonitrile but also in non-ionizing solvents such as
dichloromethane, Km in the former solvent being in the
range 120–160 and in the latter 40–50 Xꢀ1 cm2 molꢀ1
[10]. Finally, derivatives 8, 9, 14, 16, 20 and 21, containing
the dpa ligand, which forms hydrogen-bonding networks in
the solid state involving interaction of the N–H compo-
nents with the carboxylate groups (see crystallographic
studies below), are 1:1 electrolytes in acetonitrile but essen-
tially non-electrolytes in dichloromethane [10], presumably
in consequence of ion-pair formation.
2.2.1.18. Agtfa:P(o-tol)3:phen (1:1:1) Æ H2O (18 Æ H2O).
ꢀ
C35H31AgF3N2O3P, M = 723.5. Triclinic, space group P1,
˚
˚
˚
a = 10.256(2) A, b = 10.686(2) A, c = 16.360(3) A, a =
3
˚
98.152(3)ꢁ, b = 91.514(3)ꢁ, c = 114.408(3)ꢁ, V = 1609 A .
Dcalc (Z = 2) = 1.493 g cmꢀ3. lMo = 7.3 cmꢀ1; specimen:
0.20 · 0.15 · 0.10 mm; ‘Tmin/max’ = 0.66. 2hmax = 50ꢁ;
Nt = 15895;
N = 5665
(Rint = 0.046),
No = 5045;
R = 0.054, Rw = 0.064.
Variata. The heavy atom components (Ag, P) were
modelled as disordered in concert over sets of sites, occu-
pancies refining to 0.946(3) for the major component and
2· (complement/2) for the minor.
2.2.1.19. Agtfa:P(o-tol)3:bq (1:1:1) (19). C41H33AgF3-
N2O2P, M = 781.6. Monoclinic, space group P21/c,
˚
˚
˚
a = 10.5386(9) A,
b = 10.981(1) A,
c = 30.137(3) A,
b = 96.168(2)ꢁ, V = 3467 A . Dcalc (Z = 4) = 1.497 g cmꢀ3
.
3
˚
l
Mo = 6.8 cmꢀ1
;
specimen:
0.18 · 0.10 · 0.10 mm;
‘Tmin/max’ = 83. 2hmax = 58ꢁ; Nt = 33511; N = 8790
(Rint = 0.027), No = 7550; R = 0.032, Rw = 0.042.
Variata. Fluorine atoms were modelled over two sets of
sites, occupancies set at 0.5 after trial refinement.
3.2. Spectroscopy
The infrared spectra (Section 2) are consistent with the
formulations proposed, showing all of the bands required
by the presence of the organic N-donor and bidentate
phosphine or arsine ligands [11]. In the far-IR spectra of
all phosphino derivatives we assigned, on the basis of pre-
vious reports, the broad absorptions near 500 cmꢀ1 and
those at 480–400 cmꢀ1 to Whiffen’s y and t vibrations [12].
In the IR spectra of derivatives 5–8, the difference D
between masym(CO2) and msym(CO2) falls in the range 65–
75 cmꢀ1, consistent with the presence of symmetrically
bidentate carboxylate groups [13]. Derivatives 2 and 10,
which are ionic in the solid state (see below) show Dm
(CO2) values of 196 and 243 cmꢀ1, respectively, consistent
with the CF3COO group being involved in some hydrogen-
bonding interaction (see below). Derivatives 1, 3, 11–14,
2.2.1.20. Agtfa:P(o-tol)3:dpa (1:1:1) Æ ½MeCN (20 Æ ½
MeCN). C34H31.5AgF3N3.5O2P, M = 717.0. Triclinic,
˚
˚
ꢀ
space group P1, a = 11.519(2) A, b = 15.814(2) A,
˚
c = 17.459(2) A, a = 93.595(2)ꢁ, b = 92.993(2)ꢁ, c =
3
˚
94.724(2)ꢁ,
V = 3158 A .
Dcalc
specimen:
(Z = 4) = 1.508
0.40 · 0.35 ·
g cmꢀ3
.
l
Mo = 7.4 cmꢀ1
;
0.25 mm; ‘Tmin/max’ = 0.76. 2hmax = 58ꢁ; Nt = 35986,
N = 15151
Rw = 0.042.
(Rint = 0.023),
No = 12800;
R = 0.030,
2.2.1.21. Agac:P(o-tol)3:dpa (1:1:1)(2) Æ 2MeCN (21 Æ2
MeCN). C70H72Ag2N8O4P2, M = 1367.1. Triclinic, space
˚
˚
ꢀ
group
P1,
a = 11.196(1) A,
b = 11.525(1) A,
˚
18–20 show Dm (CO2) values in the range 204–252 cmꢀ1
,
c = 12.957(1) A, a = 98.484(2)ꢁ, b = 99.340(1)ꢁ, c =
3
˚
100.393(2)ꢁ, V = 1596 A . Dcalc (Z = 1 dimer) =
typical of unidentate CF3COO [13]. Similarly, acetate
derivatives 4, 9, 17 and 21 present Dm (CO2) values between
97 and 160 cmꢀ1, in accordance with unidentate or bridg-
ing unidentate CH3COO [13].
1.423 g cmꢀ3
. l ; specimen: 0.40 · 0.25 ·
Mo = 7.2 cmꢀ1
0.20 mm; ‘Tmin/max’ = 0.91. 2hmax = 58ꢁ; Nt = 15489,
N = 7696
(Rint = 0.014),
No = 7052;
R = 0.025,
Rw = 0.038.
The IR spectra of the dpa-containing derivatives 8, 9,
14, 16, 20 and 21 exhibit broad bands over 3100 cmꢀ1 aris-
ing from N–HO(carboxylate) hydrogen-bonding, observed
also in their crystal structures. Finally also that of deriva-
tive 10, containing the hydrolyzed dpk Æ H2O ligand, shows
a broad absorption at 3150 cmꢀ1, clearly due to O–
H. . .OC(O)CF3 H-bonding.
3. Results and discussion
3.1. Syntheses
The adducts 1–21 (Chart 1) of general formula
AgX:ER3:L (1:1:1), have been synthesized by the reaction
of one equivalent of N,N0-bidentate aromatic ligands, L,
derivative of 2,20-bipyridyl, with one equivalent of silver(I)
carboxylate and one equivalent of a unidentate ER3 ligand
according to
1
In the H NMR spectra of derivatives 1–21, all of the
signals due to the phosphine and N-donor ligands are
found to be detected slightly shifted with respect to those
of the free donors, in agreement with the existence of com-
plexes also in solutions in chlorinated solvents.

1458
Effendy et al. / Inorganica Chimica Acta 360 (2007) 1451–1465
O
O
_
F3C
H3C
F3C
F3C
C
C
O
C
C
H
H
O
O
O
O
O
+
O
N
Ag
N
N
Ag PPh3
N
Ag
Ag
PPh3
PPh3
PPh3
N
N
N
N
3
2
1
4
F3C
C
CF3
CH3
F3C
C
O
C
O
C
O
O
O
O
CH3
O
O
CH3
N
N
Ag
N
N
Ag
N
Ag
Ag
H
PPh3
PPh3
PPh3
PPh3
N
N
N
N
CH3
CH3
5
8
6
7
F3C
F3C
H3C
N
O
Ph3P
H
C
N
C
+
N
O
O
O
O
O
HO
O
H
Me
Ag
H
Ag
C
PPh3
O
N
N
Ag
Ag
N
Ag
N
N
CF3COO-
Pcy3
PPh3
Pcy3
N
O
N
N
N
CH3
Me
12
9
10
11
CF3
C
CF3
CF3
CF3
C
C
O
O
C
O
O
O
O
O
O
N
N
Ag
Ag
H
N
Pcy3
N
Ag
N
Ascy3
N
Ag
N
H
N
Ascy3
Pcy3
N
N
13
14
15
16
F3C
H3C
C
F3C
C
C
O
O
O
O
O
O
N
N
Ag
Ag
N
Ag
P(o-tol)3
P(o-tol)3
P(o-tol)3
N
N
N
17
18
19
O
H3C
N
O
C
CF3
(o-tol)3P
N
N
O
O
H
H
Ag
O
Ag
H
N
N
O
N
Ag
N
N
P(o-tol)3
N
P(lot-o)3
CH3
20
21
Chart 1.

Effendy et al. / Inorganica Chimica Acta 360 (2007) 1451–1465
1459
In the 19F NMR spectra of the tfa-containing deriva-
tives 1–3, 5, 7–8, 10–16 and 18–20, a unique resonance at
ca. ꢀ75 ppm is always observed, independent of the mode
of coordination of the CF3COO – unidentate, bidentate or
ionic – found in the solid state, indicating that the tfa is
essentially ionic in nature in chlorinated solvent solution,
in accordance also with conductance values (see above).
While at room temperature, the 31P NMR spectra of
complexes 1–14 and 17–21 consist of single broad reso-
nances, presumably due to exchange equilibria which are
fast in relation to the NMR time scale, the exchange is
quenched at low temperature (223 K), and one unresolved
doublet or resolved pairs of doublets, arising from coupling
between the phosphorus and silver atom, are observed in
the accessible temperature range.
We have assigned AgPN2 coordination environments in
solution for all derivatives 1–14 and 17–21 on the basis of
their J(Ag–P) (in the range 600–750 Hz) derived from the
major 31P resonance. In fact the spin–spin constant (J)
between phosphorus and silver depends on the number of
coordinated phosphorus atoms in the silver complex, as
previously shown by Muetterties and Alegranti [14] and
Goel and Pilon [15].
terion or nearby solvent or ‘impurity’ (H2O). Solvent or
impurity approaches, given the nature of the species
employed, should be unidentate; in fact, no close solvent
approaches are observed at all. By contrast, in the complex
where interaction with a water molecule is observed,
[(Ph3P)Ag(bpy)(OH2)](tfa), 2, the interaction is close and
strong, displacing the potentially ligating tfa anion, which
in other situations may be quite strongly bound, an inter-
esting observation in that, given that the crystallizations
were effected in ambience, with no special precautions
taken to exclude water, its incorporation in the complex
is found in only the one case here, and with the carboxylate
system, more basic than nitrate or perchlorate where no
such interactions are found [7,8]. Interactions with carbox-
ylate anions are widespread and diverse in their nature and
strength: all species employed are capable of bidentate
approaches and the species observed may range in all cases
from O,O0-bidentate to O,O0-semibidentate, one oxygen
atom being more strongly bound than the other, to O-unid-
entate, to unbound, with a number of interactions between
the latter pair in strength. In general, the EAgN2 in-plane
angle sum, 360ꢁ for a completely planar array, diminishes,
as expected, broadly in parallel with the strength of the
interaction with the approaching species, asymmetry in
the E–Ag–N,N0 angles broadly correlating in the manner
expected with Ag–N; for a given anion, the strength of
interaction tends to be greater in E = As complexes, cf.
counterpart E = P, as expected and in keeping with the
diminished base strength of AsR3, with concomitant
change in Ag–N. Although the more basic carboxylate sys-
tems interact more strongly generally than the anions of the
nitrate and perchlorate counterparts presented in Refs.
[7,8], the generally planar, exposed environments of the sil-
ver atoms suggest possible application in catalysis for all
three types of systems.
Moreover, in the low temperature 31P NMR spectra of
derivatives 3–8, 12 and 13, one or two minor doublets or
pair of doublets have been detected, their J(Ag–P) being in
the range 380–540 Hz, in accordance with the presence in
solution of additional AgP2-containing species [14,15], pre-
sumably formed from dissociation equilibria such as the
following:
2[Ag(PR3)(L)](OOCR) ¡ [Ag(PR3)2(OOCR)]
+ [Ag(L)2](OOCR)
(R = CF3 or CH3)
ð2Þ
The ligands L offer a range of ‘bites’, those of bpy, phen,
dmp, and bq being similar, the latter pair offering different,
more hindered profiles, while dpa, with a six- cf. a five-
membered chelate ring, has a greater ’bite’, also true of
dpk – but here with a further O donor (two in the case
of the hydrate) introduced between the peripheral pair,
the ligand is potentially tridentate, although it could func-
tion as a simple chelate or a pair of chelates. Interestingly,
in two of the dpa complexes, one with E = P, the other
E = As, both with the acetate (rather than the less basic tri-
fluoroacetate) oxyanion, the strength of the anion/base
interaction is such as to overcome the chelate effect of the
dpa ligand so that it becomes unidentate. In both of these
cases, a binuclear species is found, creating, in effect, via
the bridging oxygen atoms, an alternative (l-O)2-chelate.
The ligands generally are extended planar arrays, although
in those cases (bpy, bq, and dpa) where there is no central
aromatic ring fusing the two donor rings, there may be an
appreciable dihedral angle between the latter. The ligand
planes, in general, are dominant determinants of crystal
packing in many cases. Core geometries for all of the
species are summarized in Tables 1 and 2, with individual
3.3. Single crystal X-ray studies
All adducts 1–21 have also been characterized by single
crystal X-ray diffraction studies (Fig. 1; Tables 1 and 2).
Except in two cases, the complexes are mononuclear, based
on a quasi-planar three-coordinate AgN2 coordination
environment in an [(R3E)AgL]+ complex, with complemen-
tary counterion and, on occasion, accompanying solvent.
The usual symmetry of the ER3 arrays is 3 (or very rarely
m) (or less), that of the ligand is 2 mm (or less), these being
normally incompatible, so that it is unsurprising that the
asymmetric unit of the structures is never less than one for-
mula unit (thus, devoid of symmetry); in only one case, the
complex Agtfa:P(o-tol)3:dpa (1:1:1), does it rise to two.
Although the symmetry of the coordination sphere itself
can be as high as m, there is usually a significant asymme-
try in the pair of E–Ag–N angles, consequent on the pres-
ence of an unsymmetrical disposition relative to the ER3
group, or other less internal effects. Any potential symme-
try of the array may be degraded further by interaction of
the (thus far) cationic [(R3E)AgL]+ species with the coun-

1460
Effendy et al. / Inorganica Chimica Acta 360 (2007) 1451–1465
Fig. 1. Projections of the complex aggregates of the following (R3P)Ag(N,N0-aromatic base)/(ac/tfa) systems: (a) [(Ph3P)Ag(N,N0-bpy)(O-tfa)] in
+
0
0
1 Æ MeOH; (b) [(Ph3P)Ag(N,N0-bpy)(OH2)] in 2; (c) [(Ph3P)Ag(N,N -phen)(O-tfa)] in 3 Æ MeOH; (d) [(Ph3P)Ag(N,N -phen)(O-ac)] in 4 Æ 2MeOH; (e)
[(Ph3P)Ag(N,N0-dmp)(O-tfa)], 5; (f) [(Ph3P)Ag(N,N0-dmp)(O,O0-ac)] in 6 Æ MeOH; (g) [(Ph3P)Ag(N,N0-bq)(O,O0-tfa)], 7; (h) [(Ph3P)Ag(N,N0-dpa)(O-tfa)],
8; (i) [{(Ph3P)Ag(N-dpa)Ag}2(l-O-ac)2], 9; (j) [(Ph3P)Ag{N,N0,O-(dpk Æ H2O)}](tfa) in 10 Æ MeCN; (k) [(cy3P)Ag(N,N0-bpy)(O-tfa)], 11; (l) [(cy3P)Ag(N,N0-
dmp)(O-tfa)], 12; (m) [(cy3P)Ag(N,N0-bq)(O-tfa)], 13; (n) [(cy3P)Ag(N,N0-dpa)(O,O0-tfa)], 14; (o) [(cy3As)Ag(N,N0-bpy)(O-tfa)], 15; (p) [(cy3As)Ag(N,N0-
dpa)(O-tfa)], 16; (q) [{(o-tol)3P}Ag(N,N0-bpy)(O-ac)] in 17 Æ H2O; (r) [{(o-tol)3P}Ag(N,N0-phen)(O,O0-tfa)] in 18 Æ H2O; (s) [{(o-tol)3P}Ag(N,N0-bq)-
(O-tfa)], 19; (t) [{(o-tol)3P}Ag(N,N0-dpa)(O-tfa)], (mol. 1) in 20 Æ ½MeCN; (u) [{((o-tol)3P)Ag(N,N0-dpa)}2(l-O-ac)2] in 21 Æ 2MeCN.
:
species depicted in Fig. 1. We comment individually on the
various structures as follows:
methanol solvate molecule, which, with hydrogen atoms
smoothly refining, interacts closely with the uncoordinated
oxygen of the anion ((MeOH)O,H. . .O(2) 2.686(3),
˚
3.3.1. Agtfa:PPh3:bpy:MeOH (1 Æ MeOH)
1.73(4) A). The query concerning mode and nature of
An imponderable thread throughout the present array is
the determinant(s) of mode and strength of interaction of
the anion with the 1:1:1 complex substrate, seemingly
devoid of systematic behaviour or trend. Here in the pres-
ent complex, the base tfa affords a unidentate coordination.
A salient factor in the present array may be the well-defined
anion interaction is reinforced in the structure of the
adventitious 2:
3.3.2. Agtfa:PPh3:bpy:H2O (1:1:1:1) (2)
This is unequivocally defined as displaying a solvent,
rather than an anionic, interaction with the substrate.

Effendy et al. / Inorganica Chimica Acta 360 (2007) 1451–1465
1461
Fig. 1 (continued)
[(Ph3P)Ag(N,N0-bpy)(OH2)]+(‘tfa’)ꢀ, the water molecule
bridging a pair of symmetry related anions in the lattice
(O,H(2)ꢁ ꢁ ꢁO(1), 2.741(4), 1.93(6); O,H(1)ꢁ ꢁ ꢁO(2) (2 ꢀ x,
˚
Ag–O(H2), 2.340(3) A, is one of the shortest/strongest
approaches of any oxo-moiety to the substrate in the pres-
ent array, reflected in the considerable ‘distortions’ in the
silver environment. The compound is thus ionic,
˚
1 ꢀ y, ꢀz) 2.751(5), 2.03(5) A).

Table 1
Silver atom environments, AgX:ER3:L(:S) (1:1:1(:1))
a
0
(S/X)–Ag–N,N0 (ꢁ)
E–Ag–N,N0 (ꢁ)
N–Ag–N0 (ꢁ)
R (ꢁ)
˚
˚
˚
ER3:L(:S/X)
Ag–X(/S) (A)
Ag–E (A)
Ag–N,N (A)
(S/X)–Ag–E (ꢁ)
(1) PPh3:bpy:O,(O-tfa)
(2) PPh3:bpy:OH2(tfa)
(3) PPh3:phen:O,(O-tfa)
(4) PPh3:phen:O,(O-ac)
(5) PPh3:dmp:O2-tfa
2.503(2)
2.340(3)
2.370(6)(,3.416(7))
2.292(2)(,3.316(3))
2.583(3),
2.824(4)
2.3993(9),
2.875(1)
2.671(6),
2.3547(5)
2.3535(7)
2.351(2)
2.3541(7)
2.383(1)
2.355(2), 2.315(2)
2.330(2), 2.377(3)
2.375(5), 2.319(5)
2.426(3), 2.364(3)
2.363(3), 2.372(3)
114.11(4)
130.7(1)
125.4(1)
139.55(7)
126.37(7)
105.6(1)
122.30(2)
97.52(2)
106.8(2)
104.9(2)
116.70(3)
129.28(4)
108.06(3)
121.80(6)
122.5(1)
113.38(8)
109.96(8)
131.4(1)/
102.9(2)
121.1(1)
131.80(5)
131.68(5)
121.10(4)
134.2(1)
115.0(1)
113.10(4)
130.22(4)
135.53(4)
99.12(5)
126.92(3)
117.55(3)
89.13(6), 86.02(6)
90.6(1), 95.5(1)
88.6(2), 88.2(2)
93.13(7), 88.22(9)
100.97(9), 80.1(1)
92.4(1), 121.0(1)
101.95(3), 89.94(3)
93.11(3), 132.31(3)
124.0(2), 92.1(2)
98.1(2), 122.6(2)
96.07(5), 87.66(4)
108.97(5)
132.50(4), 145.92(5)
129.50(6), 121.60(6)
129.4(1), 135.7(1)
116.52(6), 126.12(7)
128.84(8), 129.32(7)
71.36(6)
70.99(8)
71.7(2)
70.5(1)
71.2(1)
349.8
322.1
336.8
313.1
329.4
n
n
n
n
(6) PPh3:dmp:O2-ac
(7) PPh3:bq:O2-tfa
2.3792(3)
2.391(2)
2.3620(9), 2.4104(9)
2.354(5), 2.370(7)
128.96(2), 128.11(3)
126.6(2), 127.8(1)
70.23(3)
69.8(2)
327.3
324.2
344.0
2.673(6)
2.461(1)(,3.403(1))
2.278(1),
(8) PPh3:dpa:O,(Otfa)
(9) PPh3:dpa:l-O-ac
2.3589(5)
2.3609(5)
2.293(1), 2.335(1)
2.341(1) (unident.)
132.08(4), 130.51(3)
120.04(4)
81.43(5)
2.546(1)
92.77(5)
(10) PPh3:dpk,OH2(tfa)
(11) Pcy3:bpy:O,(O-tfa)
(12) Pcy3:dmp:O,(O-tfa)
(13) Pcy3:bq:O,(O-tfa)
(14) Pcy3:dpa:O,(O-tfa)
(disordered cpt.)
(15) Ascy3:bpy:O,(O-tfa)
(16) Ascy3:dpa:O,(O-tfa)
(17) P(o-tol)3:bpy:O2-ac
2.596(3)(O(dpk))
2.439(5)(,3.101(2))
2.424(3)(,3.469(5))
2.472(4)(,3.240(4))
2.508(4)(,3.153(7))
2.64(1)(,2.97(1))
2.413(4)(,3.054(5))
2.488(2)(,3.074(3))
2.322(2),
2.930(2)
2.464(4),
2.754(4)
2.418(2)(,3.048(2))
2.457(2)
2.326(1)
2.368(2)
2.3710(7)
2.384(1)
2.3758(5)
2.276(3), 2.337(3)
2.354(5), 2.383(5)
2.352(3), 2.366(2)
2.378(3), 2.353(3)
2.357(1), 2.352(2)
67.3(1), 67.44(9)
99.8(2), 91.2(2)
100.7(1), 88.7(1)
91.6(1), 100.5(1)
92.4(1), 81.4(1)
90.2(2), 121.7(2)
103.2(1), 94.0(1)
94.02(7), 85.35(7)
99.01(7), 90.12(7)
77.30(6), 119.84(6)
87.6(2), 87.3(2)
80.4(1), 129.6(2)
105.36(6), 88.00(6)
87.52(7), 84.49(6)
89.08(7), 85.03(6)
95.77(7), 134.08(6)
105.07(4)
148.04(6), 129.41(8)
127.1(1), 131.9(1)
133.52(7), 136.55(6)
136.21(7), 137.1(1)
125.85(4), 129.83(4)
82.5(1)
69.5(2)
71.5(1)
69.7(1)
78.79(5)
360.0
328.5
341.6
343.0
334.5
2.4587(9)
2.4680(5)
2.3828(6)
2.351(4), 2.373(4)
2.357(2), 2.352(2)
2.355(2), 2.450(2)
125.2(1), 131.0(1)
123.38(5), 127.07(5)
126.40(6), 119.02(5)
69.2(1)
79.41(7)
68.58(6)
325.4
329.9
314.0
n
n
(18) P(o-tol)3:phen:O2-tfa
(major component)
(19) P(o-tol)3:bq:O,(O-tfa)
(20) P(o-tol)3:dpa:O-tfa (mol. 1)
O2-tfa (mol. 2)
2.374(1)
2.344(4), 2.431(5)
136.7(1), 114.4(1)
70.6(2)
321.7
2.3937(5)
2.3855(6)
2.3952(6)
2.349(2), 2.387(2)
2.299(2), 2.353(2)
2.319(2), 2.374(2)
133.98(5), 133.83(4)
134.30(5), 121.82(5)
129.34(6), 118.66(6)
69.64(6)
80.55(6)
80.66(7)
80.66(7)
337.5
336.7
328.6
328.6
n
n
2.493(2),
2.808(2)
2.366(1),
2.539(1)
(21) P(o-tol)3:dpa:l-O-ac
2.4304(4)
2.384(1) (unident.)
125.82(3)
88.93(4)
a
˚
Contacts in parentheses lie between 3 and 3.5 A.

Effendy et al. / Inorganica Chimica Acta 360 (2007) 1451–1465
1463
Table 2
Silver atom environments, AgX:ER3:L(:S) (1:1:1(:1))
bq=bq
py=py
ðꢂÞ
ER3:L(:S/X)
h
dAg
dAgx
Ag–X(,X0)–Y
(ꢁ)
Ag–E–C(n1)–C(n2(6))
E–Ag–O–X O–X–O
(ꢁ) (ꢁ)
˚
˚
(A)
(A)
(ꢁ)
(1) PPh3:bpy:O(,O-tfa)
(2) PPh3:bpy:OH2(tfa)
(3) PPh3:phen:O(,O-tfa)
(4) PPh3:phen:O(,O-ac)
(5) PPh3:dmp:O2-tfa
13.5(1)
18.5(1)
0.010(4), 0.674(4) 0.006(8) 124.1(1)
0.436(5), 0.532(5)
34.2(2), 57.6(2), 43.2(2)
31.2(2), 42.8(2), 56.9(3)
ꢀ25.7(6), ꢀ42.2(6), ꢀ58.7(5)
ꢀ30.0(3), ꢀ47.4(3), ꢀ57.8(3)
9.6(3), 63.5(3), 32.6(3)
81.2(2)
131.9(2)
131.2(4)
132.0(9)
125.0(3)
128.5(4)
0.151(6)
0.176(3)
0.331(3)
0.39(2)
0.091(8) 122.5(2)
0.118(8)
120.5(5)
ꢀ82.1(6)
ꢀ35.2(3)
79.3(3)
o
98.1(3)
86.3(4)
o
(6) PPh3:dmp:O2-ac
(7) PPh3:bq:O2-tfa
0.343(1)
0.047(3) 104.68(2)
82.16(7)
20.0(1), 45.7(1), 16.9(1)
24.5(7), 25.3(6), 65.4(7)
68.58(8)
ꢀ125.71(6)
93.2(6)
124.2(1)
128.2(9)
o
o
2.4(2)
0.05(1), 0.01(1)
0.14(2)
91.9(6)
92.1(5)
ꢀ97.3(6)
(8) PPh3:dpa:O(,Otfa)
(9) PPh3:dpa:l-O-ac
8.06(6) 0.142(3), 0.423(3) 0.238(3) 116.8(1)
9.42(5) 0.685(3)
14.8(2), 33.4(2), 49.0(2)
ꢀ12.2(2), ꢀ26.7(2), ꢀ46.5(2)
16.5(1)
130.3(2)
124.0(2)
0.027(3) 108.6(1),
ꢀ96.8(1)
0.927(4) 144.2(1)
97.1(2)
(10) PPh3:dpk,OH2(tfa)
(11) Pcy3:bpy:O(,O-tfa)
(12) Pcy3:dmp:O2(O-tfa)
(13) Pcy3:bq:O2(O-tfa)
(14) Pcy3:dpa:O(,O-tfa)
(disordered cpt.)
(15) Ascy3:bpy:O(,O0 ꢀ tfa)
(16) Ascy3:dpa:O(,O-tfa)
(17) P(o-tol)3:bpy:O2-ac
68.4(1)
2.8(3)
0.131(6), 0.212(6)
22.5(3), 44.9(4), 43.8(3)
19.5(5), 51.6(4), ꢀ52.0(4)
58.1(2), ꢀ58.9(2), 47.7(3)
55.9(3), ꢀ58.3(3), ꢀ28.5(7)
20.4(1), 51.5(1), ꢀ49.9(1)
ꢀ168.6(6)
ꢀ78.7(6)
ꢀ81.7(3)
ꢀ89.3(3)
ꢀ43.5(4)
126.1(5)
ꢀ78.5(4)
ꢀ36.6(2)
98.7(2)
129.6(4)
124.7(10)
132.5(5)
130.6(6)
130.1(4)
124.4(8)
129.6(8)
127.9(3)
124.9(3)
0.10(1), 0.01(1)
0.033(2)
0.22(2)
0.485(8) 120.9(4)
0.035(6), 0.118(6) 0.42(1) 112.1(4)
109.7(5)
2.9(1)
4.80(5) 0.088(3), 0.213(3) 0.376(1) 109.1(3)
0.350(1) 102.3(7)
3.2(2)
5.40(6) 0.005(4), 0.069(4) 0.245(6) 107.6(2)
14.70(9) 0.243(4), 0.538(4) 0.116(6) 107.9(2)
79.2(1)
0.058(9), 0.061(9) 0.18(1)
108.5(4)
18.7(5), ꢀ49.5(4), 49.5(4)
18.6(2), 50.7(2), ꢀ48.8(2)
43.4(2), 46.6(2), 51.5(2)
(18) P(o-tol)3:phen:O2-tfa
5.4(2)
0.17(1), 0.04(1)
0.37(1)
95.4(4)
82.8(3)
41.9(8), 49.8(4), 51.6(5)
92.3(4)
ꢀ132.4(3)
ꢀ96.7(1)
44.5(3)
ꢀ52.7(2)
143.3(1)
ꢀ98.8(1)
130.5(5)
(19) P(o-tol)3:bq:O(,O-tfa)
(20) P(o-tol)3:dpa:O-tfa (mol. 1)
O2-tfa (mol. 2)
11.09(6) 0.100(3), 0.522(3) 0.228(4) 106.7(1)
9.69(7) 0.406(4), 0.474(3) 0.491(4) 143.4(2)
4.8(1)
48.6(2), 61.5(2), 16.4(2)
50.3(2), 44.3(2), 49.7(2)
ꢀ46.2(2), ꢀ43.2(2), ꢀ56.1(2)
129.7(2)
129.0(2)
129.0(2)
o
0.040(5), 0.262(4) 0.242(4)
98.2(1),
83.8(1)
o
(21) P(o-tol)3:dpa:l-O-ac
30.60(6) 0.398(3), 1.420(3) 0.172(3) 108.10(8),
134.24(9)
44.7(2), 47.2(2), 54.8(1)
124.2(2)
:
3.3.3. Agtfa:PPh3:phen (1:1:1) Æ MeOH
3.3.6. Agac:PPh3:dmp (1:1:1) Æ MeOH (6 Æ MeOH)
:
(3 Æ MeOH)
In both 5 and 6, the anions are effectively semi-biden-
tate, but differ somewhat in their orientations vis-a-vis
the substrate; displacement parameters on anion 2 in this
case are high and may be a foil for unresolved disorder.
The carboxylate anions being prone to semi-bidentate
coordination, the less strongly interacting oxygen atom
here is hydrogen-bonded by the hydroxylic solvent.
Here the anion plane (C2O2) lies effectively normal to
the plane containing PAgO and the phen bisector. How-
ever, again, despite refinement to a less-than-total occu-
pancy, we find solvent interaction to be significant, the
methanol molecule hydrogen-bonding to the uncoordi-
nated anion oxygen ((MeOH)O,H. . .O(2) 2.74(1), 2.2
˚
˚
(est.) A) and resulting in an anion orientation similar to
(MeOH)O,H. . .O(2) are 2.724(2), 1.99(3) A.
that in the bpy counterpart.
3.3.7. Agtfa:PPh3:bq (1:1:1) (7)
3.3.4. Agac:PPh3:phen (1:1:1) Æ 2MeOH (4 Æ 2MeOH)
In this species, containing the more basic anion, the
coordination mode is similar to the previous. Here there
are two solvent molecules of crystallization, one disor-
dered, the second firmly anchored by hydrogen-bonding
to the uncoordinated oxygen of the anion, (MeOH)O,
In this (unsolvated) carboxylate complex we find, for the
first time, a truly bidentate anion, its plane lying across the
molecule. Angles P–Ag–O are less than N–Ag–O as might
be expected. The O–C–O angle of the anion is considerably
reduced relative to the values observed with uni-/semi-
bidentate tfa, but still lies above the values found for the
various acetate species. Although like dmp, the bq ligand
may be considered to exhibit a ‘bulky’ profile, this does
not appear to impact on the overall geometries of arrays
containing it to any noticeable extent.
˚
H. . .O(2) being 2.754(5), 1.75 A.
3.3.5. Agtfa:PPh3:dmp (1:1:1) (5)
The geometry of this molecule is not unusual in the
light of the above. The dmp ligand is more highly hin-
dered than its parents phen or bpy, but this appears to
have little impact on the overall coordination environ-
ment of the metal, in this or its other complexes in the
present array.
3.3.8. Agtfa:PPh3:dpa (1:1:1) (8)
Here O(1) (N.B. coordinated). . .H,N (2 ꢀ x, 1 ꢀ y, z) are
˚
2.08(2), 2.867(2) A. This complex is not unusual, albeit the
semi-bidentate anion is unaccompanied by any interacting

1464
Effendy et al. / Inorganica Chimica Acta 360 (2007) 1451–1465
solvent. Given the behaviour of the ligand in the systems of 9
and 21, it is of interest to note that the Ag–N,N0 distances
vary quite widely throughout the array of complexes stud-
ied, and that the values observed for dpa here and elsewhere,
functioning as a bidentate ligand, are not unusually long.
3.3.12. Agtfa:Pcy3:dmp (1:1:1) (12)
Here the combination of hindered dmp with hindered
Pcy3 appears to have little impact on the coordination
environment.
3.3.13. Agtfa:Pcy3:bq (1:1:1) (13)
By contrast, in similar circumstances, the trifluoroace-
tate here is semi-bidentate.
3.3.9. Agac:PPh3:dpa (1:1:1)(2) (9)
With this complex, by contrast, a new form is found.
Here the dpa ligand has become unidentate, while the ace-
tate has become O-bridging, so that the array is now an
(unsolvated) neutral centrosymmetric dimer. The Ag–O–
Ag angle is 99.59(5)ꢁ. An important factor, perhaps, in
determining the stability of this form (and, perhaps, also
relevant in other similar situations involving unidentate
dpa) is an intra-species hydrogen-bond between the central
NH hydrogen and the uncoordinated carboxylate oxygen
3.3.14. Agtfa:Pcy3:dpa (1:1:1) (14)
In this complex, the semi-bidentate anion is disordered
over a pair of sites, the disorder seemingly not echoed in
the remainder of the coordination sphere, suggesting the
bulk of the anion to encounter little hindrance as a
determinant of its orientation or coordination capability,
the mode of coordination being unaffected by
orientation.
˚
(N,H. . .O(2) 2.841(2), 2.04(2) A). Relaxation of the chelate
constraint permits the uncoordinated pyridine ring of the
`
dpa to adopt the trans-disposition vis-a-vis the coordinated
ring; it is of interest to note here that the N(10). . .H(3) dis-
tance is 2.26(2) A, the angle at the central nitrogen atom
being 130.2(2)ꢁ. The dihedral angle between the Ag2O2
and acetate planes is 22.07(6)ꢁ.
3.3.15. Agtfa:Ascy3:bpy (1:1:1) (15)
˚
In the two complexes of Ascy3 defined, the feebler coor-
dination of Ascy3, cf. Pcy3, is primarily compensated by a
closer approach of the anion, but without substantial
change in coordination mode, rather than in the Ag–
N(L) distances.
3.3.10. Agtfa:PPh3:dpk Æ H2O (1:1:1:1) Æ MeCN
(10 Æ MeCN)
Here the pair of pyridine rings can and do function as
a chelate ligand; one of the gem-OH groups can function
in approaching ‘solvent’ mode, and does so, forming a tri-
dentate and displacing the anion which, unsurprisingly,
lies close by, hydrogen-bonded to the ligand, the two
hydrogen atoms to the same anion (O,H(21). . .O(1a)
3.3.16. Agtfa:Ascy3:dpa (1:1:1) (16)
Here the anions are semi-bidentate, as in the preceding
array.
Throughout all adducts of P(o-tol)3, the ligand confor-
mation approaches 3-symmetry about the Ag–P bond,
the 2-methyl substituents being directed toward the metal
rather than within the ligand core. The Ag–P distances
are generally slightly longer than in the PPh3/Pcy3
counterparts, the anion coordination modes being
similar.
˚
2.721(4), 1.93(3); O,H(22). . .O(2a) 2.697(4), 1.89(4) A).
The two O. . .O distances are similar, as are the two car-
˚
boxylate C–O distances (1.232(6), 1.215(7) A), suggesting
the two hydroxyl groups to be of similar acidity. The car-
boxylate group being uncoordinated, the complex may be
considered ionic in the solid state, albeit presenting as an
ion-pair.
3.3.17. Agac:P(o-tol)3:bpy (1:1:1)ÆH2O (17)ÆH2O
Here the EAgN2 array is well removed from planarity.
Ligands of the form Ecy3 (E = P or As) normally exhibit
a more bulky steric profile than PPh3 counterparts, as mea-
sured by their ‘cone angles’ [16]; their conformations in
projections down the M–P coordinate bond may vary, in
a manner discussed elsewhere [17], and here they are
parameterized by the Ag–E–C–C torsion angle set (Table
1). In general, given the essentially three-coordinate nature
of the metal coordination environments, the variations
therein have little impact on the latter, except to note that
the anion approaches in the relatively limited range of com-
pounds studied are as unidentate or weak semi-bidentate
ligands. In a number of complexes, the E–Ag–N,N0 angle
pairs are quite disparate, but in others they are essentially
equal.
3.3.18. Agtfa:P(o-tol)3:phen (1:1:1)ÆH2O (18)ÆH2O
Here also the anion is unsymmetrically bidentate and
the EAgN2 array well removed from planarity. A curious
feature of the structure, not uncommon in other com-
plexes, is the apparent disorder of both silver and phos-
phorus atoms (minor light atom ligand components not
resolved), being displaced to either side of a central
˚
Ag–P vector by ca. 1 A each way (Fig. 1(r)). In the dis-
˚
placed components, Ag–P is shorter (2.33(4), 2.36(4) A),
with Ag moving closer to one of the ligand nitrogen
atoms and further from the other, suggesting the possi-
bility of some admixture in the crystal of other coordina-
tion isomers, or less likely, minor impurity. Displacement
parameters on the residue modelled as water are high,
and they do not interact closely with other species in
the lattice.
3.3.11. Atfa:Pcy3:bpy (1:1:1) (11)
Here the impact of the anion approach is much more
marked, the PAgN2 angle sum falling to 328.5ꢁ.

Effendy et al. / Inorganica Chimica Acta 360 (2007) 1451–1465
1465
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Here semi-bidentate anion interaction is found.
3.3.20. Agtfa:P(o-tol)3:dpa (1:1:1) Æ ½MeCN
(20 Æ ½MeCN)
Here two independent molecules comprise the asymmet-
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3.3.21. Agac:P(o-tol)3:dpa (1:1:1)(2) Æ 2MeCN
(21 Æ 2MeCN)
Interestingly, here, we again find a binuclear form, O-ac
bridged, with unidentate dpa, as in the PPh3 counterpart,
above. The solvent is well removed from any of the sub-
strate components.
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