Synthesis and structural characterization of adducts of silver(I) perchlorate with PR3 (R = Ph, cy, o-tolyl) and oligodentate aromatic bases derivative of 2,2′-bipyridyl, L, AgClO4:PR3:L (1:1:1)

Article abstract of DOI:10.1016/j.ica.2006.07.004

Ten novel adducts of the form AgClO₄:PR₃:L (1:1:1) (R = Ph, cy, o-tolyl; L = 2,2′-bipyridyl ('bpy'), 2,2′-biquinoline ('bq'), bis(2-pyridyl)amine ('dpa'), bis(2-picolyl)amine ('dpca')) have been synthesized and characterized by analytical, spectroscopic (IR, far-IR, ¹H and ³¹P NMR) and single crystal X-ray diffraction studies. The solid state molecular structures show that the complexes predominantly take the form [(R₃P)AgL]⁺X^-, with a trigonal PAgN₂ coordination environment, where the approach of the anion or the solvent may perturb the planarity of the silver environment. The ClO₄ anion shows uni- or semi-bidentate coordination, except in the complexes AgClO₄:PR₃:dpca (1:1:1) (R = Ph and o-tolyl), where the anion remains uncoordinated and the dpca donor is a three-coordinate pincer-like ligand.

Full text of DOI:10.1016/j.ica.2006.07.004

Inorganica Chimica Acta 360 (2007) 1424–1432
www.elsevier.com/locate/ica
Synthesis and structural characterization of adducts of silver(I)
perchlorate with PR3 (R = Ph, cy, o-tolyl) and oligodentate aromatic
bases derivative of 2,20-bipyridyl, L, AgClO4:PR3:L (1:1:1)
c
c,
a
a
Effendy a,b, Fabio Marchetti , Claudio Pettinari *, 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 15 July 2006
Abstract
Ten novel adducts of the form AgClO4:PR3:L (1:1:1) (R = Ph, cy, o-tolyl; L = 2,20-bipyridyl (‘bpy’), 2,20-biquinoline (‘bq’), bis(2-pyr-
idyl)amine (‘dpa’), bis(2-picolyl)amine (‘dpca’)) have been synthesized and characterized by analytical, spectroscopic (IR, far-IR, 1H and
31P NMR) and single crystal X-ray diffraction studies. The solid state molecular structures show that the complexes predominantly take
the form [(R3P)AgL]+Xꢀ, with a trigonal PAgN2 coordination environment, where the approach of the anion or the solvent may perturb
the planarity of the silver environment. The ClO4 anion shows uni- or semi-bidentate coordination, except in the complexes
AgClO4:PR3:dpca (1:1:1) (R = Ph and o-tolyl), where the anion remains uncoordinated and the dpca donor is a three-coordinate pin-
cer-like ligand.
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: Silver perchlorate; Phosphine; Aromatic N-bases; Single crystal X-ray studies; NMR
1. Introduction
2,20:60,200-terpyridyl (‘tpy’), in combination with unidentate
bases ER3, which are similarly diverse in steric and elec-
tronic characteristics. Here, E = P, R = Ph, cy (= cyclo-
hexyl), o-tol (= o-tolyl), and AgX, X = oxyanion, of
systematically increasing basicity/donor capability, where
X = ClO4, and, in the following papers, NO3 [3] and car-
boxylate (H3CCO2 and F3CCO2) [4], the resulting com-
plexes being overwhelmingly of 1:1:1 AgX:L:ER3
stoichiometry except when L = tpy. We present the results
for X = ClO4 in this paper.
As a part of the extension of our study on systematic
structural chemistry of complexes of simple coinage
metal(I) salts with important group 15 donor bases, we
described, in the preceding pair of papers, the study of
adducts of AgX, X = oxyanion ðClO4ꢀ; NO3ꢀÞ with contri-
butions of bi- (or oligo-) dentate ligands, L, with nitrogen
as a donor, and bidentate ligands Ph2E(CH2)xEPh2 for
diverse x, with E = P, as a donor [1,2]. We now turn to
explore the nature of arrays formed with the same or sim-
ilar nitrogen donor ligands, L = 2,20-bipyridyl (‘bpy’),
1,10-phenanthroline (‘phen’), 2,9-dimethyl,1,10-phenan-
throline (‘dmp’), bis(2-pyridyl)amine (‘dpa’), bis(2-pyr-
idyl)ketone (‘dpk’) and its hydrate (‘dpk Æ H2O’), 2,2-
biquinoline (‘bq’), bis(2-picolyl)amine (‘dpca’), and
2. Experimental
The experimental procedures follow those that are
recorded in an accompanying paper [1]; in the majority
of cases, crystals suitable for the X-ray work 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 (exceptions: 5 (acetone); 10 (MeCN/ethanol)).
*
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 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2006.07.004

Effendy et al. / Inorganica Chimica Acta 360 (2007) 1424–1432
1425
2.1. Syntheses
t(ClO4), 522s, 505s, 494s, 463m, 441m, 433m, 428m,
407m t(PPh3), 367w, 331m, 273m, 260m, 239w, 215w,
202m. 1H NMR (CDCl3, 293 K): d, 7.47 m (15H,
PC18H15), 6.85t, 7.42m, 7.67dd, 7.95d (8H, CHdpa),
9.10br (1H, NHdpa). 31P NMR (CDCl3, 293 K): d, 14.8br.
31P NMR (CDCl3, 223 K): d, 8.9dd (1J(31P–109Ag):
Safety note. Perchlorate salts of metal complexes with
organic ligands are potentially explosive! Only small
amounts of materials should be prepared, and these should
be handled with great caution.
1
452.1 Hz; J(31P–107Ag): 391.6 Hz); 16.8dd (1J(31P–109Ag):
1
2.1.1. Synthesis of AgClO4:PPh3:bpy (1:1:1) (1)
738.8 Hz; J(31P–107Ag): 640.1 Hz).
A solution containing AgClO4 (0.207 g, 1.0 mmol), PPh3
(0.262 g, 1.0 mmol), and bpy (0.156 g, 1.0 mmol) in 5 mL
of acetonitrile was stirred after warming for 1 h and then
cooled at room temperature. A colourless crystalline pre-
cipitate was slowly formed, which was filtered off, washed
with CH3CN (5 mL), dried under reduced pressure and
shown to be compound 1 (0.588 g, yield 94%); m.p. 168–
172 ꢁC. Anal. Calc. for C28H23AgClN2O4P: C, 53.74; H,
3.70; N, 4.48. Found: C, 53.57; H, 3.76; N, 4.44%. Km
2.1.4. Synthesis of AgClO4:PPh3:dpca (1:1:1) (4)
Compound 4 (0.609 g, yield 91%) was prepared follow-
ing a procedure similar to that reported for 1 by using an
acetonitrile solution of AgClO4 (0.207 g, 1.0 mmol), PPh3
(0.262 g, 1.0 mmol), and dpca (0.199 g, 1.0 mmol); m.p.
186–188 ꢁC. Anal. Calc. for C30H28AgClN3O4P: C, 53.87;
H, 4.22; N, 6.28. Found: C, 54.02; H, 4.14; N, 6.38%. Km
(CH3CN, 10ꢀ4 M): 158 Xꢀ1 cm2 molꢀ1
10ꢀ4 M): 58 Xꢀ1 cm2 molꢀ1. IR (nujol, cmꢀ1): 3305m,
. . . . . .
. Km (CH2Cl2,
(CH3CN, 10ꢀ4 M): 124 Xꢀ1 cm2 molꢀ1
10ꢀ4 M): 56 Xꢀ1 cm2 molꢀ1. IR (nujol, cmꢀ1): 1644s,
. . . . . .
. Km (CH2Cl2,
3071m t(N–Hdpca), 1597s, 1570s t(C C, C N), 1100s
•
•
1584m t(C C, C N), 1071s, 1065s, 1008s, 649w, 622s
br, 654m, 634m t(ClO4), 527s, 510vs, 493vs, 453m, 427s,
411s t(PPh3), 394w, 354m, 302m, 280w, 247m, 227w,
•
•
t(ClO4), 543m, 524s, 513vs, 489s, 437m, 421m, 407m
t(PPh3), 352w, 279m, 247m, 226m, 212w, 205m. 1H
NMR (CDCl3, 293 K): d, 7.40m (15H, PC18H15), 7.58m,
8.10t, 8.41d, 8.62d (8H, CHbpy). 31P NMR (CDCl3,
223 K): d, 15.4dbr (1J(31P–107/109Ag): 672.5 Hz).
1
208m. H NMR (CDCl3, 293 K): d, 4.18s (4H, CH2dpca),
7.14dt, 7.28dd, 7.64dt, 8.14dd (8H, CHdpca), 7.43m (15H,
PC18H15), 10.10br (1H, NHdpca). 31P NMR (CDCl3,
1
223 K): d, 15.7dd (1J(31P–109Ag): 692.1 Hz; J(31P–107Ag):
603.0 Hz).
2.1.2. Synthesis of AgClO4:PPh3:bq (1:1:1) (2)
Compound 2 (0.638 g, yield 88%) was prepared follow-
ing a procedure similar to that reported for 1 by using an
acetonitrile solution of AgClO4 (0.207 g, 1.0 mmol), PPh3
(0.262 g, 1.0 mmol), and bq (0.256 g, 1.0 mmol); m.p.
276–278 ꢁC. Anal. Calc. for C36H27AgClN2O4P: C, 59.57;
H, 3.75; N, 3.86. Found: C, 59.35; H, 3.86; N, 3.92%. Km
2.1.5. Synthesis of AgClO4:Pcy3:bpy (1:1:1) (5)
Compound 5 (0.528 g, yield 82%) was prepared follow-
ing a procedure similar to that reported for 1 by using an
acetone solution of AgClO4 (0.207 g, 1.0 mmol), Pcy3
(0.280 g, 1.0 mmol), and bpy (0.156 g, 1.0 mmol); m.p.
184–186ꢁC. Anal. Calc. for C28H41AgClN2O4P: C, 52.23;
H, 6.42; N, 4.35. Found: C, 52.06; H, 6.38; N, 4.12%. Km
(CH3CN, 10ꢀ4 M): 138 Xꢀ1 cm2 molꢀ1
10ꢀ4 M): 51 Xꢀ1 cm2 molꢀ1. IR (nujol, cmꢀ1): 1617m,
. . . . . .
. Km (CH2Cl2,
(CH3CN, 10ꢀ4 M): 121 Xꢀ1 cm2 molꢀ1
10ꢀ4 M): 57 Xꢀ1 cm2 molꢀ1. IR (nujol, cmꢀ1): 1592m,
. . . . . .
. Km (CH2Cl2,
1590s, 1548m br, 1501s t(C C, C N), 1088vs, 1053vs,
•
•
1024sh, 997s, 654m, 622s t(ClO4), 523vs, 498s, 491vs,
443m, 436m, 418w, 397m t(PPh3), 377w, 328w, 304w,
1578m br t(C C, C N), 1094vs, 1076vs, 1024s, 648m,
• •
620vs t(ClO4), 523m, 515s, 494w, 470m, 460m, 422w,
1
1
279m, 268m, 255w, 248w, 243w, 224m, 202m. H NMR
410s t(Pcy3), 383w, 280w, 265w, 224m, 205m. H NMR
(CDCl3, 293 K): d, 7.51m (15 H, PC18H15), 7.62m, 7.94dd,
8.18m, 8.67dt (12 H, CHbq). 31P NMR (CDCl3, 223 K): d,
(CDCl3, 293 K): d, 1.40m, 1.96m (33H, PC18H33), 7.66dd,
8.18dt, 8.46d, 8.67dd (8H, CHbpy). 31P NMR (CDCl3,
1
1
10.1dd (1J(31P–109Ag): 435.7 Hz; J(31P–107Ag): 377.0 Hz);
223 K): d, 46.5dd (1J(31P–109Ag): 716.5 Hz; J(31P–107Ag):
1
15.4dd (1J(31P–109Ag): 372.3 Hz; J(31P–107Ag): 322.2 Hz);
621.3 Hz).
1
17.4dd (1J(31P–109Ag): 272.3 Hz; J(31P–107Ag): 224.7 Hz);
1
17.8dd (1J(31P–109Ag): 718.9 Hz; J(31P–107Ag): 623.9 Hz).
2.1.6. Synthesis of AgClO4:Pcy3:bq (1:1:1) (6)
Compound 6 (0.632 g, yield 85%) was prepared follow-
ing a procedure similar to that reported for 1 by using an
acetonitrile solution of AgClO4 (0.207 g, 1.0 mmol), Pcy3
(0.280 g, 1.0 mmol), and bq (0.256 g, 1.0 mmol); m.p.
258–260 ꢁC. Anal. Calc. for C36H45AgClN2O4P: C, 58.11;
H, 6.10; N, 3.76. Found: 57.93; H, 6.14; N, 3.89%. Km
2.1.3. Synthesis of AgClO4:PPh3:dpa (1:1:1) (3)
Compound 3 (0.545 g, yield 85%) was prepared follow-
ing a procedure similar to that reported for 1 by using an
acetonitrile solution of AgClO4 (0.207 g, 1.0 mmol), PPh3
(0.262 g, 1.0 mmol), and dpa (0.171 g, 1.0 mmol); m.p.
200–202 ꢁC. Anal. Calc. for C28H24AgClN3O4P: C, 52.48;
H, 3.78; N, 6.56. Found: C, 52.58; H, 3.62; N, 6.47%. Km
(CH3CN, 10ꢀ4 M): 108 Xꢀ1 cm2 molꢀ1. Km (CH2Cl2,
10ꢀ4 M): 5 Xꢀ1 cm2 molꢀ1. IR (nujol, cmꢀ1): 3300m,
3210m, 3200m t(N–Hdpa), 1630s, 1584m, 1578s, 1528m
(CH3CN, 10ꢀ4 M): 128 Xꢀ1 cm2 molꢀ1
10ꢀ4 M): 53 Xꢀ1 cm2 molꢀ1. IR (nujol, cmꢀ1): 1618w,
. . . . . .
. Km (CH2Cl2,
1592m, 1571sh, 1558m, 1548m, 1504s t(C C, C N),
•
•
1096vs, 1070vs, 1024sh, 1004s, 654m, 622vs t(ClO4),
514m, 501m, 483s, t(Pcy3), 452w, 443w, 419m, 399m,
384m, 352w, 336w, 327w, 303w, 281m, 268m, 247m,
. . .
. . .
t(C C, C N), 1098s, 1080s, 1060s, 1000s, 638m, 620s
•
•

1426
Effendy et al. / Inorganica Chimica Acta 360 (2007) 1424–1432
1
224m, 211m. H NMR (CDCl3, 293 K): d, 1.39m, 1.88m
(33H, PC18H33), 7.70t, 7.82t, 8.02dd, 8.30d, 8.76q (12H,
CHbq). 31P NMR (CDCl3, 223 K): d, 39.3dd
ortho-CH3)3), 6.80dt, 6.93dd, 7.52dt, 7.70dd (8 H, CHdpa),
9.10br (1H, NHdpa). 31P NMR (CDCl3, 223 K): d, ꢀ17.6d
br (1J(31P–109/107Ag): 671.4 Hz). The compound recrystal-
lized from MeCN was modelled in the X-ray study as 9ƽ
MeCN.
(1J(31P–109Ag): 705.4 Hz; J(31P–107Ag): 610.5 Hz); 38.3br.
1
2.1.7. Synthesis of AgClO4:P(o-tolyl)3:bpy (1:1:1) (7)
Compound 7 (0.634 g, yield 95%) was prepared follow-
ing a procedure similar to that reported for 1 by using
an acetonitrile solution of AgClO4 (0.207 g, 1.0 mmol),
P(o-tolyl)3 (0.304 g, 1.0 mmol), and bpy (0.156 g,
1.0 mmol); m.p. 242–244 ꢁC. Anal. Calc. for C31H29AgCl-
N2O4P: C, 55.75; H, 4.38; N, 4.19. Found: 55.38; H,
2.1.10. Synthesis of AgClO4:P(o-tolyl)3:dpca (1:1:1) (10)
Compound 10 (0.647 g, yield 91%) was prepared follow-
ing a procedure similar to that reported for 1 by using an
acetonitrile/ethanol solution of AgClO4 (0.207 g,
1.0 mmol), P(o-tolyl)3 (0.304 g, 1.0 mmol), and dpca
(0.199 g, 1.0 mmol); m.p. 204–206 ꢁC. Anal. Calc. for
C33H34AgClN3O4P: C, 55.75; H, 4.82; N, 5.91. Found: C,
55.84; H, 5.01; N, 6.08%. Km (CH3CN, 10ꢀ4 M):
136 Xꢀ1 cm2 molꢀ1. Km (CH2Cl2, 10ꢀ4 M): 54 Xꢀ1 cm2
molꢀ1. IR (nujol, cmꢀ1): 3295m t(N–Hdpca), 1587s, 1570m
4.02; N, 4.24%. Km (CH3CN, 10ꢀ4 M): 102 Xꢀ1 cm2 molꢀ1
Km (CH2Cl2, 10ꢀ4 M): 58 Xꢀ1 cm2 molꢀ1. IR (nujol, cmꢀ1):
. . . . . .
.
1589s, 1574m, 1566m t(C C, C N), 1119sh, 1005vs,
•
•
1054vs, 1010s, 646m, 623vs t(ClO4), 565s, 557m, 519m,
512m, 469vs, 463vs, 441w, 410m t(P(o-tol)3), 385w, 353w,
304w, 268m, 247w, 227w, 203m. 1H NMR (CDCl3,
293 K): d, 2.59s (9H, P(C6H4-ortho-CH3)3), 6.93dd, 7.27t,
7.46m (12H, P(C6H4–ortho-CH3)3), 7.63dt, 8.18dt, 8.41dd,
8.50d (8H, CHbpy). 31P NMR (CDCl3, 223 K): d, ꢀ18.9d
br (1J(31P–109/107Ag): 667.7 Hz).
. . .
. . .
t(C C, C N), 1090vs, 654m, 622vs t(ClO4), 564s, 557s,
•
•
521sh, 513m, 497m, 470vs, 460vs, 438w, 405m t(P(o-tol)3),
384w, 352w, 312w, 263m, 248w. 1H NMR (CDCl3,
293 K): d, 2.41s (9H, P(C6H4-ortho-CH3)3), 4.10br (4H,
CH2dpac), 7.20t, 7.33m, 7.41dt (12H, P(C6H4–ortho-
CH3)3), 6.88t, 7.06dd, 7.67dt, 7.77 d (8 H, CHdpca), NHdpca
not observed. 31P NMR (CDCl3, 223 K): d, 17.6d br
(1J(31P–109/107Ag): 615.3 Hz).
2.1.8. Synthesis of AgClO4:P(o-tolyl)3:bq (1:1:1) (8)
Compound 8 (0.714 g, yield 93%) was prepared follow-
ing a procedure similar to that reported for 1 by using
an acetonitrile solution of AgClO4 (0.207 g, 1.0 mmol),
P(o-tolyl)3 (0.304 g, 1.0 mmol), and bq (0.256 g, 1.0 mmol);
m.p. 266–268 ꢁC. Anal. Calc. for C39H33AgClN2O4P: C,
61.00; H, 4.33; N, 3.65. Found: 61.24; H, 4.45; N, 3.72%.
Km (CH3CN, 10ꢀ4 M): 115 Xꢀ1 cm2 molꢀ1. Km (CH2Cl2,
10ꢀ4 M): 59 Xꢀ1 cm2 molꢀ1. IR (nujol, cmꢀ1): 1618m,
2.2. Structure determinations
General procedures are described in an accompanying
paper [1]; specific details are given below. For 1 and 5
unique data sets were measured at ca. 295 K, using a single
counter instrument in 2h/h scan mode, the ‘observed’ crite-
rion being I > 3r(I), Gaussian absorption corrections being
applied. CCDC 299442–299450; 299452.
. . .
. . .
1590s, 1563m, 1556m, 1545m, 1504s t(C C, C N),
•
•
1094vs, 1064vs, 1032sh, 653m, 620vs t(ClO4), 563s, 520m,
512m, 490m, 472s, 462s, 441w, 403w t(P(o-tol)3), 385w,
352w, 327w, 303w, 280m, 270m, 254w, 247w, 227m,
2.2.1. Crystal/refinement data
2.2.1.1. AgClO4:PPh3:bpy (1:1:1) (1). C28H23AgClN2O4P,
M = 625.8. Monoclinic, space group P21/c (C52h, No. 14),
1
207m. H NMR (CDCl3, 293 K): d, 2.43s (9H, P(C6H4–
˚
a = 15.484(6), b = 9.140(4), c = 21.58(1) A, b = 118.80(4)ꢁ,
ortho-CH3)3), 7.23m, 7.35m, 7.48m (12H, P(C6H4–ortho-
CH3)3), 7.61m, 8.02d, 8.79q (12H, CHbq). 31P NMR
(CDCl3, 223 K): d, ꢀ18.1d br (1J(31P–109/107Ag): 674.1 Hz).
3
V = 2676 A . Dc (Z = 4) = 1.553 g cmꢀ3. lMo = 9.5 cmꢀ1
;
˚
specimen:
0.22 · 0.28 · 0.42 mm;
Tmin/max = 0.92.
2hmax = 50ꢁ; N = 4703, No = 2891; R = 0.058, Rw = 0.064.
2.1.9. Synthesis of AgClO4:P(o-tolyl)3:dpa (1:1:1) (9)
Compound 9 (0.533 g, yield 78%) was prepared following
a procedure similar to that reported for 1 by using an aceto-
nitrile solution of AgClO4 (0.207 g, 1.0 mmol), P(o-tolyl)3
(0.304 g, 1.0 mmol), and dpa (0.171 g, 1.0 mmol); M.p.
220–222 ꢁC. Anal. Calc. for C31H30AgClN3O4P: C, 54.52;
H, 4.43; N, 6.15. Found: 54.40; H, 4.58; N, 6.34%. Km
2.2.1.2. AgClO4:PPh3:bq (1:1:1) (2). C36H27AgClN2O4P,
M = 725.9. Triclinic, space group P1 (C1i , No. 2),
ꢀ
˚
a = 9.6710(8), b = 9.8878(8), c = 16.097(1) A, a = 97.004
3
˚
(1), b = 95.224(1), c = 94.973(1)ꢁ, V = 1514 A . Dcalc
(Z = 2) = 1.592 g cmꢀ3. lMo = 8.5 cmꢀ1; specimen: 0.32 ·
0.25 · 0.10 mm; Tmin/max = 0.85. 2hmax = 58ꢁ; Nt = 17397,
N = 7309 (Rint = 0.019), No = 6395; R = 0.031, Rw = 0.039.
(CH3CN, 10ꢀ4 M): 112 Xꢀ1 cm2 molꢀ1
. Km (CH2Cl2,
10ꢀ4 M): 4 Xꢀ1 cm2 molꢀ1. IR (nujol, cmꢀ1): 3355m,
3245w, 3216w, 3151w t(N–H), 1629s, 1584sh, 1577s,
2.2.1.3. AgClO4:PPh3:dpa (1:1:1) (3). C28H24AgClN3O4P,
M = 640.8. Orthorhombic, space group P212121 (D42, No.
. . .
. . .
1528m t(C C, C N), 1095vs, 1043vs, 999s, 638m, 621vs
˚
•
•
19),
a = 8.966(2),
b = 14.523(3),
c = 20.666(4) A,
3
V = 2691 A . Dcalc (Z = 4) = 1.581 g cmꢀ3
.
lMo = 9.5
t(ClO4), 564s, 557m, 518m, 469vs, 462vs, 440w, 419w, 406s
t(P(o-tol)3), 385w, 352w, 326m, 302w, 267m, 255w, 247w,
227m, 203m. 1H NMR (CDCl3, 293 K): d, 2.52s (9H,
P(C6H4–ortho-CH3)3), 7.26t, 7.39m, 7.64dd (12H, P(C6H4–
˚
cmꢀ1; specimen: 0.20 · 0.18 · 0.05 mm; Tmin/max = 0.80.
2hmax = 58ꢁ; Nt = 32088, N = 3820 (Rint = 0.069),
No = 2741; R = 0.045, Rw = 0.042. xabs = 0.06(4).

Effendy et al. / Inorganica Chimica Acta 360 (2007) 1424–1432
1427
2.2.1.4. AgClO4:PPh3:dpca (1:1:1) (4). C30H28AgCl-
N3O4P, M = 668.9. Monoclinic, space group P21/n (C52h,
2.2.1.10. AgClO4:P(o-tolyl)3:dpca (1:1:1) (10). C33H34-
ꢀ
AgClN3O4P, M = 710.9. Triclinic, space group P1, a =
˚
No. 14 (variant)), a = 13.670(1), b = 14.961(2), c = 14.183
10.3650(9), b = 10.6585(9), c = 16.511(1) A, a = 75.539(1)ꢁ,
3
3
˚
˚
˚
(2) A, b = 100.847(2)ꢁ, V = 2849 A . Dcalc (Z = 4) =
b = 72.707(1)ꢁ, c = 66.737(1)ꢁ, V = 1582 A . Dcalc (Z = 2) =
1.559 g cmꢀ3
.
l
Mo = 9.0 cmꢀ1
;
specimen: 0.35 · 0.30 ·
1.493 g cmꢀ3
.
l
Mo = 8.1 cmꢀ1
;
specimen: 0.20 · 0.12 ·
0.07 mm; Tmin/max = 0.67. 2hmax = 58ꢁ; Nt = 28325, N =
7261 (Rint = 0.027), No = 5922; R = 0.029, Rw = 0.035.
(x, y, z, Uiso)H refined.
0.10 mm; Tmin/max = 0.86. 2hmax = 58ꢁ; Nt = 15666, N =
7728 (Rint = 0.020), No = 6600; R = 0.029 Rw = 0.034.
(x, y, z, Uiso)H refined.
2.2.1.5. AgClO4:Pcy3:bpy (1:1:1) (5). C28H41AgClN2O4P,
15
3. Results and discussion
M = 643.9. Orthorhombic, space group Pbca (D , No. 61),
2h
3
˚
˚
a = 16.852(2), b = 38.330(2), c = 9.165(2) A, V = 5920 A .
Dc (Z = 8) = 1.445 g cmꢀ3
0.41 · 0.31 · 0.57 mm; Tmin/max = 0.92.
N = 5182, No = 3287; R = 0.036, Rw = 0.037. (x,y,zUiso H
.
l
Mo = 8.6 cmꢀ1
;
specimen:
3.1. Syntheses
2hmax = 50ꢁ;
The adducts 1–10 (Chart 1), of general formula
AgClO4:PR3:L (1:1:1) have been synthesized by the reac-
tion of one equivalent of N,N0-bidentate aromatic ligand,
L, derivative of 2,20-bipyridyl, with one equivalent of sil-
ver(I) perchlorate and one equivalent of a unidentate phos-
phine according to the following equation:
)
refined.
2.2.1.6. AgClO4:Pcy3:bq (1:1:1) (6). C36H45AgClN2O4P,
ꢀ
M = 744.1. Triclinic, space group P1, a = 9.490(1),
˚
b = 10.085(1), c = 19.568(3) A, a = 77.109(2), b = 80.394
3
˚
(2), c = 66.386(2)ꢁ,V = 1666 A . Dcalc(Z = 2) = 1.483 g
S
cmꢀ3. lMo = 7.8 cmꢀ1; specimen: 0.40 · 0.35 · 0.10 mm;
Tmin/max = 0.82. 2hmax = 58ꢁ; Nt = 19237; N = 8055
(Rint = 0.020), No = 7394; R = 0.031, Rw = 0.051.
AgClO4 þ PR3 þ L ! AgClO4 : PR3 : Lð1 : 1 : 1Þ
ð1Þ
(R = Ph, cy or o-tolyl, L = bpy, bq, dpa, dpca, S = aceto-
nitrile or acetone).
Variata. The perchlorate was modeled as disordered
over two sets of sites, occupancies set at 0.5 after trial
refinement. Phenyl ring 2 was also modeled as disordered,
occupancies refining to 0.78(1) and complement.
All compounds, which are air-stable, and colourless
materials, are insoluble in diethyl ether and ethanol,
and soluble in chlorinated solvents, acetone, acetonitrile
and DMSO. The conductivity measurements are in
accordance with the ionic formulations found in the solid
state for the derivatives 4 and 10. In addition, com-
pounds 1–2 and 5–8, containing the weakly coordinated
ClO4, undergo complete ionic dissociation, not only in
acetonitrile 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
[5]. Derivatives 3 and 9, containing the dpa ligand, which
forms hydrogen-bonding networks in the solid state
involving interaction of its N–H component with the per-
chlorate group (see crystallographic studies below), are
1:1 electrolytes in acetonitrile but non-electrolytes in
dichloromethane [5].
2.2.1.7. AgClO4:P(o-tolyl)3:bpy (1:1:1) (7). C31H29AgCl-
ꢀ
N2O4P, M = 667.9. Triclinic, space group P1, a =
˚
9.9795(8), b = 10.4107(8), c = 15.714(1) A, a = 89.907(1)ꢁ,
3
˚
b = 89.307(1)ꢁ, c = 64.458(8)ꢁ, V = 1473 A . Dcalc (Z = 2)
= 1.506 g cmꢀ3
. l ; specimen: 0.16 · 0.10
Mo = 8.7 cmꢀ1
· 0.10 mm; Tmin/max = 0.92. 2hmax = 58ꢁ; Nt = 14671;
N = 7222 (Rint = 0.020), No = 6393; R = 0.036, Rw =
0.047.
2.2.1.8. AgClO4:P(o-tolyl)3:bq (1:1:1) (8). C39H33AgCl-
ꢀ
N2O4P, M = 768.0. Triclinic, space group P1, a = 10.611
˚
(2), b = 10.723(2), c = 16.877(3) A, a = 94.451(2)ꢁ, b =
3
˚
101.704(2)ꢁ, c = 116.311(2)ꢁ, V = 1655 A . Dcalc (Z = 2)
= 1.541 g cmꢀ3. lMo = 7.8 cmꢀ1; specimen: 0.35 · 0.30 ·
0.10 mm; Tmin/max = 0.63. 2hmax = 55ꢁ; Nt = 16186; N =
7497 (Rint = 0.049), No = 6120; R = 0.065, Rw = 0.081.
3.2. Spectroscopy
The infrared spectra of 1–10 (see Section 2) are consis-
tent with the formulations proposed, showing all of the
bands required by the presence of the organic N-donors
and unidentate phosphine ligands [6]. In the far-IR spec-
tra of all phosphino derivatives we assigned, on the basis
of previous reports, the broad absorptions near 500 cmꢀ1
and those at 480–400 cmꢀ1 to Whiffen’s y and t vibra-
tions [7].
The IR spectra of derivatives 4 and 10 show two
absorptions characteristic of ionic perchlorate groups, a
strong broad band in the range 1110–1080 cmꢀ1 (m3),
and a sharp medium or strong band at ca. 620 cmꢀ1
2.2.1.9. AgClO4:P(o-tolyl)3:dpa (1:1:1). ½MeCN (9 Æ ½
MeCN). C32H31.5AgClN3.5O4P, M = 703.4. Triclinic,
ꢀ
space group P1, a = 10.166(1), b = 10.547(1), c = 15.769
˚
(2) A, a = 86.956(2)ꢁ, b = 84.339(2)ꢁ, c = 65.548(1)ꢁ, V =
3
1519 A . Dcalc (Z = 2) = 1.538 g cmꢀ3. lMo = 8.5 cmꢀ1
;
˚
specimen: 0.30 · 0.30 · 0.10 mm; Tmin/max = 0.83. 2hmax
58ꢁ; Nt = 17354; N = 7443 (Rint = 0.020), No = 6436;
R = 0.029, Rw = 0.036. (x, y, z, Uiso H refined (solvent
excepted).
=
)
Variata. Solvent acetonitrile was modeled as disordered
about a center of symmetry.

1428
Effendy et al. / Inorganica Chimica Acta 360 (2007) 1424–1432
O
O
O
O
O
Cl
O
O
O
Cl
Cl
O
O
O
O
N
Ag
N
Ag
H
N
N
Ag
PPh3
N
PPh3
PPh3
N
N
1
3
2
O
O
O
O
O
Cl
Cl
O
O
O
PPh3
N
Ag
N
Ag
N
Ag
ClO4
N
Pcy3
H
Pcy3
N
N
N
4
5
6
O
O
O
O
O
Cl
O
O
Cl
O
Cl
O
O
O
O
P(o-tol)3
N
Ag
N
N
N
Ag
Ag
N
H
ClO4
N
Ag
N
H
P(o-tol)3
P(o-tol)3
N
N
P(o-tol)3
N
7
9
10
8
Chart 1.
(m4) [8,9], in accordance with the structures found in the
solid state (see below), and with the behaviour shown
by these complexes in solution. For derivatives 1–3 and
5–9 a different pattern has been observed, the IR spectra
showing three strong absorptions in the range 1000–
1110 cmꢀ1, typical of m8, m6 and m1, and two absorptions
at ca. 645 and 620 cmꢀ1 presumably due to m3 and m7,
indicative of uni- or semi-bidentate perchlorate groups,
as found in the highly distorted trigonal planar
[(cy3P)2CuOClO3] array which contains a unidentate per-
chlorate group [10]. The IR spectra of the dpa-containing
derivatives 3 and 9 exhibit broad bands over 3100 cmꢀ1
ascribed to N–Hꢁ ꢁ ꢁOClO3 hydrogen-bonding, observed
also in their crystal structures (see below).
perature (223 K), and one unresolved doublet or resolved
pairs of doublets, arising from coupling between the phos-
phorus and silver atoms, are observed in the accessible tem-
perature range.
Muetterties and Alegranti [11] and Goel and Pilon [12]
indicated that the spin–spin coupling constant (J) between
phosphorus and silver is dependant on the number of
coordinated phosphorus atoms in the silver complex,
and that it is also possible to determine the number of
the latter from measurement of the J values in the 31P
NMR spectra. On the basis of the detected values, a
AgPN2 coordination environment is likely in solution
for compounds 1–3 and 5–9, whereas in the cases of 4
and 10, which exhibit lower coupling constant values,
AgPN3 environments seem to persist in solution. Com-
pound 2, however, slowly dissociates in solution likely
due to steric interactions between the P-donor and the
bq ligand, four different pairs of doublets being detected
24 h after dissolution. The signal assignable to the AgPN2
core remains the most abundant, but doublets due to
AgP2-, AgP3- and AgP4-containing species emerge, pre-
sumably because of dissociation in accordance with the
following equilibria:
1
In the H NMR spectra, the signals due to the phos-
phine and N-donor ligands show a different pattern with
respect to those found for the free donors that can be taken
as evidence for the existence of complexes also in chlori-
nated solvent solution.
The room temperature 31P NMR spectra of complexes
1–10 consist of broad singlets, presumably in consequence
of exchange equilibria that are reasonably fast in relation
to the NMR time scale. Exchange is quenched at low tem-

Effendy et al. / Inorganica Chimica Acta 360 (2007) 1424–1432
1429
2½AgðPPh3ÞðbqÞꢂClO4
¡½AgðPPh3Þ2ðClO4Þꢂ þ ½AgðbqÞ2ꢂClO4
3½AgðPPh3ÞðbqÞꢂClO4
ð2Þ
¡½AgðPPh3Þ3ðClO4Þꢂ þ ½AgðbqÞ2ꢂClO4 þ ½AgðbqÞðClO4Þꢂ
ð3Þ
4½AgðPPh3ÞðbqÞꢂClO4
¡½AgðPPh3Þ4ꢂClO4 þ 2½AgðbqÞ2ꢂClO4 þ AgClO4
ð4Þ
3.3. Single crystal X-ray studies
All adducts 1–10 have been obtained in crystalline forms
suitable for single crystal X-ray diffraction studies. All
the complexes are mononuclear, based on a quasi-planar
three-coordinate AgN2 coordination environment in an
[(R3P)AgL]+ complex, with complementary counterion
and, occasionally, accompanying solvent, except for com-
plexes 4 and 10 containing the dpca ligand, where the
N-donor behaves as a tripodal tridentate and the silver
coordination geometry is typically tetrahedral with ionic
perchlorate anions. In all other complexes, the EAgN2
in-plane angle sum, ideally 360ꢁ for a completely planar
array, diminishes, as expected, broadly in parallel with
the strength of the interaction with the approaching spe-
cies, asymmetry in E–Ag–N,N0 broadly correlating in the
manner expected with the Ag–N distances.
The ligands L offer a range of ‘bites’, bpy, bq being sim-
ilar, while dpa, with a six- cf. a five-membered chelate ring,
has a greater ‘bite’, also true of dpca, a ligand potentially
and actually tridentate. The ligands generally are extended
planar arrays. The PR3 ligands also offer a diverse range of
basicities and steric profiles (‘cone angle’), the latter, in a
number of cases interacting with the ortho/syn/peri hydro-
gens of the nitrogen bases. 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 representative species depicted in
Fig. 1. In general, for the present perchlorate systems, the
N,N0-bidentate ligand complexes are quasi-ionic, with the
PAgN2 array quasi-planar and a perchlorate approach dis-
tant and quasi-unidentate. In the dpca adducts, with the
nitrogen ligands coordinating as tripods, the perchlorate
ions are excluded completely. We comment individually
on the various structures as follows:
3.3.1. AgClO4:PPh3:bpy (1:1:1) (1)
Although this complex has the least interactive anion or
solvent moiety, the pyramidalization at the silver atom,
concomitant with the anion approach, is appreciable and
evident in the projection of Fig. 1a. The conformation of
the PPh3 donor is of the less usual form, approaching
quasi-m rather than 3-symmetry, with one of the phenyl
rings (ring 2) lying quasi-parallel/coplanar with the bpy
ligand, the asymmetry of the P–Ag–N angle presumably
consequent on the concomitant interactions involving the
H(6,60) hydrogens, these ‘inner’ hydrogens being disposed

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Effendy et al. / Inorganica Chimica Acta 360 (2007) 1424–1432
Table 2
Ligand and anion descriptors, AgX:ER3:L(:S) (1:1:1(:1))
ha
dAg (A)
Ag–O–Cl (ꢁ)
Ag–P–C(n1)–C(n2(6)) (ꢁ)
˚
ER3:L(:S/X)
(1) PPh3:bpy(:OClO3)
(2) PPh3:bq:OClO3
(3) PPh3:dpa:OClO3
(4) PPh3:dpca(ClO4)
(5) Pcy3:bpy:OClO3
(6) Pcy3:bq:OClO3
(disordered cpt.)
(7) P(o-tol)3:bpy:O(OClO2)
(8) P(o-tol)3:bq:O(OClO2)
(9) P(o-tol)3:dpa:O(OClO2)
(10) P(o-tol)3:dpca(ClO4)
a
11.5(4)
7.01(5)
22.4(2)
62.22(9)
5.6(2)
0.34(1), 0.16(1)
0.504(3), 0.200(3)
0.12(1), 0.81(1)
0.337(4), 0.395(3)
0.060(7), 0.198(8)
0.118(2), 0.125(2)
16.5(7), ꢀ6.7(8), 77.5(8)
ꢀ43.6(2), ꢀ45.2(2), ꢀ60.1(2)
20.3(7), 38.6(7), 55.1(7)
ꢀ7.2(2), 15.8(2), 77.1(2)
ꢀ16.4(5), 60.6(3), ꢀ50.5(4)
66.0(2), ꢀ44.9(3), 59.4(1)
ꢀ9(1)
110.1(1)
115.8(3)
111.1(2)
145.3(8)
142.2(6)
120.5(2)
118.4(3)
108.3(1)
7.89(4)
9.3(1)
16.5(2)
5.49(8)
36.67(8)
0.484(5), 0.012(5)
0.048(8), 0.756(8)
0.296(5), 0.108(4)
0.133(4), 1.019(4)
ꢀ42.6(3), ꢀ48.9(2), ꢀ50.5(3)
42.4(6), 45.3(7), 60.4(5)
ꢀ56.6(2), ꢀ43.1(2), ꢀ47.7(2)
ꢀ58.1(2), ꢀ43.1(2), ꢀ43.7(2)
˚
hꢁ is the dihedral angle between the pair of py or bq planes of the ligand; dA are the silver atom derivations from each plane.
differently with respect to the triphenylphosphine phenyl
substituents, H(6) confronting H(22), quasi-‘edge-on’ to
ring 2 while the H(60) approach to ring 3 is quasi-normal.
except to note that the anion approaches in the relatively
limited range of compounds studied are as unidentates or
weak semi-bidentates. In a number of arrays, the E–Ag–
N,N0 angle pairs are quite disparate, but in others they
are essentially equal.
3.3.2. AgClO4:PPh3:bq (1:1:1) (2)
Here, despite the electronic similarity between bpy and
bq, the Ag–N and Ag–P distances are longer than in 1
(Table 1), and the perchlorate approach is appreciably clo-
ser than in the above bpy counterpart, becoming quasi-
semi-bidentate.
3.3.5. AgClO4:Pcy3:bpy (1:1:1) (5)
This compound is notable for the very large asymmetry
in the P–Ag–N angles, the larger confronting a cy group
which is disposed essentially ‘in-plane’.
3.3.3. AgClO4:PPh3:dpa (1:1:1) (3)
3.3.6. AgClO4:Pcy3:bq (1:1:1) (6)
Here, it is of interest to observe that, compared to (e.g.)
its bq counterpart (above), the geometries in the coordina-
tion sphere are similar, the only substantial change con-
cerning the enlarged ‘bite’ of the ligand, dpa, which
exhibits a substantial dihedral angle between the pair of
aromatic ring planes. Despite the relatively strongly per-
chlorate interaction, as evidenced by the Agꢁ ꢁ ꢁO distance,
the angle sum EAgN2 is still as high as 352.0ꢁ; inter-species
hydrogen-bonding is observed from the (uncoordinated)
central N,H of the ligand to the perchlorate of a nearby
This structure is affected by disorder; although refining
to different site occupancies for the relevant ClO4 and
cyclohexyl components, which are well removed within
the molecule, their proximity in adjacent molecules in the
lattice may be indicative that the disorder is concerted.
That of the anion entails alternative approaches of the
interacting oxygen.
3.3.7. AgClO4:P(o-tolyl)3:bpy (1:1:1) (7)
Here, the anion is only feebly semi-bidentate. In this and
other adducts of the P(o-tol)3 ligand, Ag–P is appreciably
longer than in the adducts of PPh3, Pcy3.
˚
aggregate (O(4)ꢁ ꢁ ꢁH,N (x + 1, y, z) 2.1 (est.), 2.972(8) A).
3.3.4. AgClO4:PPh3:dpca (1:1:1) (4)
Here, the approach of the central nitrogen atom of the
dpca ligand is now comparable with those of the peripheral
‘chelate’ pair, constituting a genuinely tridentate/tripod
mode. The conformations of the intermediate methylene
branches are such that the potential m-symmetry of the
ligand is obviated, becoming rather, quasi-2 locally. The
central NH group is hydrogen-bonded to a perchlorate
3.3.8. AgClO4:P(o-tolyl)3:bq (1:1:1) (8)
In 7 and 9, but not in this compound, the pyramidaliza-
tion at the silver is considerable, reflected in a shorter
Agꢁ ꢁ ꢁO distance in 7.
3.3.9. AgClO4:P(o-tolyl)3:dpa (1:1:1) Æ ½MeCN
(9 Æ ½MeCN)
Here, a semi-bidentate anion interaction is found, as
also in 7 also; the solvent residues in the present array
are disordered about a crystallographic inversion center
and are remote from the substrate.
˚
oxygen atom (H,Nꢁ ꢁ ꢁO(4) 2.20(3), 3.063(3) A).
The ligands Pcy3 and P(o-tol)3 exhibit a more bulky
steric profile than PPh3, as measured by their ‘cone
angles’ [13]; their conformations in projection down their
M–P coordinate bonds may vary from 3- to (in the case
of Pcy3) m-symmetry, here parametrized by the Ag–E–
C–C torsion angle set (Table 1). However, given the
essentially three-coordinate nature of the metal coordina-
tion environments, the change has little impact thereon,
3.3.10. AgClO4:P(o-tolyl)3:dpca (1:1:1) (10)
This compound, cf. the AgClO4:PPh3 analogue 4 above,
is ionic, neither anion nor solvent moieties interacting with
the metal, and the N3Ag chelate rings being unsymmetrical

Effendy et al. / Inorganica Chimica Acta 360 (2007) 1424–1432
1431
Fig. 1. Projections of the cationic (Ph3P)Ag(oligo-dentate Nx-base) arrays, showing, where appropriate, any close approaches or binding of the anions:
(a) [(Ph3P)Ag(N,N0-bpy)]+(OClO3)ꢀ in 1; (b) [(Ph3P)Ag(N,N0-bq)]+(OClO3)ꢀ in 2; (c) [(Ph3P)Ag(N,N0-dpa)]+(OClO3)ꢀ in 3; (d) [(Ph3P)Ag(N,N0,
N00-dpca)]+(ClO4)ꢀ in 4; (e) [(cy3P)Ag(N,N0-bpy)]+(OClO3)ꢀ in 5; (f) [(cy3P)Ag(N,N0-bq)]+(OClO3)ꢀ in 6; (g) [(((o-tol)3)P)Ag(N,N0-bpy)]+(OClO3)ꢀ in 7;
(h) [(((o-tol)3)P)Ag(N,N0-bq)]+(OClO3)ꢀ in 8; (i) (((o-tol)3)P)Ag(N,N0-dpa)]+(OClO3)ꢀ in 9 Æ ½MeCN; (j) (((o-tol)3)P)Ag(N,N0,N00-dpca)]+(ClO4)ꢀ in 10.

1432
Effendy et al. / Inorganica Chimica Acta 360 (2007) 1424–1432
[5] W.J. Geary, Coordin. Chem. Rev. 7 (1971) 81.
[6] K. Shobatake, C. Postmus, J.R. Ferraro, K. Nakamoto, Appl.
Spectrosc. 23 (1969) 12.
relative to each other, perhaps because of their dispositions
relative to the phosphine ligand substituent.
[7] J. Bradbury, K.P. Forest, R.H. Nuttall, D.W.A. Sharp, Spectrochim.
Acta 23 (1967) 2701.
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