Synthesis and structural characterization of adducts of silver(I) oxyanion salts, AgX (X = ClO4, NO3), with Ph2E(CH2)xEPh2 ('dpex'; E = P, As; x = 1-3) and oligodentate aromatic N-bases derivative of 2,2′-bipyridyl, 'L', AgX:dpex:L (2:1:1) or (1:1:1)

Article abstract of DOI:10.1016/j.ica.2006.07.018

Six new adducts of silver(I) perchlorate and nitrate, AgX, with N,N′(,-N″)-oligodentate ligands L, derivative of 2,2′-bipyridyl, together with Ph₂E(CH₂)_xEPh₂ (≡'dpex'), are reported and characterized by spectroscopic and structural studies. Two different stoichiometries were found: AgNO₃:dpex:'tpy' (2:1:1), ('tpy' = 2,2′:6′,2″-terpyridyl; 1: dpex = 'dppm' (Ph₂PCH₂PPh₂); 2: dpex = 'dpam' (Ph₂AsCH₂AsPh₂); 3: dpex = 'dppp' (Ph₂P(CH₂)₃PPh₂)) and AgClO₄:dpex:L (1:1:1), (4: dpex = 'dpae' (Ph₂As(CH₂)₂AsPh₂), L = tpy); 5: dpex = dppp; L = 'phen' (1,10-phenanthroline); 6: dpex = dppp; L = 'dmp' (2,9-dimethyl,1,10-phenanthroline)). In AgNO₃:dpem:tpy (2:1:1) (1,2), tpy acts as a bridging bis(chelate), the central pyridine donor in 'crevice' coordination mode: [(ONO₂)Ag(E-dpem-E′)(N,N′-tpy-N′,N″)Ag(O₂NO)]. A further bridging tpy is found in tetranuclear AgNO₃:dppp:tpy (2:1:1)₂ (3), in which the wrapping of a centrosymmetric Ag(μ-ONO₂)₂Ag kernel by P-dppp-P′ to form [Ag(μ-ONO₂)₂(P-dppp-P′)₂Ag] is pre-empted by the insertion of (Agtpy) into one of the potential Ag-P bonds of each ligand, the third pyridine of the bidentate tpy bridging to a kernel silver atom. AgClO₄:dpae:tpy (1:1:1)_{(∞{divides}∞)} (4) is a single-stranded polymer (?Ag(tpy)(As-dpae-As′)Ag(tpy)?)_{(∞{divides}∞)}, while AgClO₄:dppp:L (1:1:1)₂ (5,6) are dimers of the form [LAg(P-dppp-P′)₂AgL].

Full text of DOI:10.1016/j.ica.2006.07.018

Inorganica Chimica Acta 360 (2007) 1414–1423
www.elsevier.com/locate/ica
Synthesis and structural characterization of adducts of silver(I)
oxyanion salts, AgX (X = ClO4, NO3), with Ph2E(CH2)xEPh2
(‘dpex’; E = P, As; x = 1–3) and oligodentate aromatic
N-bases derivative of 2,20-bipyridyl, ‘L’, AgX:dpex:L (2:1:1) or (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
Six new adducts of silver(I) perchlorate and nitrate, AgX, with N,N0(,-N00)-oligodentate ligands L, derivative of 2,20-bipyridyl,
together with Ph2E(CH2)xEPh2 (”‘dpex’), are reported and characterized by spectroscopic and structural studies. Two different stoichi-
ometries were found: AgNO3:dpex:‘tpy’ (2:1:1), (‘tpy’ = 2,20:60,200-terpyridyl; 1: dpex = ‘dppm’ (Ph2PCH2PPh2); 2: dpex = ‘dpam’
(Ph2AsCH2AsPh2); 3: dpex = ‘dppp’ (Ph2P(CH2)3PPh2)) and AgClO4:dpex:L (1:1:1), (4: dpex = ‘dpae’ (Ph2As(CH2)2AsPh2),
L = tpy); 5: dpex = dppp; L = ‘phen’ (1,10-phenanthroline); 6: dpex = dppp; L = ‘dmp’ (2,9-dimethyl,1,10-phenanthroline)). In
AgNO3:dpem:tpy (2:1:1) (1,2), tpy acts as a bridging bis(chelate), the central pyridine donor in ‘crevice’ coordination mode: [(ONO2)-
Ag(E-dpem-E0)(N,N0-tpy-N0,N00)Ag(O2NO)]. A further bridging tpy is found in tetranuclear AgNO3:dppp:tpy (2:1:1)2 (3), in which the
wrapping of a centrosymmetric Ag(l-ONO2)2Ag kernel by P-dppp-P0 to form [Ag(l-ONO2)2(P-dppp-P0)2Ag] is pre-empted by the inser-
tion of (Agtpy) into one of the potential Ag–P bonds of each ligand, the third pyridine of the bidentate tpy bridging to a kernel silver
atom. AgClO4:dpae:tpy (1:1:1)(1j1) (4) is a single-stranded polymer (ꢀ ꢀ ꢀAg(tpy)(As-dpae-As0)Ag(tpy)ꢀ ꢀ ꢀ)(1j1), while AgClO4:dppp:L
(1:1:1)2 (5,6) are dimers of the form [LAg(P-dppp-P0)2AgL].
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: Silver salts; Diphosphine; Aromatic N-bases; X-ray single crystal studies; NMR; Oxyanions; Phosphorous; N-donor chelating ligands;
Complexes; Structures
1. Introduction
2:1:2 stoichiometry, with some novel forms described, most
being [LAg(E-dpex-E0)AgL]X2 salts, those with x even
being centrosymmetric and trans-oid, with close approaches
to the silver atoms by oxyanions or solvent (MeCN, H2O)
molecules, while those with x = 1 exhibited an AgE . . . EAg
‘cis’ form. 2,20:60,200-Terpyridyl, ‘tpy’, has been also found
in its role as a ligand able to bridge pairs of silver atoms,
linking them into a single-stranded polymer as in AgClO4:
dppp:tpy (2:1:2). For reasons concerned with solubility or
other less tangible considerations, a number of dpex:L com-
binations did not yield adducts of 2:1:2 stoichiometry, but,
In the preceding paper [1] we have described the synthe-
sis, spectroscopic properties and structural features of a
quasi-systematic and comprehensive nature of adducts of
the form AgX (X = oxyanion (NO3, ClO4)):dpex (=
(Ph2E(CH2)xEPh2)),E = P, As:L (L = oligodentate-Nn
donors, derivative of 2,20-bipyridyl), all defining arrays of
*
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.2006.07.018

Effendy et al. / Inorganica Chimica Acta 360 (2007) 1414–1423
1415
rather, other stoichiometries, specifically 2:1:1 or 1:1:1
AgX:dpex:L. We record these in the present paper.
1301s, 1008m, 822s t(NO3), 519s, 504s, 467s, 426w, 409w,
350w. 1H NMR (CD3CN, 293 K): d 3.15 (s, 2H, CH2
dppm), 7.2–7.6 (m, 20H, C6H5dppm + 2H, CHtpy), 8.00 (t,
2H, CHtpy), 8.20 (m, 5H, CHtpy), 8.30 (d, 2H, CHtpy).
2. Experimental
Experimental procedures follow those recorded in the
preceding paper [1]; in the majority of cases crystals suit-
able 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.
2.1.1.3. Synthesis of AgNO3:dppp:tpy (2:1:1) (3). Com-
pound 3 (0.124 g, 25% yield) has been prepared following
a procedure similar to that reported for 1 by using AgNO3
(0.169 g, 1 mmol), ‘dppp’ (Ph2P(CH2)3PPh2) (0.206 g,
0.5 mmol), and tpy (0.116 g, 0.5 mmol). M.p. 284–285 ꢁC.
Anal. Calc. for C42H37Ag2N6O6P2: C, 50.47; H, 3.73; N,
8.41. Found: C, 50.38; H, 3.70; N, 8.34%. IR (nujol,
cmꢁ1): 3048w (CH), 1970w, 1954w, 1881w, 1812w, 1739w
2.1. Syntheses
. . .
. . .
Safety note. Perchlorate salts of metal complexes with
organic ligands are potentially explosive! Only small
amounts of materials should be prepared, and these should
handed with great caution.
t(NO3), 1586s, 1556sh t(C C, C N), 1435s, 1376s,
•
•
1298s, 1036m, 991m, 821m, 520s, 505s, 482s, 474s, 448s,
312w. 1H NMR (CD3CN, 293 K): d 1.8 (br, 4H,
CH2dppp), 2.50 (t, 4H, CH2dppp), 7.2–7.5 (m, 20H,
C6H5dppm + 2H, CHtpy), 8.02 (t, 2H, CHtpy), 8.25 (m, 5H,
CHtpy), 8.31 (d, 2H, CHtpy). 31P NMR (CD3CN, 293 K):
d 5.5 br. 31P NMR (CD3CN, 233 K): d 0.1 (d br, J(P–
Ag): 659 Hz). It was re-crystallized from MeCN in ambi-
ence as 3 Æ H2O.
2.1.1. AgX (=NO3):dpex:L (=tpy) (2:1:1)(n)(ÆnS)
complexes
2.1.1.1. Synthesis of AgNO3:dppm:tpy (2:1:1) (1). A solu-
tion containing AgNO3 (0.169 g, 1.0 mmol), ‘dppm’
(Ph2P(CH2)PPh2) (0.199 g, 0.5 mmol), and tpy (0.116 g,
0.5 mmol) in 20 mL of CH3CN was stirred for 12 h at room
temperature. The solution was then evaporated under vac-
uum and the colorless residue washed with diethyl ether
and shown to be compound 1 (0.160 g, 35 %, yield). M.p.
225–226 ꢁC. Anal. Calc. for C40H33Ag2N6O6P2: C, 49.46;
H, 3.42; N, 8.65. Found: C, 49.33; H, 3.40; N, 8.64%. IR
(nujol, cmꢁ1): 1950w, 1891w, 1817w, 1743w t(NO3),
2.1.2. AgX (=ClO4):dpex:L (1:1:1)(2) (ÆnS) complexes
2.1.2.1. Synthesis of AgClO4:dpae:tpy (1:1:1) (4). Com-
pound 4 has been obtained as 4 Æ 2MeCN by crystalliza-
tion of millimolar stoichiometries of the silver salt with
‘dpae’ (Ph2As(CH2)2AsPh2) and tpy, from acetonitrile
solution by standing and evaporation in ambience. Anal.
Calc. for C45H41AgAs2ClN5O4: C, 53.57; H, 4.10; N,
6.94. Found: C, 53.01; H, 3.91; N, 6.72%. M.p. 213–
216 ꢁC (dec).
. . .
. . .
1615br, 1593s, 1574s t(C C, C N), 1434s, 1380sh,
•
•
1301s, 1008m, 822s t(NO3), 519s, 504s, 467s, 426w, 409w,
350w. 1H NMR (CD3CN, 293 K): d 3.60 (t, 2H, CH2 dppm),
3.75 (sbr, 1H, CH2dppm), 2.72 (sbr, 1H, CH2dppm), 7.28–7.51
(m, 20H, C6H5dppm + 2H, CHtpy), 8.02 (t, 2H, CHtpy), 8.25
(m, 5H, CHtpy), 8.31 (d, 2H, CHtpy). 13C NMR (CD3CN,
293 K): d 25.0 (br, CH2dppm), 124.6 (d, Cdppm), 126.63 (s,
Ctpy), 130.1 (br, Cdppm), 132.3 (d, Cdppm), 134.1 (br, Cdppm),
140.17 (s, Ctpy), 141.5 (s, Ctpy), 151.83 (s, Ctpy), 153.78 (s,
Ctpy), 154.52 (s, Ctpy). 31P NMR (CD3CN, 293 K): d 7.0
2.1.2.2. Synthesis of AgClO4:dppp:phen (1:1:1) (5). Com-
pound 5 (0.312 g, yield 39%) has been prepared following a
procedure similar to that reported for 1 by using AgClO4
(0.104 g, 0.5 mmol), dppp (0.206 g, 0.5 mmol), and ‘phen’
(1,10-phenanthroline) (0.091 g, 0.5 mmol). M.p. 134–
135 ꢁC. Anal. Calc. for C39H34AgClNO4P: C, 58.56; H,
4.28; N, 3.50. Found: C, 58.46; H, 4.22; N, 3.39%. IR (nujol,
cmꢁ1): 3046w, 2000br, 1890br, 1817br, 1620m, 1587m,
1
31
1
31
`
(d, J( P–Ag): 500.7 Hz); 6.0 ı(d br, J( P–Ag): 580 Hz).
The compound was re-crystallized from MeCN as 1 Æ 1½
MeCN.
. . .
. . .
1567m, 1537m t(C C, C N), 1076 sbr, 621br t(ClO4),
•
•
508w, 477w, 414w, 320w, 241w. 1H NMR (CD3CN,
293 K): d 2.02 (sbr, 2H, CH2dppp), 2.54 (sbr, 4H, CH2dppp),
7.16–7.32 (m, 20H, C6H5dppp), 7.65 (m, 2H, CHphen), 7.90
(s, 2H, CHphen), 8.43 (m, 2H, CHphen), 8.68 (sbr, 2H,
CHphen). 13C NMR (CD3CN, 293 K): d 25.0br, 29.0br
(CH2dppp), 125.22 (s, Cphen), 128.11 (s, Cphen), 129.98 (br,
Cdppp), 130.52 (s, Cphen), 131.51 (br, Cdppp), 133.23 (br,
Cdppp), 138.61 (s, Cphen), 144.97 (s, Cphen), 151.34 (s, Cphen).
31P NMR (CD3CN, 293 K): d 3.8 (d, J(31P–Ag): 410.6 Hz).
It was re-crystallized from MeCN/CHCl3 in ambience as
5 ꢀ CHCl3 ꢀ ½H2O.
2.1.1.2. Synthesis of AgNO3:dpam:tpy (2:1:1) (2). A solu-
tion of tpy (0.116 g, 0.5 mmol) in 10 mL of CH3CN was
added to a solution containing AgNO3 (0.169 g, 1.0 mmol)
and ‘dpam’ (Ph2As(CH2)AsPh2) (0.286 g, 0.5 mmol). A
precipitate was immediately formed and the suspension
was stirred 12 h at room temperature, then filtered off;
the precipitate was re-crystallized from MeCN/ethanol
and washed with ethanol and shown to be compound 2.
2EtOH (0.318 g, 56%, yield). M.p. >141 ꢁC. Anal. Calc.
for C44H45Ag2As2N5O8: C, 46.46; H, 3.99; N, 6.16. Found:
C, 46.60; H, 4.15; N, 6.32%. IR (nujol, cmꢁ1): 3300br
(OH), 3060 (CH) 1955br, 1890w, 1815w, 1740w t(NO3),
2.1.2.3. Synthesis of AgClO4:dppp:dmp (1:1:1) (6). Com-
pound 6 (0.360 g,% yield) has been prepared following a
procedure similar to that reported for 1 by using AgClO4
. . .
. . .
1615br, 1593s, 1574s t(C C, C N), 1434 s, 1380sh,
•
•

1416
Effendy et al. / Inorganica Chimica Acta 360 (2007) 1414–1423
3
˚
(0.208 g, 1.0 mmol), dppp (0.412 g, 1.0 mmol), and ‘dmp’
(2,9-dimethyl,1,10-phenanthroline) (0.208 g, 1.0 mmol).
M.p. 241–242 ꢁC. Anal. Calc. for C41H38AgClN2O4P2: C,
59.47; H, 4.63; N, 3.38. Found: C, 59.30; H, 4.58; N,
3.34%. IR (nujol, cmꢁ1): 3048 (CH), 2007w, 1955w,
1895w, 1805w t(ClO4), 1618s, 1590s, 1556m, 1502s
83.766(5), b = 89.204(6), c = 74.579(7)ꢁ, V = 3885 A . Dc
(Z = 2) = 1.700 g cmꢁ3. lMo = 1.15 mmꢁ1; specimen: 0.23
· 0.15 ·
0.14 mm;
‘T’min/max = 0.87.
2hmax = 55ꢁ;
Nt = 36970, N = 17573 (Rint = 0.037), No = 13682;
R = 0.061, Rw = 0.092.
Variata. Water molecule hydrogen atoms were not
located.
. . .
. . .
t(C C, C N), 1083 sbr, 622s t(ClO4), 548m, 512s,
•
•
481s, 468m, 445m, 429w, 395m, 327w, 311w. 1H NMR
(CD3CN, 293 K): d 1.91 (s, 2H, CH2dppp), 2.53 (br, 12H,
CH3dmp), 2.70 (br, 4H, CH2dppp), 7.28 (m br, 20H,
C6H5dppp), 7.67 (d, 2H, CHdmp), 7.99 (s, 2H, CHdmp), 8.47
(d, 2H, CHdmp). 13C NMR (CD3CN, 293 K): d 27.11 (s,
CH3dmp), 27.9 (br, CH2dppp), 124.72 (s, Cdmp), 126.08 (s,
Cdmp), 127.71 (s, Cdmp), 128.95 (s, Cdppp), 130.39 (s, Cdppp),
131.98 (br, Cdppp), 139.87 (s, Cdmp), 142.53 (s, Cdmp), 159.99
(s, Cdmp). 31P NMR (CD3CN, 293 K): d 2.5br, ꢁ0.1br,
2.2.1.2. AgX (=ClO4):dpex:L (1:1:1)(2) (ÆnS) complexes.
2.2.1.2.1.
AgClO4:dpae:tpy
(1:1:1)(1j1) Æ 2MeCN
(4 Æ 2MeCN). C45H41AgAs2ClN5O4, M = 1009.0. Mono-
clinic, space group C2/c ðC62h; No: 15Þ, a = 26.943(3),
˚
b = 12.647(1), c = 27.331(3) A, b = 112.303(2)ꢁ, V = 8616
A . Dc (Z = 8) = 1.555 g cmꢁ3. lMo = 2.10 mmꢁ1; speci-
3
˚
men: 0.24 · 0.17 · 0.04 mm; ‘T’min/max = 0.73. 2hmax = 60ꢁ;
Nt = 62491, N = 12556 (Rint = 0.060), No = 9089; R =
0.043, Rw = 0.056.
1
ꢁ2.9s br; ꢁ5.6 (d, J(31P–Ag): 231.8 Hz). It was re-crystal-
lized from MeCN as 6 Æ 2MeCN.
2.2.1.2.2. AgClO4:dppp:phen (1:1:1)2 Æ CHCl3 Æ ½H2O
(5 Æ CHCl3 Æ ½H2O). C79H70Ag2Cl5N4O8.5P4, M = 1728.3.
16
Orthorhombic, space group Pnma (D , No. 62), a =
2h
˚
2.2. Structure determinations
3
˚
25.110(2), b = 24.185(1), c = 12.6723(7) A, V = 7695 A .
Dc (Z = 4) = 1.492 g cmꢁ3. lMo = 0.82 mmꢁ1; specimen:
0.30 · 0.20 · 0.17 mm; ‘T’min/max = 0.90. 2hmax = 68ꢁ;
Nt = 159800, N = 15947 (Rint = 0.092), No = 8894; R =
0.044, Rw = 0.047.
General procedures are described in an accompanying
paper [1]; specific details are given below. CCDC 295270–
295275.
Variata. Perchlorate, chloroform and water molecules
were modelled as disordered.
2.2.1. Crystal/refinement data
2.2.1.1. AgX (=NO3):dpex:L (=tpy) (2:1:1)(n)(ÆnS)
complexes.
2.2.1.1.1. AgNO3:dppm:tpy (2:1:1) Æ 1½MeCN (1 Æ 1½
MeCN. C43H37.5Ag2N6.5O6P2, M = 1019.0. Monoclinic,
space group P21/c (C25h, No. 14), a = 10.400(3), b =
2.2.1.2.3. AgClO4:dppp:dmp (1:1:1)2 Æ 2MeCN (6 Æ 2Me-
CN). C86H82Ag2Cl2N6O8P4, M = 1738.2. Triclinic, space
ꢀ
group P1, a = 11.1399(6), b = 13.5758(7), c = 13.7822(7)
˚
A, a = 105.572(1), b = 99.532(1), c = 91.127(1)ꢁ, V =
3
1976 A . Dc (Z = 1) = 1.461 g cmꢁ3. lMo = 0.71 mmꢁ1
;
˚
3
˚
˚
15.902(4), c = 26.033(6) A, b = 100.705(3)ꢁ, V = 4230 A .
Dc (Z = 4) = 1.600 g cmꢁ3. lMo = 1.06 mmꢁ1; specimen:
0.42 · 0.05 · 0.05 mm; ‘T’min/max = 0.80. 2hmax = 58ꢁ;
Nt = 43029, N = 11196 (Rint = 0.099), No = 5522; R =
0.053, Rw = 0.050.
specimen: 0.25 · 0.13 · 0.11 mm; ‘T’min/max = 0.90. 2hmax
75ꢁ; Nt = 40210, N = 20148 (Rint = 0.021), No = 15213;
R = 0.034, Rw = 0.038. (x, y, z, Uiso H refined.
=
)
3. Discussion
Variata. Acetonitriles 3, 4 were modelled as disordered,
the former over a pair of sites (occupancies set at 0.5), the
latter about a centre of symmetry, with geometrical con-
straints. Displacement parameters throughout the structure
were generally rather high.
3.1. Syntheses
The reaction of two equivalents of AgNO3 with 1
equivalent of 2,20:60,200-terpyridyl (tpy) and 1 equivalent of
bis(diphenyl)phosphinomethane (dppm) or bis(diphenyl)-
arsinomethane (dpam) in acetonitrile at room temperature
gave rise to compounds AgNO3:dppm:tpy (2:1:1), (1), and
AgNO3:dpam:tpy (2:1:1), (2), respectively (Chart 1), vari-
ously solvated, in which tpy and dppm bridge together
two silver metal centers. Both compounds formed only
when this reactant stoichiometry was rigorously used.
When dppp (=1,3-bis(diphenylphosphino)propane) was
employed as ligand, AgNO3:dppp:tpy (2:1:1)2 (3) (Chart 2),
characterized as having the same stoichiometry but differ-
ent nuclearity, has been obtained, formed, presumably, as
a consequence of the longer methylene chain in dppp.
The reaction between 1 equivalent of dpae, AgClO4 and
tpy produces the polymeric species AgClO4:dpae:tpy
(1:1:1). 2MeCN (4) (Chart 3).
2.2.1.1.2. AgNO3:dpam:tpy (2:1:1) Æ 2EtOH (2 Æ 2EtOH).
ꢀ
C44H45Ag2As2N5O8, M = 1137.5. Triclinic, space group P1
(C1i , No. 2), a = 10.5899(7), b = 13.5459(9), c = 15.6398
˚
(10) A, a = 94.108(2), b = 90.491(2), c = 101.240(2)ꢁ,
3
V = 2194 A . Dc (Z = 2) = 1.721 g cmꢁ3
.
lMo = 2.45
˚
mmꢁ1; specimen: 0.29 · 0.22 · 0.11 mm; ‘T’min/max = 0.70.
2hmax = 65ꢁ; Nt = 43890, N = 15783 (Rint = 0.037), No =
11774; R = 0.045, Rw = 0.059.
Variata. Phenyl ring 12x was modelled as disordered
over two sites of equal occupancy after trial refinement
(rigid body constraints). The hydroxylic hydrogen atom
of EtOH (2) was not located.
2.2.1.1.3. AgNO3:dppp:tpy (4:2:2) Æ H2O (3 Æ H2O). C84-
ꢀ
H76Ag4N10O13P4, M = 1989.0. Triclinic, space group P1,
˚
a = 10.556(4),
b = 18.557(7),
c = 20.700(7) A,
a =

Effendy et al. / Inorganica Chimica Acta 360 (2007) 1414–1423
1417
N
N
N
N
N
N
O
O
O
O
Ag
As
Ag
Ag
P
Ag
P
O
N
O
N
N
O
N
O
O
O
O
O
As
Ph
Ph
Ph
Ph
Ph
Ph
CH2
2
CH2
1
Ph
Ph
Chart 1.
Ph
Compound 5 formed also when an excess of AgClO4 and
dppp was employed.
Ph
CH2
CH2
P
Complexes 1–3, 5 and 6 are air-stable colorless materi-
als, soluble in polar solvents such as acetonitrile, dimethyl-
formamide and dimethylsulfoxide. They are, however,
insoluble in water, ether and tetrahydrofuran, and exhibit
moderate solubility in chlorinated hydrocarbons.
Solid samples of these compounds generally show no
sensitivity to light, although their solutions are sometimes
unstable, darkening after 1 day. Conductivity data are in
accordance with an ionic nature in acetonitrile solution.
N
CH2
Ph
Ag
P
Ph
O
O
N
N
O
Ag
O
N
N
O
N
N
O
Ph
Ph
P
3.2. Spectroscopy
N
CH2
CH2
CH2
P
The infrared spectra of 1–6 (see Section 2) are consistent
with the formulations proposed, showing all the bands
required by the presence of the nitrato or perchlorato coun-
ter-ions, phosphino or arsino donors, and N-donor ligands.
The IR spectra of the nitrate derivatives 1 and 2 are very
similar, showing broad bands at ca. 1300 cmꢁ1 due to m4,
and sharp bands at ca. 1000, 800 and 750 cmꢁ1 due to m2,
m3 and m5, consistent with the bidentate O2NO coordination
mode found in the crystal structures [2]. The IR spectrum of
3 is very complex in the same region, as expected for the
presence of bridging bidentate and ionic nitrate group.
The IR spectra of the perchlorato silver complexes 4–6
Ph
Ph
3
Chart 2.
Similarly the reaction between equimolar quantities of
AgClO4, dppp, and phenanthroline (phen) or 2,9-dim-
ethylphenanthroline (dmp) in MeCN at room temperature
always yielded the derivatives AgClO4:dppp:phen (1:1:1)
(5) and AgClO4:dppp:dmp (1:1:1) (6) respectively (Chart 4).
N
N
Ph
Ph
As
Ph
Ph
As
Ph
Ph
As
N
N
N
N
Ag
CH2
CH2
Ag
H
CH2
CH2
CH2
CH2
H
Ag
Ag
As
As
Ph
As
N
N
N
N
Ph
Ph
Ph
Ph
Ph
N
N
-
(2ClO4 )
4
Chart 3.

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Effendy et al. / Inorganica Chimica Acta 360 (2007) 1414–1423
Ph
Ph
Ph
Ph
Ph
Me
CH2
CH2
Ph
CH2
CH2
Ph
Ph
N
P
CH2
P
P
CH2
P
Me
N
N
N
N
N
Ag
Ag
Ag
P
Ag
P
N
N
Me
Ph
P
CH2
P
CH2
6
Me
Ph
Ph
Ph
CH2
CH2
CH2
CH2
Ph
Ph
Ph
Ph
-
-
2 ClO4
2 ClO4
5
Chart 4.
show two absorptions characteristic of ionic perchlorate
groups: in each case, a strong band at ca. 1080 cmꢁ1 (m3)
and a sharp medium or strong band at ca. 625 cmꢁ1 (m4) [3].
The room temperature 31P NMR spectrum of 1 consists
of a more intense doublet at 7.0 ppm, flanked by a broad
doublet at ca. 6.0 ppm, both arising from coupling between
1
1
In the H NMR spectra of 1–6 the signals due to the
the phosphorus and silver atoms. The J(Ag–P) coupling
diphosphine or diarsine show a different pattern cf. those
found for the free donors, confirming the existence, at least
partial, of complexes in solution.
constant values for the first signal lie intermediate between
those expected for the AgP and AgP2 moieties and are
lower than those expected for AgPN2 and AgPN3 coordi-
nation cores [4–6]. These values are analogous to those
found in systems containing AgPO2N2 cores, supporting
the retention of complex 1 in solution, while the second
signal could be assigned to an ionic species originating
from nitrate dissociation in solution. The d and coupling
31P chemical shifts (CD3CN) solution and 31P–Ag cou-
pling constants for derivatives 1, 3, 5 and 6 are reported in
Section 2. They have been found to be slightly dependent on
the dilution of the solution. Our experiments have been car-
ried out in the range of concentration 0.003–0.005 mol/L.
Fig. 1. Projections of the molecules of (a), (b) [(ONO2)Ag(E-dppm,dpam-E0)(N,N0-tpy-N0,N00)Ag(O2NO)] (= AgNO3:dpem:tpy (2:1:1)2), in 1 ꢀ 1½MeCN,
2 Æ EtOH.
Table 1
Geometrical descriptors of AgNO3:dpem:tpy (2:1:1) (1, 2)
˚
˚
˚
X/dpem/L
Ag
Ag–E (A)
Ag–N (A)
Agꢀ ꢀ ꢀAg (A)
2.9965(8)
E–Ag–N (ꢁ)
N–Ag–N (ꢁ)
Ag–E–C (ꢁ)
E–C–E (ꢁ)
(NO3/)dppm/tpy (1)a
Ag(1)
2.356(2)
2.390(2)
2.4694(4)
2.4702(5)
2.243(8)(p)
2.737(5)(c/b)
2.311(5)(p)
2.582(5)(c/b)
2.324(3)(p)
2.450(3)(c/b)
2.262(4)(p)
2.804(3)(c/b)
147.0(2)(p)
127.4(1)(c/p)
119.7(1)(p)
137.5(1)(c/p)
115.35(8)(p)
142.82(7)(c/p)
145.27(8)(p)
121.10(7)(c)
68.4(2)
113.3(2)
111.1(3)
Ag(2)
Ag(1)
Ag(2)
68.0(2)
69.4(1)
66.2(1)
112.6(2)
109.4(1)
113.4(1)
(NO3/)dpam/tpy (2)a
3.0154(4)
110.1(2)
˚
Ag–O(11,12;21,22) 2.462(5), 2.718(6); 2.379(5), 2.955(4)(dppm adduct); 2.390(3), 2.857(3); 2.445(3), 2.690(4) A (dpam adduct). O(11)–Ag(1)–
E(1),N(11,110); O(21)–Ag(2)–E(2), N(10,100) are: 113.8(1), 98.2(2), 72.9(2); 131.1(1), 80.9(2), 100.6(2)(dppm): 125.72(6), 108.8(1), 81.7(9); 113.2(1), 71.5(1),
101.4(1)ꢁ(dpam). ‘c’ and ‘p’ denote central and peripheral rings of the tpy ligand.
a
In these two adducts, the silver coordination spheres are augmented by chelating nitrate approaches.

Effendy et al. / Inorganica Chimica Acta 360 (2007) 1414–1423
1419
constant values found for compound 3 are close to those
found for 2:1:2 species as reported in the preceding paper
[1], and support the existence of an AgPN2 coordination
environment in solution, all nitrates being ionic, in accor-
dance with conductivity data. As previously found, the
Dd(31P) = d(31Pcomplex) ꢁ d(31Pligand), the differences in
shift between each free diphosphine and corresponding sil-
ver(I) derivatives, are greater in the derivatives 1 and 3, in
which only a P-donor atom is coordinated to silver, than
those in 5 and 6 in which two P-donor atoms are coordi-
nated to the metal.
The 31P NMR spectrum of 5 is in accordance with a tet-
rahedral silver center, four-coordinated by two P atoms
from two bridging dppm and a chelating N2-donor, the
1J(Ag–P) coupling constant being in the range typical of
AgP2N2 cores.
The 31P NMR spectrum of 6 is more complex than in
the previous, four different signals being found, suggesting
considerable dissociation and the formation of new com-
1
pounds in solution. The J(Ag–P coupling constant) value
determined for the unique sharp doublet found at room
temperature is in the range typical of an AgP4 coordination
core [7], suggesting formation of the [Ag(dppp)2]+ cation.
The different behaviour with respect to compound 5 is pre-
sumably a consequence of the greater steric hindrance of
dmp with respect to phen.
3.3. Single crystal X-ray studies
3.3.1. AgNO3:dpem:tpy (2:1:1)(ÆnS) (1 ꢀ 1½MeCN (E = P),
2 Æ 2EtOH (E = As))
This pair of complexes, diversely solvated, crystallise
each with one formula unit, devoid of crystallographic
symmetry, as the asymmetric unit of the structure; they
Fig. 2. Projection of the centrosymmetric [Ag4(NO3)2(tpy)2(dppp)2]2+
cation, in 3 Æ H2O (cation 1; cation 2 is similar).

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Effendy et al. / Inorganica Chimica Acta 360 (2007) 1414–1423
Fig. 3. (a) Projections of the cations of: (i) ½fðtpyÞAggdpaeꢂðþ1j1Þ, in 4 Æ 2MeCN; (ii) [(phen)Ag(dppp)2Ag(phen)]2+, in 5 ꢀ CHCl3 ꢀ ½H2O; (iii) [(dmp)Ag-
(dppp)2Ag(dmp)]2+, in 6 Æ 2MeCN. (b) Unit cell contents of: (i) [{(tpy)Ag}dpae](1j1)(ClO4) (4) Æ 2MeCN, projected down b; (ii) [(phen)Ag(dppp)2Ag-
(phen)](ClO4)2 ð5Þ ꢀ CHCl ꢀ ½H2O, projected down c; (iii) [(dmp)Ag(dppp)2Ag(dmp)](ClO4)2 (6) Æ 2MeCN projected down a.
are not isomorphous. In aspect they may be considered as
similar to the cis-(2:1:2) adducts described in the previous
paper [1], with the pair of Ag–E bonds quasi-parallel.
The role of the tpy, however, is unusual in that the central
pyridine performs the uncommon role previously described
as ‘crevice’ coordination [8–10]. In lying between the two
metal atoms and coordinating to both (via the nitrogen)
to either side of the plane, with each peripheral pyridine

Effendy et al. / Inorganica Chimica Acta 360 (2007) 1414–1423
1421
viously described in AgClO4:tpy:MeCN (3:5:1) [11]). In
consequence, the N2AgE coordination environment is
compact, amply accommodating a chelating O,O0-nitrate
approach (Fig. 1, Tables 1,2). The two complexes may be
considered as having quasi-2 symmetry and as binuclear
neutral molecules [(ONO2)Ag(E-dpem-E)(N,N0-tpy-
N0,N00)Ag(O2NO)], the totality comprising the asymmetric
unit of the structure in each case.
3.3.2. AgNO3:dppp:tpy (4:2:2) Æ H2O (3 Æ H2O)
Binuclear ‘parcel’ compounds, of the form AgX:dppx
(1:1)2 ” Ag(l-X)2(P-dppx-P)2Ag, have been described pre-
viously [12], the central Ag(l-X)2Ag four-membered kernel
being ‘wrapped’ by a pair of bridging dppx ligands: exam-
ples are recorded therein for O-nitrate, dppx = dppb, dpph.
Such may be regarded as a take-off point for the present
array (Fig. 2, Table 3) in which two independent centro-
symmetric tetramers are found, one half of each pertaining
to the asymmetric unit; in the pair of centrosymmetric ker-
˚
nels, Ag–O are 2.418(4), 2.591(5); 2.436(4), 2.567(4) A, with
˚
Agꢀ ꢀ ꢀAg 4.245(1), 4.184(2) and Oꢀ ꢀ ꢀO 2.665(6), 2.748(6) A,
similar to the previously recorded binuclear adducts; Ag–P
˚
is 2.354(2) A, the other Ag–P interaction preempted by the
insertion of an independent silver as (AgL, L = tpy), the
latter linking to the second phosphorus of the ligand, and
one of the peripheral oxygens of the nitrate. The tpy
behaves only as a bidentate, the third (peripheral) pyridine
completing the coordination sphere of the kernel silver.
The pair of silver atoms are cis-oid about the dppp ligand,
and not coplanar with the PCCCP spine. The nitrate is
rather unsymmetrically bound in the kernel (despite similar
Ag–O), Ag–O–N being 115.7(4), 126.0(4), 115.1(3),
128.9(4)ꢁ; O–N–O range between 119.0(5)ꢁ and 120.9(5)ꢁ,
˚
with N–O 1.226(7)–1.249(6) A, the longer being to the ker-
nel oxygen. Kernel; peripheral Ag lie 0.49(1), 0.67(1);
˚
0.23(1), 0.12(1); 1.52(1), 1.38(1) A out of the NO3 planes,
with the latter making dihedral angles of 15.9(2), 18.0(2)ꢁ
with the central (obligate) Ag2O2 planes. The kernel Ag–
˚
N(tpy) distances (2.233(6) A (2·)) are shorter than the
outer Ag–N(c,p) distances (2.346(5), 2.326(5); 2.253(7),
˚
˚
2.280(6) A). The peripheral O–Ag approaches (2.609(5),
2.567(4) A) may be considered as a perturbing approach
to a typical PAgN2 environment, the angle sums being
354.4ꢁ, 354.0ꢁ.
The final group of compounds is of 1:1:1 AgX:dpex:L
stoichiometry.
3.3.3. Complexes of AgX:dpex:L (1:1:1) stoichiometry
3.3.3.1. AgClO4:dpae:tpy (1:1:1)(1j1) Æ 2MeCN (4 Æ 2Me-
CN). This complex is essentially simple, one formula unit
(plus solvent) comprising the asymmetric unit of the struc-
ture, with successive silver atoms linked into a single-
stranded polymer chain by As-dpae-As0 ligands, the tpy
ligands coordinating to the silver as simple tridentates, thus
, the roles of
anions and solvents simply those of spectators filling lattice
voids (Fig. 3, Tables 4 and 5), with the central axis of the
Fig. 3 (continued)
ring associated exclusively with one of the metal atoms, the
role of the tpy is as a bridging bis(chelate), fulfilling the role
of the pair of N,N0-chelates found in the (2:1:2) complexes.
(Although rare, such a mode of coordination has been pre-
(ꢀ ꢀ ꢀAg(tpy)(As-dpae-As0)Ag(tpy)ꢀ ꢀ ꢀ)(1j1)

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Effendy et al. / Inorganica Chimica Acta 360 (2007) 1414–1423
Table 3
Selected geometries: [Ag4(NO3)(tpy)2(dppp)2](NO3)2 (3)
Atoms Parameter Atoms
Parameter
˚
Distances (A)
Ag(1)–O(11)
Ag(1)–O(11)
Ag(1)–P(1)
Ag(1)–N(11)
Ag(1)ꢀ ꢀ ꢀAg(2)
Ag(1)ꢀ ꢀ ꢀAg(1)
Ag(2)–O(12)
Ag(2)–P(2)
2.591(5) Ag(3)–O(21)
2.418(4) Ag(3)–O(21)
2.354(2) Ag(3)–P(3)
2.233(6) Ag(3)–N(21)
3.179(1) Ag(3)ꢀ ꢀ ꢀAg(4)
4.245(2) Ag(3)ꢀ ꢀ ꢀAg(3)
2.609(5) Ag(4)–O(22)
2.340(2) Ag(4)–P(4)
2.346(5) Ag(4)–N(210)
2.253(7) Ag(11)–N(2100)
2.567(4)
2.436(4)
2.345(2)
2.233(6)
3.302(1)
4.183(2)
2.660(5)
2.344(2)
2.326(5)
2.280(6)
Ag(2)–N(110)
Ag(2)–N(1100)
Angles (ꢁ)
O(11)–Ag(1)–O(11)
O(11)–Ag(1)–P(1)
O(11)–Ag(1)–N(11)
O(11)–Ag(1)–P(1)
O(11)–Ag(1)–N(11)
P(1)–Ag(1)–N(11)
Ag(1)–O(11)–Ag(1)
O(12)–Ag(2)–P(2)
O(12)–Ag(2)–N(110)
O(12)– Ag(2)–N(1100)
P(2)–Ag(2)–N(110)
O(2)–Ag(2)–N(1100)
N(110)–Ag(2)–N(1100)
Ag(2)–O(12)–N(1)
64.2(1)
104.9(1)
88.6(2)
105.0(1)
111.0(2)
142.9(1)
115.8(2)
90.2(1)
124.5(2)
81.3(2)
139.3(2)
141.2(1)
71.4(2)
O(21)–Ag(3)–O(21)
O(21)–Ag(3)–P(3)
O(21)–Ag(3)–N(21)
O(21)–Ag(3)–P(3)
O(21)–Ag(3)–N(21)
P(3)–Ag(3)–N(21)
Ag(3)–O(21)–Ag(3)
O(22)–Ag(4)–P(4)
O(22)–Ag(4)–N(210)
O(22)–Ag(4)–N(2100)
P(4)–Ag(4)–N(210)
P(4)–Ag(4)–N(2100)
N(210)–Ag(4)–N(2100)
Ag(4)–O(22)–N(2)
66.6(1)
104.8(1)
88.5(2)
104.1(1)
111.2(2)
144.8(1)
113.4(2)
91.3(2)
121.9(2)
79.1(2)
140.5(2)
142.8(1)
70.6(2)
124.0(4)
126.1(4)
Torsion angles (ꢁ)
Ag(1)–P(1)–C(1)–C(2)
P(1)–C(1)–C(2)–C(3)
C(1)–C(2)–C(3)–P(2)
C(2)–C(3)–P(2)-Ag(2)
ꢁ66.4(6)
165.6(5)
ꢁ178.5(5)
63.3(5)
Ag(3)–P(3)–C(4)–C(5) ꢁ66.5(6)
P(3)–C(4)–C(5)–C(6)
C(4)–C(5)–C(6)–P(4)
C(5)–C(6)–P(4)–Ag(4)
168.8(5)
179.7(5)
61.4(6)
Centrosymmetrically related atoms are italicized. tpy C5N/C5N interpla-
nar dihedral angles (c/p, c/p00; p/p00) (degrees): 31.5(3), 20.1(3), 39.6(3)
(ligand 1); 42.4(3), 10.6(3); 44.2(3) (ligand 2). Deviations of silver atoms
are: ligand 1 Ag(1)/p, 0.56(1), Ag(2)(c,p00) 0.86(1), 0.11(1); ligand 2:
00
˚
Ag(3)/p, 0.35(1), Ag(4)(c,p ) 0.73(1), 0.18(1) A. Nitrates 1,2 make dihe-
dral angles of 15.9(2), 18.0(2)ꢁ with the associated Ag2O2 planes; silver
atom deviations are: nitrate 1: Ag(1), 0.49(1); Ag(1) 0.23(1); Ag(2) 1.52(1);
˚
nitrate 2: Ag(3) 0.67(1); Ag(3) 0.12(1); Ag(4) 1.38 (1) A.
tpy approximately parallel to b, and the ligand parallel to
the bc plane. The five-coordinate geometry about the
metal, (tpy-N3)AgAs2, provides an As2 counterpart of that
already defined for [(tpy-N3)Ag(PPh3)2](ClO4), [13], in
which Ag–N,N0,N00 are 2.614(2), 2.457(2), 2.561(2), Ag–P
˚
are 2.492(1) and 2.525(1) A, and P–Ag–P 121.8(1)ꢁ.
3.3.3.2. The AgClO4:dppp:L (L = phen, dmp) (1:1:1)(2)
-
(ÆnS) dimers (5 Æ CHCl3 Æ ½H2O, 6 Æ 2MeCN). This pair of
complexes, although not isomorphous, and distinctly differ-
ent, are similar, being of the form [LAg(P–dppp–P)2AgL]
with no close interactions between the dimer and anions
or solvent. In each case one half of the dimer comprises
the asymmetric unit. However, whereas the dmp complex
is centrosymmetric, the phen complex lies on a crystallo-
graphic mirror plane (in space group Pnma), which passes
through the central carbon atoms of the two ligands, the
C3 chains lying normal to that plane and to each other
(Fig. 3), whereas in the dmp adduct they are obligate paral-

Effendy et al. / Inorganica Chimica Acta 360 (2007) 1414–1423
1423
lel; for all ligands, the pair of apparent silver atoms are
essentially cis-oid. The silver environments of the two struc-
tures are very similar, perhaps the most striking difference
being in the P–Ag–P angle (139.24(1) (dmp), 145.49(3)ꢁ
(phen)). As might be expected in arrays containing substan-
tial planar components, parallel packing of these, often cen-
trosymmetrically related, is a feature of a number of the
lattice arrays; a number of the more spectacular are dis-
played in the projections of Fig. 3(b).
References
[1] A. Cingolani, Effendy, C. Pettinari, R. Pettinari, B.W. Skelton, A.H.
White, Inorg. Chim. Acta 360 (2007) 1388.
[2] A.B.P. Lever, E. Mantovani, B.S. Ramaswamy, Can. J. Chem. 49
(1971) 1957.
[3] M.R. Rosenthal, J. Chem. Ed. 50 (1973) 331.
[4] R.G. Goel, P. Pilon, Inorg. Chem. 17 (1978) 2876.
[5] E.L. Muetterties, C.W. Alegranti, J. Am. Chem. Soc. 94 (1972) 6386.
[6] A. Cingolani, Effendy, F. Marchetti, C. Pettinari, B.W. Skelton,
A.H. White, J. Chem. Soc., Dalton Trans. (1999) 4047.
[7] Effendy, J.V. Hanna, F. Marchetti, D. Martini, C. Pettinari, R.
Pettinari, B.W. Skelton, A.H. White, Inorg. Chim. Acta 357 (2004)
1523.
[8] G.A. Bowmaker, Effendy, P.J. Harvey, P.C. Healy, B.W. Skelton,
A.H. White, J. Chem. Soc., Dalton Trans. (1996) 2459.
[9] M.G.B. Drew, P.J. Baricelli, P.C.H. Mitchell, A.R. Read, J. Chem.
Soc., Dalton Trans. (1983) 649.
[10] M.G.B. Drew, P.C.H. Mitchell, A.R. Read, J. Chem. Soc., Chem.
Commun. (1982) 238.
[11] S. bin Silong, J.D. Kildea, W.C. Patalinghug, B.W. Skelton, A.H.
White, Aust. J. Chem. 47 (1994) 1545.
[12] Effendy, C. Di Nicola, M. Fianchini, C. Pettinari, B.W. Skelton, N.
Somers, A.H. White, Inorg. Chim. Acta 358 (2005) 763, and
references therein.
[13] E.W. Ainscough, A.M. Brodie, S.L. Ingham, J.M. Waters, J. Chem.
Soc., Dalton Trans. (1994) 215.