Gold and silver complexes with the diselenium ligand [Ph2P(Se)NP(Se)Ph2]-

Article abstract of DOI:10.1016/S0020-1693(02)01440-8

The treatment of potassium diselenoimidodiphosphinato with silver(I) or gold(III) derivatives leads to the synthesis of three-coordinated, [Ag{(SePPh₂)₂N}(PPh₃)], tetranuclear, [Ag₄{(SePPh₂)₂

Full text of DOI:10.1016/S0020-1693(02)01440-8

Inorganica Chimica Acta 347 (2003) 16ꢂ22
/
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Gold and silver complexes with the diselenium ligand
[Ph2P(Se)NP(Se)Ph2]ꢀ
Silvia Canales a, Olga Crespo a, M. Concepcio´n Gimeno a, Peter G. Jones b,
Antonio Laguna a,*, Anca Silvestru c, Cristian Silvestru c
a Departamento de Qu´ımica Inorga´nica, Instituto de Ciencia de Materiales de Arago´n, Universidad de Zaragoza-CSIC, 50009 Zaragoza, Spain
b Institut fur Anorganische und Analytische Chemie, Technische Universitat Braunschweig, Postfach 3329, D-38023 Braunschweig, Germany
¨
¨
c Faculty of Chemistry and Chemical Engineering ‘Babes-Bolyai’ University, Arany Janos 11, 3400 Cluj-Napoca, Romania
Received 4 March 2002; accepted 7 June 2002
Dedicated to Professor Rafael Uso´n
Abstract
The treatment of potassium diselenoimidodiphosphinato with silver(I) or gold(III) derivatives leads to the synthesis of three-
coordinated, [Ag{(SePPh2)2N}(PPh3)], tetranuclear, [Ag4{(SePPh2)2N}3]OTf (4) (OTfꢁOSO2CF3), or square-planar,
[Au(C6F5)2{(SePPh2)2N}] (5), complexes. The crystal structures of [Au2{(SePPh2)2N}(PPh3)2]OTf (2), 4 and 5 have been established
by X-ray diffraction. Complex 2 is associated by goldꢂgold interactions forming tetranuclear dimers. In complex 4 four silver atoms
/
/
forming a distorted tetrahedron are bridged by three ligands, and 5 shows the expected square-planar coordination at gold.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Crystal sturucture; Silver complexes; Gold complexes; Selenium complexes
1. Introduction
of these studies, a parallel work by Schmidbaur et al. has
appeared, reporting the synthesis of several gold com-
Gold and silver have a remarkable affinity for
selenium donor ligands and the number of known
selenolate or selenide [1,2] and phosphineselenide [3,4]
complexes is growing rapidly, probably as a conse-
quence of their interesting structures or their potential
applications in chemotherapy [5].
Recently, interest has been focussed on the coordina-
tion properties of the diselenoimidodiphosphinato anion
[Ph2P(Se)NP(Se)Ph2]ꢀ as a flexible ligand, and a size-
able number of metal complexes have been reported [6].
However, not much work has been carried out in gold
and silver chemistry with this ligand. Until recently the
only such gold complex described was [Au{(SeP-
Ph2)2N}{PPh2NHP(O)Ph2}] [7], but during the course
plexes, [Au{(SePPh2)2N}L] (LꢁPMe3, PPh3, CNC6H3-
/
Me2), [Au{(SePPh2)2N}(PMe3)2], [Au2{(SePPh2)2N}(P-
Ph3)2]ꢃ [BF4]ꢀ, [Au2{(SePPh2)2N}(dppm)]ꢃ[OSO2C-
F3]ꢀ and [Au2{(SePPh2)2N}2] [8]. As part of an ongoing
study of the coordination of ligands containing sulfur or
selenium donor atoms, we present here the results of the
reaction of K[Ph2P(Se)NP(Se)Ph2] with silver(I) or
gold(III) derivatives; these lead to three-coordinated,
[Ag{(SePPh2)2N}(PPh3)], tetranuclear, [Ag4{(SePPh2)2-
N}3](OTf), or square-planar, [Au(C6F5)2{(SePPh2)2N}],
complexes. We also present the crystal structure of the
dinuclear [Au2{(SePPh2)2N}(PPh3)2](OTf).
2. Results and discussion
We have studied the coordination behaviour of the
anion [Ph2P(Se)NP(Se)Ph2]ꢀ in gold and silver com-
plexes obtained according to Scheme 1.
* Corresponding author. Tel.: ꢃ
187.
E-mail address: alaguna@posta.unizar.es (A. Laguna).
/
34-976-761-185; fax: ꢃ34-976-761-
/
0020-1693/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 0 - 1 6 9 3 ( 0 2 ) 0 1 4 4 0 - 8

S. Canales et al. / Inorganica Chimica Acta 347 (2003) 16ꢂ
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17
K[Ph2P(Se)NP(Se)Ph2] reacts with [AuCl(PPh3)] to
give [Au{(SePPh2)2N}(PPh3)] (1), which further reacts
with [Au(OTf)(PPh3)] to give the dinuclear [Au2{(SeP-
Ph2)2N}(PPh3)2]OTf (2), both previously described by
Schmidbaur [8]. We have obtained crystals of 2 and the
crystal structure is described below.
The gold atoms exhibit almost linear geometries
[Se(1)ꢂ
/
Au(1)ꢂ
/
P(3)ꢁ
/
177.340(17) Se(2)ꢂ
/
Au(2)ꢂ
/
P(4)ꢁ
/
178.008(17)8] (Fig. 1, Table 1). The Auꢀ ꢀ ꢀAu distance
˚
(ꢀ5 A) rules out any intramolecular metallic interac-
/
tion. Both in 2 and [Au2{(SePPh2)2N}(dppm)]OTf [8]
tetranuclear cationic dimers are formed, although in
[Au2{(SePPh2)2N}(dppm)]OTf they are formed through
Auꢀ ꢀ ꢀSe interactions of different cations (Auꢀ ꢀ ꢀSeꢁ
/
˚
3.447(1), 3.331(1) A), whereas in 2 goldꢀ ꢀ ꢀgold contacts
˚
3.1712 A)
over an inversion centre (Au(1)ꢀ ꢀ ꢀ Au(2)#ꢁ
/
are responsible; this distance is shorter than the intra-
molecular contacts found in [Au2{(SePPh2)2N}(dpp-
˚
m)]OTf (3.2687(4) A). AuꢂSe distances (2.4231(3),
/
˚
2.4352(3) A) are of the same order as Au(I)ꢂSe found
/
Fig. 1. Structure of the cation in 2. Radii are arbitrary and hydrogen
atoms have been omitted for clarity.
in other complexes, with the same or different ligands, in
which the gold atom displays linear coordination
([Au2{(SePPh2)2N}(dppm)]OTf (2.4280(7), 2.4209(8)
The reaction of the diselenoimidodiphosphinato salt
with [Ag(OTf)(PPh3)], in a molar ratio 1:1 and at room
temperature, gives the new complex [Ag{(SePPh2)2N}-
(PPh3)] (3). It is a white, air- and moisture-stable solid
and behaves as non-conducting in acetone solution. The
˚
˚
A), [Se{AuPPh3)}2{m-Au(C6F5)2}2] 2.4225(9) A [9]).
˚
The AuꢂP distances (2.2788(6), 2.2737(6) A) are very
close to those in [Au{(SePPh2)2N}(PPh3)] [8] (2.2786(9)
/
˚
A) (trigonal geometry at gold) or the Au(I)ꢂP distance
/
Se) vibration at 543 cmꢀ1
.
˚
in [{Se(AuPPh3)}2{m-Au(C6F5)2}2] [9] (2.273(2) A), and
somewhat longer than those in [Au2{(SePPh2)2N}(dpp-
IR spectrum shows the n(Pꢁ
The positive-ion LSI MS exhibits a peak corresponding
to the molecular cation [M]ꢃ at m/zꢁ913 (5%). The 1H
/
˚
m)]OTf (2.265(2), 2.263(2) A). Weak interactions of the
/
hydrogen bonding type Cꢂ
/
Hꢀ ꢀ ꢀO also form a feature of
˚
NMR spectrum shows a multiplet at 7.6 ppm (Ph) and
the 31P{1H} NMR spectrum shows a singlet at 27.6 ppm
[2P, PPh2, J(PSe) 562 Hz] and a doublet [1P, PPh3,
Jave(PAg) 459 Hz].
the packing, with Hꢀ ꢀ ꢀO distances from 2.33 to 2.59 A
(Table 2) involving the triflate oxygen atoms and three
phenyl hydrogens.
Scheme 1. (i) [AuCl(PPh3)]; (ii) [Au(OTf)(PPh3)]; (iii) [Ag(OTf)(PPh3)]; (iv) [Ag(OTf)]; (v) [Au(C6F5)2Cl]2.

18
S. Canales et al. / Inorganica Chimica Acta 347 (2003) 16ꢂ22
/
Table 1
in each case. The trigonal geometry at Ag(1) arises from
coordination by selenium atoms from three different
ligands. The extended structure of the complex consists
of an Ag4Se6 adamantane-type cluster and can be
considered as a tetrahedron of silver atoms inscribed
in a distorted octahedron of selenium atoms (Fig. 2).
This atom framework is known in the structures of
[Cu4(SMe)6] [10], [Cu4(SPh)6] [10,11] and also in other
silver clusters as [Ag4(SCH2C6H4CH2S)3]2ꢀ [12], [Ag4-
{Te(SC4H3)}6]2ꢀ [13] or [Ag4(Se4)3]2ꢀ [14] but only in
˚
Selected bond lengths (A) and bond angles (8) for 2
Bond lengths
Au(1)ꢂ
Au(1)ꢂ
Au(1)ꢂ
Au(2)ꢂ
Au(2)ꢂ
/
P(3)
2.2788(6)
2.4352(3)
3.1712(3)
2.2737(6)
2.4231(3)
Se(1)ꢂ
/
P(1)
P(2)
2.1980(7)
2.2034(7)
1.598(2)
1.590(2)
/
Se(1)
Au(2)#1
P(4)
Se(2)ꢂ
/
/
P(1)ꢂ
/
N
N
/
P(2)ꢂ
/
/Se(2)
Bond angles
P(3)ꢂAu(1)ꢂ
P(3)ꢂAu(1)ꢂ
Se(1)ꢂ
P(4)ꢂAu(2)ꢂ
P(4)ꢂAu(2)ꢂ
Se(2)ꢂAu(2)ꢂ
P(1)ꢂSe(1)ꢂ
P(2)ꢂSe(2)ꢂ
NꢂP(1)ꢂ
NꢂP(1)ꢂ
NꢂP(1)ꢂ
/
/
Se(1)
177.340(17) Nꢂ
/
P(2)ꢂ
P(2)ꢂ
P(2)ꢂ
178.008(17) C(51)ꢂ
Au(1)#1 106.615(16) C(71)ꢂ
Au(1)#1 73.524(7) C(61)ꢂ
/
C(31)
C(41)
Se(2)
105.39(11)
111.01(11)
111.59(8)
/
/Au(2)#1
97.702(16) Nꢂ
/
/
one which includes Agꢂ
Se bonding, [Ag4(SePh)6]2ꢀ
/
/Au(1)ꢂ
/
Au(2)#1 84.468(8) Nꢂ
/
/
/
/Se(2)
/
P(3)ꢂ
P(3)ꢂ
P(3)ꢂ
P(4)ꢂ
P(4)ꢂ
105.34(11) C(101)ꢂP(4)ꢂ
111.96(12) P(2)ꢂNꢂP(1)
118.00(8)
/
Au(1) 114.50(8)
Au(1) 114.28(8)
Au(1) 109.58(8)
Au(2) 114.24(8)
Au(2) 111.12(8)
[2b]. A different geometry has been described for
[Ag4(Se4)4]2ꢀ [14], it consists of a planar rhombus of
four silver atoms, symmetrically disposed around an
inversion centre, which is held together by four Se42ꢀ
ligands, two silver atoms are tetrahedrally coordinated,
whereas the other display trigonal planar coordination.
/
/
/
/
/
/
/
/
/
/
Au(1)
98.169(18) C(81)ꢂ
/
/
/
/
Au(2)
103.821(19) C(91)ꢂ
/
/
/
/
C(11)
C(21)
Se(1)
/
/
Au(2) 113.45(8)
132.64(13)
/
/
/
/
/
/
˚
The Agꢀ ꢀ ꢀAg distances (Table 3) average in 4 3.12 A
˚
(2.9889(10)ꢂ
/
3.3101(13) A), similar values have been
Symmetry transformations used to generate equivalent atoms: #1 ꢀ
/
reported for [Ag4{Te(SC4H3)}6]2ꢀ (3.13 A). A narrower
˚
xꢃ1, ꢀyꢃ1, ꢀzꢃ1.
/
/
/
/
/
range of distances was found in [Ag4(SePh)6]2ꢀ
˚
(2.958(1)ꢂ/3.151(1)
A),
[Ag4(SCH2C6H4CH2S)3]2ꢀ
˚ ˚
3.085(1) A, mean value 3.044 A) or in
(2.998(1)ꢂ
/
Table 2
Hydrogen bonds (A, 8) for 2
[Ag4(Se4)3]2ꢀ (2.990(1)ꢂ
/
˚
3.193(1) A, mean value 3.05
˚
˚
A). The Agꢂ
/
Se distances in the cation vary from
˚
d(Cꢂ
/
H) d(Hꢀ ꢀ ꢀO) d(Cꢀ ꢀ ꢀO)
Ú
/
(Cꢂ
/
2.5922(10) to 2.6446(12) A, this range is narrower than
in the species [Ag4(SePh)6]2ꢀ (2.704(1)ꢂ
Hꢀ ꢀ ꢀO)
˚
2.567(1) A) and
/
[Ag4(Se4)3]2ꢀ (2.545(1)ꢂ
2.710(1) A).
˚
/
C(53)ꢂ
C(94)ꢂ
C(75)ꢂ
C(84)ꢂ
/
H(53)ꢀ ꢀ ꢀO(1)#2 0.95
2.33
2.42
2.59
2.38
3.246(4) 161.3
3.363(3) 171.2
/
H(94)ꢀ ꢀ ꢀO(1)#3 0.95
H(75)ꢀ ꢀ ꢀO(2)#4 0.95
The diselenoimidodiphosphinato salt reacts with the
dimer [Au(C6F5)2Cl]2 to give the neutral gold(III)
complex [Au(C6F5)2{(SePPh2)2N}] (5). It is an air- and
moisture-stable, pale cream solid. It is non-conducting
in acetone solution. The positive-ion LSI MS shows the
/
3.439(3) 149.3
3.191(3) 143.7
/
H(84)ꢀ ꢀ ꢀO(3)
0.95
Symmetry transformations used to generate equivalent atoms: #2 ꢀ
/
x, ꢀyꢃ1, ꢀzꢃ1; #3 x, yꢀ1, z; #4 x, y, zꢀ1.
/
/
/
/
/
/
The treatment of K[Ph2P(Se)NP(Se)Ph2] with
Ag(OTf), in the molar ratio 1:1 or 3:4, gives the ionic
tetranuclear [Ag4{(SePPh2)2N}3]OTf (4) derivative as a
white solid. It behaves as a 1:1 electrolyte in acetone
solution. The positive-ion LSI MS shows the cation
molecular peak [Mꢀ
peaks appear at m/zꢁ
N}2]ꢃ, and m/zꢁ752 (100%), [Ag2{(SePPh2)2N}]ꢃ.
/
OTf]ꢃ [m/zꢁ
1409 (70%), [Ag3{(SePPh2)2-
/
2060 (55%)]. Other
/
/
The IR spectrum shows, apart from the bands arising
from the diselenoimidodiphosphinato ligand, those of
the triflate at 1254(s), 1225(s), 1178(m), 1038(s) cmꢀ1
and those corresponding to n(Pꢁ .
Se) at 529(s) cmꢀ1
/
The 31P{1H} NMR spectrum at room temperature
shows two broad signals at 24.4 and 22.5 ppm, although
at ꢀ55 8C they split to give four singlets at 24.8 [J(PSe)
/
541 Hz], 23.7 (br), 22.9 (br), and 22.1 (br) ppm.
The X-ray stucture determination shows that the
cation contains four silver atoms bridged by three
ligands. The atoms Ag(2), Ag(3) and Ag(4) are bridged
by two selenium atoms of the same and one from a
different ligand, affording distorted trigonal geometries
Fig. 2. Structure of the cation in 4. Radii are arbitrary and hydrogen
atoms have been omitted for clarity.

S. Canales et al. / Inorganica Chimica Acta 347 (2003) 16ꢂ
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19
Table 3
exactly the same plane (the dihedral angle between
C(41)/Au/C(51) and Se(1)/Au/Se(2) planes is 4.38). The
six-membered ring formed by Au, Se(1), P(1), N, P(2),
Se(2) has a twist conformation, as was also described for
[Au{(SePPh2)2N}(PPh3)] or [Au{(SePPh2)2N}(PMe3)2]
˚
Selected bond lengths (A) and bond angles (8) for 4
Bond lengths
Ag(1)ꢂ
Ag(1)ꢂ
Ag(1)ꢂ
Ag(1)ꢂ
Ag(1)ꢂ
Ag(1)ꢂ
Ag(2)ꢂ
Ag(2)ꢂ
Ag(2)ꢂ
Ag(2)ꢂ
Ag(2)ꢂ
Ag(3)ꢂ
Ag(3)ꢂ
Ag(3)ꢂ
Ag(3)ꢂ
/
Se(4)
Se(6)
Se(1)
Ag(3)
Ag(4)
Ag(2)
Se(2)
Se(3)
Se(4)
Ag(4)
Ag(3)
Se(6)
Se(3)
Se(5)
Ag(4)
2.6170(11) Ag(4)ꢂ
2.6259(11) Ag(4)ꢂ
2.6446(12) Ag(4)ꢂ
3.0164(10) Se(1)ꢂ
3.151(2) Se(2)ꢂ
3.1597(12) Se(3)ꢂ
2.5854(14) Se(4)ꢂ
2.6019(9) Se(5)ꢂ
2.6121(17) Se(6)ꢂ
2.9889(10) P(1)ꢂ
3.0979(11) P(2)ꢂ
2.5866(14) P(3)ꢂ
2.6077(10) P(4)ꢂ
2.6103(16) P(5)ꢂ
3.3101(13) P(6)ꢂ
/
Se(1)
Se(2)
Se(5)
2.5850(12)
2.5878(10)
2.5922(10)
2.2118(18)
2.2199(17)
2.216(2)
2.206(2)
2.209(2)
2.218(2)
1.584(6)
1.602(5)
1.606(6)
1.602(5)
1.594(6)
1.611(6)
/
/
/
/
[8].
The Auꢂ
similar range to those Au(III)ꢂ
Ph3)}2{m-Au(C6F5)2}2] (2.4802(8)A) or in [Se{Au2(m-
dppf)}{Au(C6F5)3}] (2.5038(13) A [9]). The AuꢂC
/
/
P(1)
P(2)
P(3)
P(4)
P(5)
P(6)
˚
Se distances (2.4808(3), 2.4832(3) A) lie in a
/
/
/
/
Se found in [{Se(AuP-
˚
/
/
/
/
˚
/
/
/
/
/
distances are very close to those obtained for
[{Se(AuPPh3)}2{m-Au(C6F5)2}2] or [Se{Au2(m-dppf)}-
{Au(C6F5)3}].
Concerning the diselenoimidodiphosphinato moiety,
despite its different coordination pattern, i.e. monome-
tallic biconnective (a) in 5, bimetallic biconnective
(bridging) (b) in 2, or trimetallic tetraconnective (c) in
/
/
N(1)
N(1)
N(2)
N(2)
N(3)
N(3)
/
/
/
/
/
/
/
/
/
/
Bond angles
Ag(3)ꢂAg(1)ꢂ
Se(2)ꢂAg(2)ꢂ
Se(2)ꢂAg(2)ꢂ
Se(3)ꢂAg(2)ꢂ
Ag(4)ꢂAg(2)ꢂ
Ag(4)ꢂAg(2)ꢂ
Ag(3)ꢂAg(2)ꢂ
Se(6)ꢂAg(3)ꢂ
Se(6)ꢂAg(3)ꢂ
Se(3)ꢂAg(3)ꢂ
Ag(1)ꢂAg(3)ꢂ
Ag(1)ꢂAg(3)ꢂ
Ag(2)ꢂAg(3)ꢂ
Se(1)ꢂAg(4)ꢂ
Se(1)ꢂAg(4)ꢂ
Se(2)ꢂAg(4)ꢂ
Se(2)ꢂAg(4)ꢂ
Se(5)ꢂAg(4)ꢂ
Ag(2)ꢂAg(4)ꢂ
Se(1)ꢂAg(4)ꢂ
Se(2)ꢂAg(4)ꢂ
Se(5)ꢂAg(4)ꢂ
Ag(2)ꢂAg(4)ꢂ
Ag(1)ꢂAg(4)ꢂ
Ag(4)ꢂSe(1)ꢂ
/
/
Ag(4)
64.87(4) Ag(2)ꢂ
122.98(4) Ag(2)ꢂ
118.52(4) Ag(4)ꢂ
118.50(4) Ag(3)ꢂ
65.86(3) P(1)ꢂN(1)ꢂ
61.59(4) P(4)ꢂN(2)ꢂ
57.63(2) P(5)ꢂN(3)ꢂ
134.47(4) N(1)ꢂP(1)ꢂ
117.71(5) N(1)ꢂP(2)ꢂ
107.43(4) N(2)ꢂP(3)ꢂ
62.21(3) N(2)ꢂP(4)ꢂ
59.54(4) N(3)ꢂP(5)ꢂ
55.49(2) N(3)ꢂP(6)ꢂ
119.30(3) P(1)ꢂSe(1)ꢂ
121.15(3) P(1)ꢂSe(1)ꢂ
118.94(4) P(2)ꢂSe(2)ꢂ
107.82(3) P(2)ꢂSe(2)ꢂ
100.44(4) P(3)ꢂSe(3)ꢂ
61.87(3) P(3)ꢂSe(3)ꢂ
102.66(4) P(4)ꢂSe(4)ꢂ
108.18(3) P(4)ꢂSe(4)ꢂ
50.73(4) P(5)ꢂSe(5)ꢂ
58.65(3) P(5)ꢂSe(5)ꢂ
55.59(3) P(6)ꢂSe(6)ꢂ
74.10(5) P(6)ꢂSe(6)ꢂ
/
Se(2)ꢂ
Se(3)ꢂ
Se(5)ꢂ
Se(6)ꢂ
/
Ag(4)
Ag(3)
Ag(3)
Ag(1)
70.59(3)
72.98(3)
79.03(4)
70.71(3)
140.2(4)
129.3(4)
134.7(4)
118.5(2)
119.0(2)
115.5(2)
119.6(2)
119.1(2)
120.0(2)
101.97(5)
91.19(6)
95.53(7)
99.80(6)
91.56(6)
104.95(6)
101.80(6)
94.82(6)
93.45(5)
100.60(7)
92.29(6)
92.29(6)
4 (Fig. 4), the Pꢂ
/
Se bond lengths [range 2.195(1)ꢂ
2.220(1) A] within a ligand unit are not significantly
different. They corresponds to single phosphorusꢂ
selenium bonds, while the PꢂN bonds [range 1.584(6)ꢂ
1.611(6) A] are intermediate between single and double
phosphorusꢂnitrogen bonds [cf. the free acid (SeÄ
PPh2)2NH [6a]: PÄ
/
/
/
/
Se(3)
Se(4)
Se(4)
/
/
˚
/
/
/
/
/
/
/
/
/
/
/
/
/
Ag(3)
Ag(1)
Ag(1)
/
/P(2)
˚
/
/
/
/P(3)
/
/
/
/P(6)
/
/
/
/
Se(3)
Se(5)
Se(5)
/
/
Se(1)
Se(2)
Se(3)
Se(4)
Se(5)
Se(6)
˚
/
Se 2.085(1), 2.101(1) A, PꢂN
/
/
/
/
/
˚
1.686(3), 1.678(4) A; [2ꢂ
PPh2ÄNꢂPPh2ÄS [15]: PꢂN 1.612(3), PÄ
A]. By contrast, magnitude of the PꢂNꢂP angle varies
/
(Me2NCH2)C6H4]Teꢂ
/
Sꢂ
/
/
/
/
/
/
/
/
/
N 1.557(3)
/
/
Ag(2)
Ag(4)
Ag(4)
/
/
˚
/
/
/
/
/
/
/
/
/
/
considerably with the coordination pattern, i.e. from
132.64(13)8 in the dinuclear cation of 2, to 116.46(7)8 in
the mononuclear 5 derivative.
/
/
Se(2)
Se(5)
Se(5)
Ag(1)
Ag(1)
/
/
Ag(4)
Ag(1)
Ag(2)
Ag(4)
Ag(2)
Ag(3)
Ag(2)
Ag(1)
Ag(4)
Ag(3)
Ag(3)
Ag(1)
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
Ag(1)
/
/
/
/
Ag(3)
Ag(3)
Ag(3)
/
/
3. Experimental
/
/
/
/
/
/
/
/
Infrared spectra were recorded on a Perkinꢂ
883 spectrophotometer, over the range 4000ꢂ
/
Elmer
200 cmꢀ1
/
/
Ag(3)
Ag(3)
/
/
/
,
/
/
/
/
/
/
Ag(1)
/
/
cation molecular peak, ([M]ꢃ, m/zꢁ
cation [Mꢀ
C6F5]ꢃ is also observed at m/zꢁ
The n(PÄSe) stretching vibration appears in the IR
/
1076 (10%)). The
906 (5%).
/
/
/
spectra at 547(s) cmꢀ1. Other bands arising from the
pentafluorophenyl groups appear at 1511(s), 969(s),
805(m), 795(m) cmꢀ1. The 31P{1H} NMR spectrum
presents only a singlet resonance at 29.7 ppm and the
19F NMR corresponds to the presence of 2 equiv. C6F5
groups, with signals at ꢀ
/
121.8 (m, 4F, o-F), ꢀ
/
158.0 (t,
2F, p-F, J(FF) 18 Hz) and ꢀ
/
162.2 (m, 4F, m-F) ppm.
The X-ray structure of 5 shows that the gold centre
exhibits a significant distortion from square planar
geometry (Fig. 3), attributable to the wide bite angle
of the [Ph2P(Se)NPPh2)]ꢀ ligand [(Se(1)ꢂ
/
Auꢂ
/
Se(2)ꢁ
/
102.718(9) 8] (Fig. 3, Table 4) but also to its rigidity.
The Se(1), Se(2), C(41) and C(42) atoms do not lie in
Fig. 3. Molecular structure of 5. Radii are arbitrary and hydrogen
atoms have been omitted for clarity.

20
S. Canales et al. / Inorganica Chimica Acta 347 (2003) 16ꢂ22
/
Table 4
3.1. Syntheses
˚
Selected bond lengths (A) and bond angles (8) for 5
3.1.1. [Ag{(SePPh2)2N}(PPh3)] (3)
Bond lengths
[Ag(OTf)(PPh3)] (0.0519 g, 0.1 mmol) was added to a
solution of K[Ph2P(Se)NP(Se)Ph2] (0.0581 g, 0.1 mmol)
in dichloromethane (20 cm3) and the mixture was stirred
for 30 min. After separation of the KOTf formed,
concentration of the solution to ca. 5 cm3 and addition
of diethyl ether (10 cm3) gave complex 3 as a white solid.
Yield 75%. LM 16 Vꢀ1 cm2 molꢀ1. Elemental analysis:
Anal. Found: C, 55.40; H, 3.04; N, 1.43. Calc. for
C42H35AgNP3Se2: C, 55.26; H, 3.84; N, 1.53%. 1H
Auꢂ
Auꢂ
Auꢂ
Auꢂ
/
C(41)
C(51)
Se(2)
Se(1)
2.052(2)
2.055(2)
2.4808(3)
2.4832(3)
P(1)ꢂ
P(1)ꢂ
P(2)ꢂ
P(2)ꢂ
/
N
1.604(2)
2.1970(6)
1.596(2)
2.1953(7)
/
/Se(1)
/
/N
/
/Se(2)
Bond angles
C(41)ꢂAuꢂ
C(41)ꢂAuꢂ
C(51)ꢂAuꢂ
C(41)ꢂAuꢂ
C(51)ꢂAuꢂ
Se(2)ꢂAuꢂ
NꢂP(1)ꢂ
NꢂP(1)ꢂ
NꢂP(1)ꢂ
C(1)ꢂ
/
/
C(51)
Se(2)
Se(2)
Se(1)
Se(1)
88.25(10) C(11)ꢂ
/P(1)ꢂ
/
Se(1)
110.07(8)
108.09(11)
111.07(11)
115.31(8)
104.05(8)
109.54(8)
121.37(12)
102.050(19)
101.465(18)
/
/
84.11(6)
171.39(7)
172.90(7)
85.06(7)
Nꢂ
Nꢂ
Nꢂ
C(21)ꢂ
/
P(2)ꢂ
P(2)ꢂ
P(2)ꢂ
/
C(21)
C(31)
Se(2)
/
/
/
/
/
/
/
/
/
/
/
P(2)ꢂ
P(2)ꢂ
NꢂP(1)
Se(1)ꢂ
Se(2)ꢂ
/Se(2)
/
/
Se(1)
102.718(9) C(31)ꢂ
107.07(11) P(2)ꢂ
111.64(10) P(1)ꢂ
116.46(7)
106.65(8)
/
/Se(2)
NMR, ꢀ
/
55 8C, d: 6.8ꢂ8.2 (m, Ph) ppm.
/
/
/
C(1)
/
/
/
/
C(11)
Se(1)
/
/
Au
3.1.2. [Ag4{(SePPh2)2N}3](OTf) (4)
/
/
P(2)ꢂ
/
/
Au
Ag(OTf) (0.0519 g, 0.1 mmol) was added to a solution
of K[Ph2P(Se)NP(Se)Ph2] (0.0581 g, 0.1 mmol) in
dichloromethane (20 cm3) and the mixture was stirred
for 30 min. After separation of the KOTf formed,
concentration of the solution to ca. 5 cm3 and addition
of diethyl ether (10 cm3) gave complex 4 as a white solid.
Yield 78%. LM 84 Vꢀ1 cm2 molꢀ1. Elemental analysis:
Anal. Found: C, 39.26; H, 2.95; N, 1.77; S, 1.87. Calc.
/P(1)ꢂSe(1)
/
for C73H60Ag4F3NO3P6SSe2: C, 39.69; H, 2.71; N, 1.90;
1
S, 1.45%. H NMR, ꢀ
/
55 8C, d: 7.2ꢂ8. (m, Ph) ppm.
/
3.1.3. [Au(C6F5)2{(SePPh2)2N}] (5)
[Au(C6F5)2Cl]2 (0.1133 g, 0.1 mmol) was added to a
solution of K[Ph2P(Se)NP(Se)Ph2] (0.1162 g, 0.2 mmol)
in dichloromethane (20 cm3) and the mixture was stirred
for 30 min. Concentration of the solution to ca. 5 cm3
and addition of hexane (10 cm3) gave complex 5 as a
pale orange solid. Yield 60%. LM 5.0 Vꢀ1 cm2 molꢀ1
.
Elemental analysis: Anal. Found: C, 40.43; H, 1.72; N,
Fig. 4. Different coordination modes of the [Ph2P(Se)NP(Se)Ph2]ꢀ
anion.
1.19. Calc. for C36H20AuF10NP2Se2: C, 40.26; H, 1.86;
1
N, 1.30%. H NMR, d: 7.4ꢂ
/
8 (m, Ph) ppm.
using Nujol mulls between polyethylene sheets. Con-
ductivities were measured in ca. 5ꢄ
10ꢀ4 mol dmꢀ3
3.2. Crystallography
/
solutions with a Philips 9509 conductimeter. C, H, N
and S analyses were carried out with a Perkin Elmer
2400 microanalyser. Mass spectra were recorded on a
VG Autospec, with the liquid secondary-ion mass
spectra (LSI MS) technique, using 3-nitrobenzyl alcohol
as matrix. NMR spectra were recorded on a Varian
UNITY 300 or Bruker ARX 300 apparatus in CDCl3
solutions. Chemical shifts are quoted relative to SiMe4
The crystals were mounted in inert oil on a glass fibre
and transferred to the cold gas stream of a Siemens
Smart 1000 CCD diffractometer equipped with a Sie-
mens LT-2 low temperature attachment. Data were
collected using monochromated Mo Ka radiation (lꢁ
/
˚
0.71073 A). Scan type v and f. Absorption corrections
were based on multiple scans (program SADABS). The
structures were refined on F2 using the program
SHELXL-97 [18]. All non hydrogen atoms were refined
anisotropically. Hydrogen atoms were included using a
riding model.
1
(external, H), CFCl3 (19F, external), and 85% H3PO4
(external, 31P).
AgOTf was purchased from Aldrich and used as
given. [Ag(OTf)(PPh3)] was obtained by reaction of
equimolecular amounts of [AgCl(PPh3)] [16] and
AgOTf. Compound [Au(C6F5)2Cl]2 [17], the potassium
Special refinement details: 2*the complex crystallises
/
with two molecules of dichloromethane. One dichlor-
omethane molecule is disordered over an inversion
centre, the other over two general positions with half
diselenoimidodiphosphinato, K[Ph2P(Se)NP(Se)Ph2]
[6b], and compounds 1 and 2 [8] were prepared
according to literature methods.
occupancies. 4*
/
the structure contains three poorly
resolved acetone molecules, a further region of feature-

S. Canales et al. / Inorganica Chimica Acta 347 (2003) 16ꢂ
/22
21
Table 5
Details of data collection and structure refinement for the complexes 2, 4 and 5
Compound
Chemical formula
Crystal habit
Crystal size (mm3)
Crystal system
Space group
2×
62.5H53Au2Cl3F3NO3P4SSe2
colourless prism
0.37ꢄ0.20ꢄ0.17
triclinic
/
1.5CH2Cl2
4×
/
3(CH3)2CO
5
C
C82H78Ag4F3N3O6P6SSe6
colourless prism
C36H20AuF10NP2Se2
colourless tablet
/
/
0.37ꢄ
triclinic
¯
P1
/
0.11ꢄ
/
0.04
0.24ꢄ
monoclinic
P21/c
/
0.16ꢄ0.06
/
¯
P1
˚
a (A)
14.8441(10)
15.4681(12)
16.0972(12)
91.915(3)
107.702(3)
117.158(3)
3067.5(4)
2
14.188(3)
18.222(4)
20.273(4)
108.08(3)
99.58(3)
109.21(3)
4489.4(16)
2
16.4622(12)
21.4322(16)
10.2734(8)
90
˚
b (A)
˚
c (A)
a (8)
b (8)
g (8)
106.177(3)
90
3
˚
U (A )
3481.2(5)
4
2.048
Z
Dcalc (g cmꢀ3
M
)
1.881
1737.20
1678
1.762
2381.59
2352
1073.36
2040
F(000)
T (8C)
2umax (8)
ꢀ
/
130
60
6.28
ꢀ
/
130
53
3.48
ꢀ
/
130
60
6.492
m(Mo Ka) (mmꢀ1
)
Transmission
0.620ꢂ
65100
17883
0.0266
0.0214
0.0536
17883
751
/0.928
0.743ꢂ
64212
18355
0.0519
0.0467
0.1483
18335
940
/
0.972
0.505ꢂ
74906
10194
0.0482
0.0222
0.0510
10194
469
/0.930
No. of reflections measured
No. of unique reflections
Rint
a
R
(F ꢀ4s(F))
/
b
wR (F2, all reflections)
No. of reflections used
No. of parameters
No. of restraints
c
661
1.002
1.418
137
1.029
2.474
144
0.973
1.225
S
ꢀ3
˚
Max. Dr (e A
)
a
R(F)ꢁ
/
ajjFojꢀ
wR(F2)ꢁ[a{w(Fo2ꢀ
program.
[a{w(Fo2ꢀFc2)2}/(nꢀ
/
jFcjj/ajFoj.
b
/
/
Fc2)2}/a{w(Fo2)2}]0.5; wꢀ1ꢁ
/
s2(Fo2)ꢃ
/
(aP)2ꢃ
/
bP, where Pꢁ
/
[Fo2ꢃ2Fc2]/3 and a and b are constants adjusted by the
/
c
Sꢁ
/
/
/
p)]0.5, where n is the number of data and p the number of parameters.
less electron density probably corresponds to further
solvent. Further crystallographic details are given in
Table 5.
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¨ ¨