Structural characterization of silver(I) complexes of diphenylmethanimine and (diphenylmethyleneamino)diphenylphosphine

Article abstract of DOI:10.1016/S0020-1693(02)01438-X

The reaction of NH=CPH₂ with the silver species [AgX(PPh₃)] (X=ClO₄, SO₃CF₃) affords the derivatives [Ag(PPh₃)(NH=CPh₂)]X. Complexes [Ag(Ph₂PN=CPh₂)₂

Full text of DOI:10.1016/S0020-1693(02)01438-X

Inorganica Chimica Acta 347 (2003) 9Á15
/
www.elsevier.com/locate/ica
Structural characterization of silver(I) complexes of
diphenylmethanimine and
(diphenylmethyleneamino)diphenylphosphine
Antonio Codina a, Olga Crespo b, Eduardo J. Ferna´ndez a, Peter G. Jones c,
Antonio Laguna b,*, Jose´ M. Lo´pez-de-Luzuriaga a, M. Elena Olmos a
a Departamento de Qu´ımica, Universidad de La Rioja, Grupo de S´ıntesis Qu´ımica de La Rioja, UA-CSIC, La Rioja, Spain
b Departamento de Qu´ımica Inorga´nica, Instituto de Ciencia de Materiales de Arago´n, Universidad de Zaragoza-CSIC, E-50009 Zaragoza, Spain
c Institut fur Anorganische und Analytische Chemie der Technischen Universitat, Postfach 3329, D-38023 Braunschweig, Germany
¨
¨
Received 28 September 2001; accepted 19 November 2001
Dedicated in honor of Professor R. Uso´n
Abstract
The reaction of NHÄ
/
CPH2 with the silver species [AgX(PPh3)] (Xꢀ
/
ClO4, SO3CF3) affords the derivatives [Ag(PPh3)(NHÄ
/
CPh2)]X. Complexes [Ag(Ph2PNÄ
/
CPh2)2]X (XꢀCl, ClO4, SO3CF3) have been obtained from Ph2PNÄ
/
/
CPh2 and the corresponding
silver salt AgX. X-ray diffraction studies have been carried out for four of the derivatives.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Crystal structures; Silver complexes; Ketimine complexes
1. Introduction
been employed as ligands giving rise to various mono-
nuclear gold(I) and silver species that, in some cases,
form supramolecular structures via aurophilic or hydro-
gen bonding. In case of the only reported silver(I)
complex the structure consists of a dimer in which a
Ketimines are among the most widely used functional
groups in organic chemistry, notably in the stereoselec-
tive synthesis of organic derivatives, which is nowadays
a rapidly growing research area. In spite of their
importance in organic chemistry, and although an
enormous variety and number of nitrogen-containing
ligands have been tested in inorganic or organometallic
chemistry, ketimines have seldom been used as sub-
strates or ligands. Regarding the coinage metals, for
instance, ketimine copper complexes have been pro-
posed as intermediates in the oxidative coupling of
tetrafluoroborate anion connects two [Ag(NHÄ
/
CPh2)2]ꢁ units by hydrogen bonding of the form NÁ
/
Hꢀ ꢀ ꢀF [6].
We have reported recently the structural characteriza-
tion of silver(I) complexes of stoichiometries [Ag(CF3-
SO3)L]) (Lꢀ
(CF3SO3) (Lꢀ
/
PPh3, PPh2Me, SC4H8) and [AgL2]-
PPh3, PPh2Me) in which the solid state
/
structures display a wide variety of nuclearities, silver
co-ordination numbers, trifluoromethanesulfonate co-
ordination modes and secondary interactions; these
depend variously on the nature of the neutral ligand
and the donor capabilities of the anion [8]. In the present
research we synthesized and structurally characterized
ammonia to produce hydrazine, [1Á4] but the inter-
/
mediates have never been characterized. In a few recent
studies benzophenoneimine [5,6] or its derivative (di-
phenylmethyleneamino)diphenylphosphine [7] have
silver(I) complexes with the nitrogen-donor ligand NHÄ
/
CPh2 and its phosphine derivative Ph2PÁ CPh2
starting from silver(I) salts with the anions chloride,
perchlorate or trifluoromethanesulfonate.
/
NÄ
/
* Corresponding author. Tel.: ꢁ
187.
E-mail address: alaguna@posta.unizar.es (A. Laguna).
/
34-976-761-185; fax: ꢁ34-976-761-
/
0020-1693/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0020-1693(02)01438-X

10
A. Codina et al. / Inorganica Chimica Acta 347 (2003) 9Á15
/
2. Results and discussion
ppm [J(107AgÁ
/
P)ꢀ
/
510.5; J(109AgÁ
/
P)ꢀ589.1 Hz] 3,
/
respectively. These coupling constants are in accordance
with an s contribution to the hybridization at the silver
centres corresponding to a linear geometry, as reported
for other phosphine complexes [8,11]. No signal splitting
is observed for complex 2; in the NMR spectrum in
The reaction between AgClO4, AgCl or AgCF3SO3
and 2 equiv. of Ph2PNÄ
/
CPh2 at room temperature leads
to the complexes [Ag(Ph2PNÄ
/
CPh2)2]X (XꢀClO4 1, Cl
/
2, CF3SO3 3) in high yields (Scheme 1). The products are
yellow crystalline solids stable to air and moisture; their
composition has been confirmed by elemental analysis.
The IR spectra (nujol mulls) show imino stretching
CDCl3 at ꢂ50 8C, nevertheless, the multiplet separa-
/
tion of about 448 Hz is smaller than for the triflate and
perchlorate derivatives and is in accordance with a
frequencies at nꢀ ,
1602 (1), 1610 (2) and 1619 (3) cmꢂ1
/
decrease of the PÁ
/
AgÁP angle [11]. This result has
/
and bands due to the anions perchlorate [9] or triflate
[10] at 1103 and 622 cmꢂ1 or 1287, 1244 and 1146 cmꢂ1
for complexes 1 and 3, respectively. Complex 2 also
shows a weak band at 376 cmꢂ1 which could be
been confirmed in structural studies (see below).
Complexes 1 and 2 (Figs. 1 and 2, Tables 1 and 2)
each consist of a three-coordinate silver centre bonded
to the two phosphorus atoms of two different Ph2PNꢀ
/
assigned to a stretching n(AgÁCl) mode and may
/
CPPh2 ligands and to one oxygen atom of a perchlorate
group (1) or a chlorine ligand (2). In compound 2 the
silver and chlorine atoms lie on a twofold axis and thus
the metal coordination is exactly planar. The silver atom
in compound 1 is essentially coplanar with the donor
atoms P(1), P(2) and O(1) (mean deviation of four
indicate tricoordination at the silver center. The struc-
tural situation is not clear for the other derivatives 1 and
3 because of the overlapping of the vibrational modes.
1
In the H NMR spectra in HDA or CDCl3 solutions
only the phenyl resonances are observed. The conduc-
tivity in acetonitrile solutions are: 158 (1), 92 (2) and 140
(3) Vꢂ1 cm2 molꢂ1, in accordance with a 1:1 ionic
formulation; nevertheless the different values are con-
sistent with a greater dissociation of the perchlorate or
triflate anions than the chloride, for which the coordi-
nating capability at silver is stronger.
The solution structure was first studied by means of
31P{1H} NMR experiments. In the three complexes the
data are indicative of a regioselective coordination of
the silver centre to the phosphorus atoms. Thus, the
NMR spectra at room temperature show resonances at
46.8(m) and 51.2(m) for 1, at 44.7(m) and 50.1(m) for 2
and at 42.9(m) and 46.5(m) for 3, different from that of
˚
atoms 0.014 A). The angles around the metal centers are
dissimilar. Compound 1 exhibits a P(1)Á
of 154.22(2)8, are P(1)ÁAgÁO(1) 109.23(4)8, P(2)Á
O(2) 96.46 with (4)8. In compound 2 the P#1ÁAgÁ
angle is 134.62(3)8; PÁAgÁCl 112.690(14)8. This may be
/
AgÁ/P(2) angle
/
/
/
AgÁ
/
/
/P
/
/
attributed to the weaker coordination of the triflate
ligand than the chloride, with a concomitant decrease in
the perturbation of the otherwise ideally linear geome-
the free ligand (dꢀ36.4 ppm). The fluxionality in these
/
complexes seems to be responsible for the broad
resonances observed. In fact, this fluxionality is typical
in the co-ordination chemistry of silver and can be
attributed to exchange phenomena involving the neutral
ligands. These processes can be stopped in some cases at
low temperature, showing the coupling constants of a
unique kind of magnetically active phosphorus with the
107Ag and 109Ag isotopomers. Thus in the spectra for
complexes 1 and 3 in HDA at ꢂ
signals split into two doublets centered at 42.2 ppm
[J(107AgÁ 511.6; J(109AgÁ
P)ꢀ P)ꢀ590.5 Hz] 1 and 43.1
/
50 8C the multiplet
Fig. 1. Molecular structure of compound 1. Hydrogen atoms are
omitted for clarity. Radii are arbitrary.
/
/
/
/
Scheme 1.

A. Codina et al. / Inorganica Chimica Acta 347 (2003) 9Á
/15
11
Table 2
˚
Selected bond lengths (A) and bond angles (8) for compound 2
Bond lengths
AgÁ
AgÁ
PÁ
/
P
Cl
2.4193(5)
2.5058(7)
1.7132(18)
PÁ
/
C(21)
1.811(2)
1.822(2)
1.285(3)
/
PÁ
/
C(11)
/
N(1)
N(1)ÁC(1)
/
Bond angles
P#1ÁAgÁ
PÁAgÁCl
N(1)ÁPÁ
N(1)ÁPÁ
C(21)Á
N(1)ÁPÁ
/
/
P
134.62(3)
112.690(14)
104.65(9)
100.30(9)
102.28(9)
117.29(6)
C(21)Á
C(11)Á
C(1)Á
N(1)Á
N(1)Á
/
PÁ
PÁ/
/
Ag
118.89(7)
110.90(7)
/
/
/
Ag
/
/
C(21)
/
N(1)Á
C(1)Á
C(1)Á
/
P
122.21(15)
118.01(18)
125.15(19)
/
/
C(11)
/
/
C(31)
C(41)
/
PÁ/
C(11)
/
/
/
/
Ag
Fig. 2. Molecular structure of compound 2. Hydrogen atoms are
omitted for clarity. Radii are arbitrary.
AgÁ
/
Cl distance to that found in 2 has been observed in
˚
[AgCl{P(C6H11)3}2] (2.489(1) A) [16]. Possible CÁ
/
Hꢀ ꢀ ꢀO
Table 1
hydrogen bonds in 1, involving Hꢀ ꢀ ꢀO distances of 2.48
˚
Selected bond lengths (A) and bond angles (8) for compound 1
˚
and 2.52 A, are shown in Table 3 and their effect is to
link the molecules in chains parallel to the y axis.
The reaction of equimolecular quantities of
Bond lengths
AgÁ
AgÁ
AgÁ
/
P(1)
P(2)
O(1)
2.4020(6)
2.4101(6)
C(1)Á
/
C(31)
C(41)
N(2)
1.495(3)
1.496(3)
/
C(1)Á
/
[AgX(PPh3)] (Xꢀ
neimine in dichloromethane at room temperature af-
fords high yields of the corresponding nitrogenÁ
phosphorus-donor ligand complexes [Ag(PPh3)(NHÄ
/ClO4 4, CF3SO3 5) and benzopheno-
/
2.5554(17) C(2)Á
1.7029(18) C(2)Á
/
1.284(3)
1.482(3)
P(1)Á
P(1)Á
P(1)Á
P(2)Á
P(2)Á
P(2)Á
C(1)Á
/
N(1)
/
C(81)
/
/
C(11)
C(21)
N(2)
1.815(2)
1.823(2)
1.712(2)
1.810(2)
1.818(2)
1.285(3)
C(2)Á
/
C(71)
1.498(3)
/
/
ClÁ
ClÁ
ClÁ
ClÁ
/
O(3)
O(2)
O(4)
O(1)
1.4283(18)
1.4377(18)
1.4410(17)
1.4492(17)
CPh2)]X as white solids. Reactions with more than 1
equiv. of benzophenoneimine did not lead to an increase
of the coordination number and, by spectroscopical
methods, the excess ligand was detected unchanged in
the reaction mixtures. The composition of the complexes
4 and 5 has been confirmed by elemental analysis. The
IR spectra show imino stretching frequencies at 1602 (4)
and 1609 cmꢂ1 (5) and the molar conductivities in
acetonitrile solutions confirm their ionic nature, with
values of 177 (4) and 164 Vꢂ1 cm2 molꢂ1 (5) typical of
1:1 electrolytes. Their 31P{1H} NMR spectra in acetone
solutions show similar features. In both cases at room
temperature there are two multiplets at 17.9 and 12.7
/
/
/C(61)
/
/C(51)
/
/
N(1)
Bond angles
P(1)Á
P(1)Á
P(2)Á
N(1)Á
N(1)Á
C(11)Á
N(1)ÁP(1)Á
C(11)ÁP(1)Á
C(21)ÁP(1)Á
N(2)ÁP(2)Á
N(2)ÁP(2)Á
C(61)Á
N(2)ÁP(2)Á
C(61)ÁP(2)Á
C(51)ÁP(2)Á
/
AgÁ
AgÁ
AgÁ
/
P(2)
O(1)
O(1)
154.22(2)
109.23(4)
96.46(4)
N(1)Á
N(1)Á
C(31)Á
C(2)Á
C(2)Á
103.52(10) C(81)Á
/
C(1)Á
C(1)Á
/
C(31)
125.40(19)
117.12(19)
117.44(17)
118.4(2)
/
/
/
/C(41)
/
/
/C(1)ÁC(41)
/
/
P(1)Á
P(1)Á
P(1)Á
Ag
Ag
Ag
/
C(11)
C(21)
C(21)
105.88(10) N(2)Á
/
/C(81)
/
/
100.42(9) N(2)Á
/
/C(71)
125.1(2)
/
/
/C(2)Á
/C(71)
116.50(19)
110.66(12)
109.63(11)
109.46(11)
109.35(11)
109.04(11)
108.67(11)
116.35(10)
122.64(16)
121.73(17)
/
/
118.83(7)
112.93(7)
113.48(8)
O(3)Á
O(3)Á
O(2)Á
/
ClÁ
ClÁ
ClÁ
ClÁ
ClÁ
ClÁ
O(1)Á
C(1)Á
C(2)Á
/
O(2)
O(4)
O(4)
O(1)
O(1)
O(1)
Ag
/
/
/
/
/
/
/
/
/
/C(61)
105.57(10) O(3)Á
99.91(10) O(2)Á
104.24(10) O(4)Á
117.68(7)
114.14(8)
113.55(7)
/
/
/
/C(51)
/
/
/
P(2)Á
Ag
Ag
Ag
/
C(51)
/
/
Table 3
/
/
ClÁ
/
/
˚
Hydrogen bonds (A, 8)
/
/
/
N(1)Á
N(2)Á
/P(1)
/
/
/
/P(2)
DÁ
/
Hꢀ ꢀ ꢀA
d(DÁ
/
H) d(Hꢀ ꢀ ꢀA) d(Dꢀ ꢀ ꢀA)
Ú(DHA)
/
a
Compound 1
C(22)Á
/
H(22)ꢀ ꢀ ꢀO(2)
0.95
H(75)ꢀ ꢀ ꢀO(4)#1 0.95
2.52
2.48
3.420(3)
3.425(3)
158.8
171.6
try. The AgÁP bond distances are similar for both
/
C(75)Á
/
˚
˚
derivatives [2.4020(6), 2.4101(6) A (1), 2.4193(5) A (2)].
b
Compound 4
NÁ
/
H(01)ꢀ ꢀ ꢀO(3)
0.83(2)
2.27(2)
3.051(3)
156(2)
These values are longer than those found in
˚
[Ag4Cl4(dppm)2] [12] (2.366(2) A for three-coordinated
˚
and 2.379(2) A for four-coordinated silver) or in other
‘AgPPh3’ fragments [13], but they are shorter than in
c
Compound 5
NÁ
C(23)Á
C(16)Á
/
H(01)ꢀ ꢀ ꢀO(1)#1
0.77(3)
2.32(3)
2.37
2.56
2.933(4)
3.289(5)
3.395(5)
137(3)
162.2
146.8
/
H(23)ꢀ ꢀ ꢀO(2)#2 0.95
H(16)ꢀ ꢀ ꢀO(3)#1 0.95
/
[Ag(dppf)(PPh3)]ClO4 (dppfꢀ
no)ferrocene) [14] (2.4386(3)Á
trigonal silver centre. The AgÁ
/
1,2-bis(diphenylphosphi-
a
˚
Symmetry transformations used to generate equivalent atoms: #1
/
2.4870(12) A) with a
distance in
(2.5554(17) A) is similar to the longest found in
[Ag(CF3SO3)(PPh3)] (two determinations 2.357(2)Á
x, yꢁ
/1, z.
/O
1
b
Symmetry transformations used to generate equivalent atoms: #1
˚
ꢂ
/
xꢁ
/
1/2, ꢂ
Symmetry transformations used to generate equivalent atoms: #1
xꢁ1, y, ꢂzꢁ1/2.
/
yꢁ
/
1/2, zꢁ
/
1/2. #2 x, ꢂ
/
yꢁ
/
1, zꢁ
/
1/2.
c
/
˚
˚
ꢂ/
/
/
/
2.572(3) A [8], 2.29(2)Á2.546(12) A [15]). A similar
/

12
A. Codina et al. / Inorganica Chimica Acta 347 (2003) 9Á15
/
ppm (4) and 17.6 and 12.1 ppm (5), respectively. These
split at low temperature into two doublets centred at
Table 4
˚
Selected bond lengths (A) and bond angles (8) for compound 4
14.3 ppm [J(109AgÁ
/
P)ꢀ
/
743.0, J(107AgÁ
/
P)ꢀ
/
643.6 Hz]
Bond lengths
4 and at 14.0 ppm [J(109AgÁ
/
P)ꢀ
/
744.5; J(107AgÁ
/
P)ꢀ
/
AgÁ
AgÁ
NÁ
C(1)Á
PÁC(41)
ClÁ
ClÁ
/
N
2.1402(16)
2.9153(17)
1.282(2)
AgÁ
/
P
O(4)
2.3565(5)
3.0166(19)
1.485(3)
644.9 Hz] 5, respectively. In the 1H NMR spectra, only a
single NH proton is observed for both complexes over
/
O(2)
AgÁ
/
/
C(1)
C(21)
C(1)ÁC(11)
/
/
1.490(3)
PÁ/C(31)
1.8158(18)
1.820(2)
the whole temperature range investigated (ꢂ
/
50 to ꢁ
/
/
1.8185(19)
1.4271(16)
1.4356(18)
PÁ/C(51)
25 8C). These data seem to indicate that the coordina-
tion at silver in both complexes is similar; this situation
is different from that mentioned above for the phos-
phine derivatives 1 and 2. Attempts to prepare for
comparison purposes the corresponding chloride com-
plex by reaction of [AgCl(PPh3)] and equimolecular
amounts of benzophenoneimine left the starting materi-
als unchanged.
Despite the similarity of the chemical formula of
complexes 4 and 5, the environment at silver is very
different. In both complexes the phosphorus atom of a
triphenylphosphine ligand and the nitrogen of the
HNCPh2 group are bonded to the metal atom. Never-
theless, compound 5 (Fig. 3) resembles complexes 1 and
2 in the distorted trigonal planar geometry at the silver
/O(1)
ClÁ/O(4)
1.4300(18)
1.4386(17)
/O(3)
ClÁ/O(2)
Bond angles
NÁAgÁ
PÁAgÁ
PÁAgÁ
C(1)Á
NÁC(1)Á
C(31)Á
C(41)Á
C(41)Á
O(1)ÁClÁ
O(4)ÁClÁ
O(4)ÁClÁ
/
/
P
170.34(5)
101.91(4)
113.08(4)
134.64(14)
121.21(17)
105.92(8)
103.17(8)
119.55(6)
110.09(11)
108.44(13)
108.42(12)
NÁ
NÁ
O(2)Á
NÁC(1)Á
C(11)ÁC(1)Á
C(31)Á
C(31)Á
C(51)Á
O(1)ÁClÁ
O(1)ÁClÁ
O(3)ÁClÁ
/AgÁ
/O(2)
87.73(6)
73.96(6)
46.15(5)
/
/
O(2)
/AgÁ
/O(4)
/
/
O(4)
/
AgÁ
C(11)
C(21)
/
O(4)
/
NÁ
/
Ag
/
/
119.30(17)
119.39(16)
106.53(9)
110.00(6)
110.76(6)
110.59(11)
110.72(11)
108.51(11)
/
/
C(21)
/
/
/
PÁ
PÁ
PÁ
/
C(41)
C(51)
Ag
/
PÁ
PÁ
PÁ
/
C(51)
Ag
/
/
/
/
/
/
/
/
Ag
/
/
O(4)
O(3)
O(2)
/
/
O(3)
O(2)
O(2)
/
/
/
/
/
/
/
/
˚
centre (Ag, P, N and O(3) coplanar to within 0.026 A,
PÁAgÁ 155.96(8)8). The AgÁ bond distance
(2.3482(10) A) is shorter than those found in 1 and 2;
/
/N
/P
˚
˚
that corresponding to the AgÁO bond is 2.616(2) A. The
/
˚
N distance in 5 (2.149(3) A) lies in the range found
AgÁ
in [Ag(NHÄ
the shortest values found in [Ag{P(C6H4MeÁ
/
˚
/
CPh2)2]BF4 (2.2223(2) A) [6] and is close to
/
˚
Pyrazolyl) (2.194(4), 2.411(4) A)
4)3}{BPh2(pz)2}] (pzꢀ
/
[13c]; longer AgÁN bond distances have been found in
/
˚
[Ag(dppf)(phen)]ClO4 (2.343(3), 2.361(3) A [14]. A
selection of bond lengths and angles is shown in Table 4.
In compound 4 (Fig. 4) the environment of silver is
almost linear, with an NÁ
/
AgÁP angle of 170.34(5)8.
/
This is essentially linear geometry, marginally distorted
by the weak coordination to two oxygen atoms of a
perchlorate ligand (AgÁ
/
O
distances (2.9153(17),
Fig. 4. Molecular structure of compound 4. Hydrogen atoms except
NH are omitted for clarity. Radii are arbitrary.
˚
3.0166(19) A). This geometry has been observed in
silverÁtriflurosulphonate derivatives such as [Ag(CF3-
SO3)(PPh2Me)2] [8]. Despite the different geometry both
the AgÁP and AgÁN distances are close to those found
in 5. A selection of bond lengths and angles is given in
Table 5. Possible NÁ
Hꢀ ꢀ ꢀO hydrogen bonds have been
observed in both complexes, involving Hꢀ ꢀ ꢀO distances
/
/
/
/
˚
2.27(2) (4), 2.32(3) A (5) (see Table 3). Compound 5 also
shows CÁ
/
Hꢀ ꢀ ꢀO hydrogen bonds involving Hꢀ ꢀ ꢀO
˚
distances of 2.37, 2.56 A. In this complex the effect of
the two shortest hydrogen bonds is to connect the
molecules to layers parallel to the yz plane (two layers
per cell) (see Fig. 5).
Fig. 3. Structure of compound 5. Hydrogen atoms except NH are
omitted for clarity. Radii are arbitrary.

A. Codina et al. / Inorganica Chimica Acta 347 (2003) 9Á
/15
13
Table 5
3. Anal. Found (1): C, 63.25; H, 4.18; N, 2.65. Calc. for
C50H40N2O4AgClP2: C, 64.0; H, 4.3; N, 3.0%. Anal.
Found (3): C, 59.39; H, 3.96; N, 2.46. Calc. for
C51H40P2AgO3SF3: C, 62.01: H, 4.08; N, 2.83%. 1H
˚
Selected bond lengths (A) and bond angles (8) for compound 5
Bond lengths
AgÁ
AgÁ
AgÁ
PÁ
/
N
2.149(3)
2.3482(10)
2.616(2)
1.818(3)
PÁ
PÁ
NÁ
/
C(31)
1.822(3)
1.828(3)
1.273(4)
NMR (1) (298 K) 7.94Á
(m, PhÁ
H). 31P{1H} NMR (1) (298 K) 46.8 (m, PPh2),
51.2 (m, PPh2), (223 K) dꢀ P)ꢀ
42.2 dd (J(107AgÁ
511.5; J(109AgÁ
P)ꢀ590.5 Hz), 3 (298 K) 42.9 (m,
PPh2), 46.5 (m, PPh2), (223 K) dꢀ
43.1 dd (J(107AgÁ
P)ꢀ P)ꢀ589.1 Hz).
510.5; J(109AgÁ
/
7.19 (m, PhÁ
/
H), (3) 7.95Á7.11
/
/P
/C(51)
/O(3)
/C(1)
/
/
C(41)
/
/
/
Bond angles
/
/
NÁ
NÁ
PÁAgÁ
C(41)ÁPÁ
C(41)ÁPÁ
C(31)ÁPÁ
/AgÁ
/
P
155.96(8)
90.07(10)
113.56(6)
104.80(16)
106.29(16)
103.98(16)
C(41)Á
C(31)Á
C(51)Á
C(1)ÁNÁ
SÁO(3)ÁAg
/
PÁ
PÁ
PÁ
/
Ag
Ag
Ag
114.50(11)
112.06(12)
114.22(13)
124.8(2)
/
/
/AgÁ
/
O(3)
/
/
/
/
/
/
/
O(3)
/
/
/
/
C(31)
C(51)
C(51)
/
/
Ag
3.2.2. [Ag(Ph2PNÄ
/
CPh2)2]Cl (2)
/
/
/
/
121.74(14)
/
/
AgCl (0.139 mmol, 20 mg) was added to an aqueous
saturated solution of KCl (20 ml) in order to get a better
solubility of AgCl. A solution of Ph2PNÄ/CPh2 (0.279
mmol, 102 mg) in OEt2 (20 ml) was then added. After
stirring for 15 min a yellow solid is filtered off, washed
with a saturated solution of KCl in water, ethanol and
Et2O sucessively and recrystallized from a mixture of
CHCl3 and Et2O. Yield 105 mg (86%). Anal. Found: C,
68.35; H, 4.3; N, 2.95. Calc. for C50H32AgClP2N2 C,
1
68.7; H, 4.6; N, 3.2%. H NMR (298 K) 7.68Á
/
7.25 (m,
H). 31P{1H} NMR (298 K) 44.7 (m, PPh2), 50.1 (m,
PPh2), (223 K) 44.7 (m, PPh2), 50.1 (m, PPh2).
PhÁ
/
3.2.3. [Ag(PPh3)(NHÄ
CF3SO3 (5))
The compound [AgX(PPh3)] (0.29 mmol, Xꢀ
/
CPh2)]X (Xꢀ
/
ClO4 (4),
/ClO4,
140 mg, CF3SO3, 150 mg) was dissolved in 15 ml of
CH2Cl2 and diphenylmethanimine (0.29 mmol, 51.5 ml)
was added. The reagents were allowed to react for 15
min. Then most of the solvent was removed, and 20 ml
of hexane was then added to produce a white solid. The
solid was filtered and washed with hexane; yield 148 mg,
(75%) 4 166 mg, (81%) 5. Anal. Found (4): C, 56.85; H,
4.75; N, 2.55. Calc. for C31H26NAgClO4P: C, 57.29; H,
3.87; N, 2.15%. Anal. Found (5): C, 54.0; H, 3.5; N, 2.4.
Fig. 5. Arrangement of the molecules in the unit cell (5).
3. Experimental
3.1. Materials
All the experiments were carried out under dry
purified nitrogen. Glassware was dried and filled with
nitrogen, solvents were distilled and kept under nitro-
Calc. for C32H26NAgF3O3PS: C, 54.85; H, 3.75; N,
1
2.0%. H NMR (4) (298 K) 9.21 (s, 1 H, HÁ
/
N), 7.76Á
H); (223 K): 8.97 (s, 1 H, HÁN),
7.32 (m, 25H, PhÁH); 5 (298 K) 9.15 (s, 1 H, HÁ
N), 7.87Á7.45 (m, 25H, PhÁH); (223K): 8.96 (s, 1 H, HÁ
N), 7.95Á7.33 (m, 25H, PhÁ
H). 31P{1H} NMR (4) (298
K) 17.9 (m, PPh2), 12.7 (m, PPh2); (223K) dꢀ14.0 dd
(J(109AgÁ 743.0, J(107AgÁ
P)ꢀ P)ꢀ643.6 Hz, PPh2); 5
(298 K) 17.6 (m, PPh2), 12.1 (m, PPh2); (223 K) dꢀ14.0
dd (J(109AgÁ 744.5, J(107AgÁ
P)ꢀ P)ꢀ644.9 Hz, PPh2).
/
7.39 (m, 25H, PhÁ
/
/
gen. NMR: Bruker ARX 300. IR: PerkinÁ/Elmer FT-IR
7.90Á
/
/
/
Spectrum 1000. Microanalyses: PerkinÁ/Elmer 240B.
/
/
/
Starting materials were prepared according to literature
CPh2 [17]. [Ag(CF3SO3)(PPh3)] was
prepared in a similar way to [Ag(ClO4)(PPh3)] [18].
/
/
procedures: Ph2PNÄ
/
/
/
/
/
/
AgClO4 and AgCF3SO3 were purchased from Aldrich.
/
/
/
/
/
3.2. Synthesis
3.3. Crystallography
3.2.1. [Ag(Ph2PNÄ
(3))
Ph2PNÄ
Et2O solution (15 ml) of AgX (0.27 mmol, Xꢀ
mg, CF3SO3, 69 mg). After stirring for 45 min the
suspension was filtered and the yellow solid obtained
washed with OEt2; yield 210 mg (82%) 1, 208 mg (77%)
/
CPh2)2]X (XꢀClO4 (1), CF3SO3
/
The crystals were mounted in inert oil on a glass fibre
and transferred to the cold gas stream of a Siemens
Smart, Nonius kCCD (4) or Siemens P4 (5) diffract-
/
CPh2 (0.547 mmol, 200 mg) was added to a
/ClO4, 56
ometers. Data were collected using monochromated Mo
˚
Ka radiation (lꢀ
/
0.71073 A). Absorption corrections
were based on psi-scans (5), multiple scans (program

14
A. Codina et al. / Inorganica Chimica Acta 347 (2003) 9Á15
/
Table 6
Details of data collection and structure refinement for complexes 1, 2, 4 and 5
Compound
Chemical formula
Crystal habit
Crystal size (mm3)
Crystal system
Space group
1
2
4
5
C
50H40AgClN2O4P2
C50H40AgClN2P2
yellow prism
C31H26AgClNO4P
colourless prism
C33.5H29AgF3NO3.5PS
colourless irreg. column
pale yellow plate
0.40ꢃ0.21ꢃ0.11
triclinic
/
/
0.34ꢃ
monoclinic
C2/c
/
0.13ꢃ
/
0.13
050ꢃ
monoclinic
P21/c
/
0.25ꢃ
/0.20
0.80ꢃ
orthorombic
Pbcn
/
0.30ꢃ0.20
/
¯
P1
˚
a (A)
10.6466(10)
10.7562(11)
21.419(2)
95.168(3)
101.082(3)
112.175(3)
2193.1(4)
2
12.3456(10)
16.3453(12)
20.9283(16)
90
17.4567(3)
9.7127(2)
18.2313(3)
90
22.211(3)
22.642(4)
12.7962(16)
90
˚
b (A)
˚
c (A)
a (8)
b (8)
g (8)
100.710(3)
90
116.4619(6)
90
90
90
3
˚
U (A )
Z
4149.6(6)
4
1.399
2767.29(9)
4
1.562
6435.2(15)
8
1.506
Dcalc (g cmꢂ3
M
)
1.421
938.10
960
874.10
1792
650.82
1320
729.48
2960
F(000)
T (8C)
2umax (8)
ꢂ
/
130
56
0.641
ꢂ
/
130
56
0.665
ꢂ
/
100
56
0.921
ꢂ
/
100
50
0.795
m(Mo Ka) (mmꢂ1
)
Transmission
0.764Á
19880
10663
0.0461
0.0360
0.0739
10663
541
/0.980
0.781Á
22214
5278
/0.928
0.656Á
25518
6535
/
0.837
0.758Á/0.847
No. of reflections measured
No. of unique reflections
Rint
7102
5664
0.0528
0.0328
0.0882
5278
0.0202
0.0271
0.0616
6535
0.0235
0.0342
0.0676
5664
a
R
(F ꢀ4s(F))
/
b
wR (F2, all reflections)
No. of reflections used
No. of parameters
254
0
456
0
419
33
No. of restraints
c
180
0.932
0.451
S
1.044
1.331
1.044
0.370
0.864
0.338
ꢂ3
˚
Max. Dr (e A
)
a
R(F)ꢀ
/
SjjFojꢂ
wR(F2)ꢀ[S{w(Fo2ꢂ
program.
[S{w(Fo2ꢂFc2)2}/(nꢂ
/
jFcjj/SjFoj.
b
/
/
Fc2)2}/S{w(Fo2)2}]0.5; wꢂ1ꢀ
/
s2(Fo2)ꢁ
/
(aP)2ꢁ
/
bP, where Pꢀ
/
[Fo2ꢁ2Fc2]/3 and a and b are constants adjusted by the
/
c
Sꢀ
/
/
/
p)]0.5, where n is the number of data and p the number of parameters.
SADABS (1,2) or SORTAV (4)). The structures were
refined on F2 using the program SHELXL-97 [19]. All
non-hydrogen atoms were refined anisotropically. Hy-
drogen atoms in 4 and all NH were refined freely, other
rigid methyl groups or using a riding model. Special
features of refinement: The acetone solvent molecule of
5 is disordered over a twofold axis. Its H atoms were not
located. Further crystallographic details are given in
Table 6.
Acknowledgements
We thank the Spanish McyT(DGI)/FEDER
BQU2001-2409-CO2-O2) and C.A.R. (ANGI2001/28)
for financial support.
References
[1] H. Hayashi, M. Mori, N. Shigemoto, T. Okazaki, Ind. Eng.
Chem., Prod. Res. Dev. 17 (1978) 179.
[2] H. Hayashi, K. Kawasaki, M. Fujii, A. Kainon, T. Okazaki, J.
Catal. 41 (1976) 367.
4. Supplementary material
[3] A. Misono, T. Osa, S. Kodo, Bull. Chem. Soc. Jpn. 41 (1968) 373.
[4] H. Kayashi, T. Tanaka, N. Shigemoto, T. Okazaki. Chem. Lett.
(1977) 981.
Crystallographic data (excluding structure factors) for
the structural analysis have been deposited with the
Cambridge Crystallographic Data Centre, CCDC Nos.
[5] W. Schneider, A. Bauer, A. Schier, H. Schmidbaur, Chem. Ber.
130 (1997) 1417.
170808Á
/
170811 for complexes 1, 3, 4 and 5, respectively.
[6] W. Schneider, A. Bauer, H. Schmidbaur, J. Chem. Soc., Dalton
Trans. (1997) 415.
Copies of this information may be obtained free of
charge from The Director, CCDC, 12 Union Road,
Cambridge, CB2 1EZ, UK (fax: ꢁ44-1223-336-033;
e-mail: deposit@ccdc.cam.ac.uk or www: http://
www.ccdc.cam.ac.uk).
[7] W. Schneider, A. Bauer, A. Schier, H. Schmidbaur, Chem. Ber.
130 (1997) 1423.
/
[8] M. Bardaj´ı, O. Crespo, A. Laguna, A.K. Fisher, Inorg. Chim.
Acta 304 (2000) 7.
[9] B.J. Hathaway, A.E. Underhill, J. Chem. Soc. (1961) 3091.

A. Codina et al. / Inorganica Chimica Acta 347 (2003) 9Á
/15
15
[10] D.H. Johnston, D.F. Shriver, Inorg. Chem. 32 (1993) 1045.
[11] (a) E.L. Muetterties, C.W. Alegranti, J. Am. Chem. Soc. 94 (1972)
6386;
(c) R. Uso´n, A. Laguna, M.C. Gimeno, P.G. Jones, C. Fittschen,
G.M. Sheldrick, J. Chem. Soc. Chem. Commun. 7 (1986) 509.
[14] M.C. Gimeno, A. Laguna, C. Sarroca, P.G. Jones, J. Chem. Soc.,
Dalton Trans. (1995) 1473.
(b) E.L. Muetterties, C.W. Alegranti, J. Am. Chem. Soc. 92 (1970)
4114;
[15] R. Terroba, M.B. Hursthouse, M. Laguna, A. Mendia, Polyhe-
dron 18 (1999) 807.
(c) N. Muller, D.E. Pritchard, J. Chem. Phys. 31 (1959)
768.
[16] G.A. Bowmaker, Effendy, P.J. Harvey, P.C. Healy, B.W. Skelton,
A.H. White, J. Chem. Soc., Dalton Trans. (1996) 2449.
[17] A. Schmidpeter, W. Zeiß, Chem. Ber. 104 (1971) 1199.
[18] R.Uso´n, A. Laguna, M. Laguna, J. Jime´nez and P.G. Jones, J.
Chem. Soc., Dalton Trans. (1991) 1361.
[12] P.A. Pe´rez-Lourido, J.A. Garc´ıa-Vazquez, J. Romero, M.S.
Louro, A. Sousa, A.Q. Chen, Y. Chang, J. Zubieta, J. Chem.
Soc., Dalton Tran. (1996) 2047
[13] (a) J. Fornie´s, E. Lalinde, J. Chem. Soc., Dalton Trans. 13 (1996)
2587;
(b) R. Uso´n, J. Fornies, Inorg. Chim. Acta 254 (1997) 157;
[19] G.M. Sheldrick, SHELXL-97, Program for Crystal Structure
Refinement, University of Gottingen, Gottingen, Germany, 1997.
¨ ¨