Five- and six-membered platinacycles derived from phenantryl and anthracenyl imines

Article abstract of DOI:10.1016/j.jorganchem.2004.03.020

The reaction of [Pt₂Me₄ (μ-SMe₂)₂] with ligands Me₂NCH₂CH₂NCHAr (2a, Ar=9-phenantryl; 2b, Ar=9-anthracenyl) carried out in acetone at room temperature produced the corresponding

Full text of DOI:10.1016/j.jorganchem.2004.03.020

Journal of Organometallic Chemistry 689 (2004) 1956–1964
www.elsevier.com/locate/jorganchem
Five- and six-membered platinacycles derived from phenantryl and
anthracenyl imines
*
Margarita Crespo , Emilia Evangelio
Departament de Quꢀımica Inorgꢁanica, Facultat de Quꢀımica, Universitat de Barcelona, Diagonal 647, Barcelona E-08028, Spain
Received 13 February 2004; accepted 17 March 2004
Abstract
The reaction of [Pt2Me4(l-SMe2)2] with ligands Me2NCH2CH2NCHAr (2a, Ar ¼ 9-phenantryl; 2b, Ar ¼ 9-anthracenyl) carried
out in acetone at room temperature produced the corresponding compounds [PtMe2{9-(Me2NCH2CH2NCH)C14H9}] (3) in which
the imines act as bidentate [N,N0] ligands. Refluxing toluene solutions of compounds 3 gave cyclometallated [C,N,N0] compounds
[PtMe{9-(Me2NCH2CH2NCH)C14H8}] (4) as a mixture of two isomers containing either a five- or a six-membered metallacycles
for 3a and as a single isomer containing a six-membered metallacycle for 3b. The reactions of compounds 4 with acetyl chloride
and with methyl iodide produced, respectively, compounds [PtCl{9-(Me2NCH2CH2NCH)C14H8}] (5) and [PtMe2I{9-
(Me2NCH2CH2NCH)C14H8}] (6). All compounds were characterised by NMR spectroscopies and analytical data.
ꢀ 2004 Elsevier B.V. All rights reserved.
Keywords: Platinum; Cyclometallation; Anthracene; Phenantrene; Imine
1. Introduction
cycles having nitrogen donor atoms have been reported
[8], they are much less common than the most prevalent
five-membered analogues [9].
Cyclometallated compounds attract a great deal of
interest due to their numerous applications in several
fields, such as organic and organometallic synthesis, the
design of new metallomesogens and biologically active
compounds [1]. The most widely studied examples are
platinum and palladium metallacycles with nitrogen
donors in which C–H activation takes place at phenylic
ortho positions. Metallation at heterocyclic [2–4] or
fused rings [5,6] systems have been less explored.
The cyclometallation of anthracen-9-ylmethylen-
ephenylamine [10] and of phenantrylamines [11] with
palladium (II) to yield, respectively, six- and five-mem-
bered metallacycles have been reported. However, in
spite of the interesting properties of anthracene and
phenanthrene derivatives [12], platinacycles derived
from these groups have not been reported yet in the
literature.
Following our studies of imines containing aromatic
groups such as benzene [7], thiophene [3], furane [4] or
naphthalenes [6], we now report the reactions of
[Pt2Me4(l-SMe2)2] with imines derived from phenan-
threne- and anthracene-9-carboxaldehydes. As shown in
Chart 1, two non-equivalent metallation sites leading to
either five- or six-membered metallacycles are available
for ligands derived from phenanthrene while metallation
at the anthracene group can only produce six-membered
metallacycles. Although several six-membered platina-
2. Results and discussion
2.1. Syntheses of cyclometallated compounds
Imines 2a and 2b derived, respectively, from 9-phen-
anthraldehyde and 9-anthraldehyde were easily obtained
from the reaction of Me2N(CH2)2NH2 and the corre-
sponding aldehyde in toluene at room temperature.
They were characterised by mass, IR, and NMR spectra.
According to NMR data, only one isomer was present
in solution and the expected E conformation was
* Corresponding author. Tel.: +934021273; fax: +934907725.
E-mail address: margarita.crespo@qi.ub.es (M. Crespo).
0022-328X/$ - see front matter ꢀ 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.03.020

M. Crespo, E. Evangelio / Journal of Organometallic Chemistry 689 (2004) 1956–1964
1957
Chart 1. Possible metallation sites for ligands derived from phenanthrene (2a and 2c) and anthracene-9-carboxaldehydes (2b and 2d) along with the
previously obtained results for ligands derived from 1- and 2-naphthaldehydes (2e and 2f).
confirmed by NOESY experiments in which cross-peak
signals between imine (Hd) and methylene (Hc) protons
were observed.
for 3b) are in the expected range for a platinum (II)
centre bound to two-carbon and to two-nitrogen atoms
[13].
As shown in Schemes 1 and 2, treatment of these
potentially terdentate ligands with [Pt2Me4(l-SMe2)2]
(1) in acetone produced readily compounds
[PtMe2(Me2NCH2CH2NCHAr)] 3a and 3b in which the
imines act as bidentate [N,N0] ligands. Compounds 3
were characterised by NMR spectroscopies, elemental
Intramolecular activation of C–H bonds followed by
methane elimination as reported for analogous systems
[3,4,6,7] was achieved when toluene solutions of com-
pounds 3 were refluxed for several hours. Work-up of
the resulting solutions revealed that a mixture of two
[C,N,N0] cyclometallated platinum (II) compounds (4a
and 4a0) were obtained from 3a, while 3b lead to a single
isomer of [C,N,N0] cycloplatinated compound 4b. These
results indicate that formation of a five fused rings sys-
tem containing a six-membered metallacycle is achieved
from 3b. The two isomers obtained from 3a are assigned
to analogous systems containing either five (4a) or six
(4a0) membered metallacycles indicating that metallation
is favoured at the two non-equivalent sites. As shown in
Chart 1, six-membered metallacycles have not been
obtained for ligands derived from 1-naphthaldehyde
which have been reported to produce regioselectively a
five-membered platinacycle [6] in agreement with the
greater stability ascribed to five-membered rings [9]. The
1
analyses and FAB-mass spectra. In the H NMR spec-
tra, two distinct resonances appear in the methyl region
both coupled with 195Pt. The one at higher field with a
larger coupling to 195Pt was assigned to the methyl trans
to the NMe2 moiety. The coordination of the ligand
through both nitrogen atoms is confirmed by the ob-
served coupling of both amine and imine protons to
platinum. The aromatic region was assigned with the aid
1
of H–1H correlation spectroscopy (COSY). As for the
free imines, the cross-peak signals between He and Hf in
1
the NOESY H–1H NMR spectra indicated an E con-
formation of the coordinated ligand. The chemical shifts
observed for 195Pt ()3432 ppm for 3a and )3458 ppm

1958
M. Crespo, E. Evangelio / Journal of Organometallic Chemistry 689 (2004) 1956–1964
2
1
10
3
9
f
e
d
c
(i)
4
NMe
N
2
[Pt2Me4(µ-SMe2)2]
+
N
Pt
5
1
8
NMe
a
Me
2
b
Me
1
6
7
3a
2a
(ii)
2
b
Me
N
a
Me
2
1
2
10
c
3
Pt
e
d
3
d
N
4
c
C
H
N
4
e
+
Pt
NMe
2
5
5
b
8
a
Me
6
7
6
7
4a
4a'
2
1
10
3
d
c
(iii)
4
b
N
(iv)
Pt
Cl
NMe
5
2
a
6
7
5a'
c
Me
N
a
Me
b
Me
2
d
10'
Pt
f'
e'
e
N
I
d'
c'
NMe
N
C
H
+
I
f
Pt
2
Me
a'
Me
b'
6a
6a'
(i): acetone, r.t.; (ii): refluxing toluene;
(iii): + CH3COCl in dichloromethane/methanol;
(iv): + CH3I in acetone.
Scheme 1.
different result obtained for ligand 2a can therefore be
related to the steric effect of the third fused ring in the
phenanthrene derivatives, which hampers formation of a
five-membered metallacycle, and thus favours formation
of the less stable six-membered metallacycle.
the methyl ligand and the dimethylamino are coupled to
platinum and the values of the coupling constants are in
the usual range for analogous compounds [7]. In
agreement with previous data, the J(H–Pt) values of the
imine group increase from the coordination compound
3a (J(H–Pt) ¼ 49 Hz) to the cyclometallated compound
4a (J(H–Pt) ¼ 59 Hz) containing a five-membered me-
tallacycle. However, lower values J(H–Pt) ¼ 37–40 Hz
were obtained for compounds 4a0 and 4b containing a
six-membered metallacycle. Moreover, while the two
methylene resonances appear at lower fields than the
Compounds 4 were characterised by NMR spectros-
copies, elemental analyses and FAB-mass spectra. Two
sets of signals are observed for the mixture of com-
pounds 4a/4a0 and their relatives intensities indicate a
slightly higher abundance for the five-membered
1
metallacycle (4a:4a0 ¼ 1.2:1). In the H NMR spectra,

M. Crespo, E. Evangelio / Journal of Organometallic Chemistry 689 (2004) 1956–1964
1959
3
2
4
10
5
1
9
f
e
d
c
[Pt2Me4(µ-SMe2)2] +
(i)
NMe2
N
N
Pt
8
a
Me
b
NMe2
1
Me
6
7
2b
3b
3
2
(ii)
4
1
e
10
d
c
N
b
5
Pt
NMe2
3
Me
a
3
2
2
6
7
4b
(iii)
b
4
10
5
1
1
4
(iv)
f
d
c
e
10
d
N
N
I
c
Pt
Cl
NMe2
a
5
Pt
NMe2
Me
a
Me
b
6
7
6
7
5b
6b
(i): acetone, r.t.; (ii): refluxing toluene;
(iii): + CH3COCl in dichloromethane/methanol;
(iv): + CH3I in acetone.
Scheme 2.
dimethylamino group for five-membered metallacycles,
a different spectral pattern with the dimethylamino res-
onance in-between the methylene resonances is observed
for the six-membered metallacycles. Assignment of the
data, which indicate a highfield shift of the platinum
resonance upon metallation [3,4,6].
Due to the low solubility and the lack of stability in
solution of compounds 4, these compounds could not
be purified by recrystallisation and adequate crystals for
X-ray analyses could not be obtained. Moreover, at-
tempts to separate compounds 4a and 4a0 either by
fractional crystallisation or by column crystallography
using CHCl3/acetone mixtures as eluent were unsucess-
ful. After several hours in solution, hydrolysis of the
coordinated imine yielding the corresponding aldehyde
and a complex mixture of platinum compounds is
obtained.
Attempts to produce cyclometallation of ligands 2a
and 2b were also carried out using [PtCl2(dmso)2] (10) as
metallation agent under the conditions previously re-
ported for ligand Me2NCH2CH2N@CHPh [14]. The
starting platinum compound and the corresponding li-
gand were refluxed in methanol during several hours to
produce insoluble orange solids in high yields. Due to
1
aromatic region was performed with the aid of H–1H
correlation spectroscopy (COSY). The presence of 16
(4a/4a0) or eight (4b) crossing peaks in the aromatic re-
gion of the {1H–13C}-heterocorrelation spectra is con-
sistent with metallation at two non-equivalent sites for
imine 2a and at the only available position for 2b. In
addition, the 195Pt NMR spectra displays either two
signals at d ¼ ꢀ3421 and )3218 ppm assigned, respec-
tively, to compounds 4a and 4a0 or only one signal at
d ¼ ꢀ3078 ppm for 4b. These values are in the expected
range for a platinum (II) centre bound to two-carbon
and to two-nitrogen atoms [13]. However, d(195Pt) is
shifted downfield compared to the corresponding com-
pound 3, and this effect is larger when a six-membered
metallacycle is formed as for compounds 4a0 and 4b.
This result is in contrast with the previously reported

1960
M. Crespo, E. Evangelio / Journal of Organometallic Chemistry 689 (2004) 1956–1964
the low solubility of these compounds, NMR spectra
could not be taken. Based on FAB mass spectra and
elemental analyses, the formula [PtCl2(Me2NCH2-
CH2NCHAr)] in which Ar is a phenantryl (3a0) or an
anthracenyl group (3b0) is assigned to these compounds.
The cyclometallation process leading to [PtCl(Me2-
NCH2CH2NCHC14H8)] was attempted under pro-
longed reflux in methanol in the presence of sodium
acetate. The obtained compounds show the same pat-
tern than the coordination compounds in the FAB mass
spectra and we assumed that due to their low solubility
the reaction proceeds no further.
reaction with acetyl chloride in methanol medium
should lead to [C,N,N0] cyclometallated compounds in
which the methyl ligand has been replaced for a chloro
ligand [15]. As stated in the previous section, this type of
compound could not be obtained from compounds 3a0
and 3b0.
The reaction of compounds 4a/4a0 and 4b with acetyl
chloride in a mixture of dichloromethane and methanol
produced, after recrystallisation in dicloromethane–
hexane, a single isomer of the corresponding compound
[PtCl(Me2NCH2CH2NCHC14H8)] (5) in each case. The
similarity of the spectral values obtained for these
compounds and in particular the spectral pattern in
which the dimethylamino resonance lies in-between the
methylene resonances, as observed for 4a0 and 4b, indi-
cates that the single isomer obtained from the mixture
4a/4a0 contains a six-membered metallacycle. Unreacted
Ar
NMe2
Cl
N
[PtCl2(dmso)2]
+
ArCH=NCH2CH2NMe2
Pt
2a Ar = phenanthrene
2b Ar = anthracene
Cl
1'
1
compound 4a was identified by H NMR in the insol-
3a' Ar = phenanthrene
3b' Ar = anthracene
uble residue obtained in the recrystallisation of the crude
product from reaction of the mixture 4a/4a0 but could
not be obtained in a pure form due to the low stability of
these compounds in solution. The fact that 4a was re-
covered unchanged while 4a0 gave the expected reaction
could be related either to a decreased reactivity or to a
lower solubility of five- versus six-membered metalla-
cycles.
The preparation of compounds 5 following this
method supports the suggestion that the failure to ob-
tain these compounds using [PtCl2(dmso)2] as metalla-
tion agent might be attributed to the low solubility of
the coordination compounds [PtCl2(Me2NCH2CH2-
NCHAr)].
Compounds 5 were characterised by NMR spectros-
copies, elemental analyses and FAB mass spectra. As for
compounds 4, attempts to crystallise compounds 5 in
several solvents did not produce pure samples due to the
low stability of the compounds in solution. The presence
of the terdentate [C,N,N0] ligand is evidenced by the
coupling of both NMe2 and imine groups to 195Pt, and
the presence of eight crossing peaks in the aromatic re-
gion of the {1H–13C}-heterocorrelation spectra. Methyl
for chloro substitution is evidenced by disappearance of
the methyl-platinum resonance and by increase of the
coupling constant J(H–Pt) for the imine proton, which
is now trans to a chloro ligand. Furthermore, d(195Pt)
values are shifted towards lower fields in agreement with
a lower electronic density on the platinum nucleus. In
the FAB mass spectra, the molecular peak as well as a
peak corresponding to the loss of a chloro ligand were
observed.
In order to attempt the syntheses of analogous [C,N]
cyclometallated compounds, imines 2c and 2d were
prepared from the reaction of PhCH2NH2with 9-
phenanthraldehyde or 9-anthraldehyde in toluene at
room temperature. The ligands were characterised by
mass, IR, and NMR spectra. According to NMR data,
only one isomer for which the expected E conformation
was assumed was present in solution. Treatment of
these potentially bidentate ligands with [Pt2Me4(l-
SMe2)2] (1) in acetone at room temperature during re-
action times up to 60 h did not produce any observable
reaction. When more drastic conditions such as re-
fluxing in acetone or toluene were tested, only decom-
position products such as metallic platinum and free
aldehyde were obtained.
In previously reported systems [3,4,6], the results
obtained for metallation processes are analogous for
potentially terdentate or bidentate ligands. However, in
the present case, ligands containing two nitrogen atoms
proved to be superior. This result could be related to the
great bulk of the antracene and phenantrene groups,
which makes coordination of the ligands to the platinum
centre more difficult. The presence of a second nitrogen
atom in ligands 2a and 2b facilitates the coordination of
the ligand as a [N,N0] chelate leading to compounds 3
which are precursors to the corresponding cyclometal-
lated compounds.
2.2. Reactivity of the obtained cyclometallated compounds
The reaction of compounds 4 with methyl iodide was
also tested in order to obtain [C,N,N0] cyclometallated
platinum (IV) compounds derived from anthracene or
phenantrene. Previous studies of the oxidative addition
of alkyl halides to platinum (II) compounds indicate
that nitrogen donor ligands impart high nucleophilicity
As shown in Schemes 1 and 2, the reactions of cy-
clometallated compounds 4 with acetyl chloride and
with methyl iodide were studied. According to previ-
ously reported results for analogous compounds, the

M. Crespo, E. Evangelio / Journal of Organometallic Chemistry 689 (2004) 1956–1964
1961
to the metal centre, increasing its reactivity, which is,
3. Experimental
however, moderated by the presence of bulky ligands
that might hinder or even inhibit the reaction [16]. In
most cases, the oxidative addition of alkyl halides to
organoplatinum (II) complexes gives trans stereochem-
istry, although subsequent isomerisation can yield
products that appear to arise from cis-oxidative addition
[17]. In spite of the presence of the bulky phenantryl or
anthracenyl groups, the reaction of 4a/4a0 and 4b with
methyl iodide in acetone at room temperature gave
the corresponding platinum (IV) compounds
[PtMe2I(Me2NCH2CH2NCHC14H8)] (6) arising from
trans-oxidative addition of the alkyl halide.
3.1. General
NMR spectra were recorded at the Unitat de RMN
d’Alt Camp de la Universitat de Barcelona using Varian
Gemini 200 (1H, 200 MHz; 13C, 50 MHz), Bruker 250
(13C, 62.5 MHz; 195Pt, 54 MHz) Varian XL300FT (13C,
75.4 MHz), Mercury 400 (1H–13C ghsqc) and Varian
500 (1H, 1H–1H COSY, 1H–1H NOESY, 500 MHz)
spectrometers, and referenced to SiMe4 (1H, 13C) and
H2PtCl6 in D2O (195Pt). d values are given in ppm and J
values in Hz. Microanalyses were performed at the
ꢀ ꢁ
Serveis Cientıfico-Tecnics de la Universitat de Barcelona
Compounds 6 were characterised by NMR spectros-
copies, elemental analyses and FAB mass spectra. As
for compounds 4a and 4a0, two sets of signals are
observed for the mixture of compounds 6a/6a0 and
their relatives intensities (6a:6a0 ¼ 1.2:1) indicate that
the relative amounts of five- and six-membered metal-
lacycles is maintained. In the 1H NMR spectra, the
methyl ligands are coupled to platinum and the values
of the coupling constants, in particular for the methyl
trans to the imine nitrogen, are reduced when compared
to the corresponding platinum (II) compounds. As
observed for analogous octahedral systems [7], the
dimethylamino and the methylene protons are non-
equivalent. In agreement with the higher oxidation state
of platinum, the J(H–Pt) values of the imine group de-
creases for 6a and 6b when compared to the corre-
sponding values for 4a and 4b, while the platinum
satellites for the imine resonance of 6a0 are overlapped
by the aromatic resonances. The presence of 16 (6a/6a0)
or eight (6b) crossing peaks in the aromatic region of the
{1H–13C}-heterocorrelation spectra is consistent with
the proposed structures. The 195Pt NMR spectra dis-
plays two signals at d ¼ ꢀ2429 and )2524 ppm as-
signed, respectively, to compounds 6a and 6a0 or one
signal at d ¼ ꢀ2433 ppm for 6b. These values show the
expected downfield shift on increasing the oxidation
state of the platinum.
In conclusion, [C,N,N0] cyclometallated platinum (II)
compounds containing five- or six-membered metalla-
cycles were easily prepared from intramolecular C–H
bond activation at phenantrene or anthracene. Studies
of reactivity of the obtained compounds [PtMe{9-
(Me2NCH2CH2N@CH)C14H8}] revealed that they are
adequate precursors for the syntheses of two other types
of [C,N,N0] cyclometallated platinum compounds: (i)
analogous platinum (II) compounds containing a chloro
ligand [PtCl{9-(Me2NCH2CH2N@CH)C14H8}] and (ii)
cyclometallated platinum (IV) compounds [PtMe2I{9-
(Me2NCH2CH2N@CH)C14H8}]. Therefore, the syn-
theses of several classes of platinacycles derived from
anthracene and phenantrene groups, including new ex-
amples of six-memebered metallacycles, have been
achieved.
ꢀ
ꢁ
and at the Servei de Recursos Cientıfics i Tecnics de la
Universitat Rovira i Virgili. Mass spectra were per-
formed at the Servei d’Espectrometria de Masses de la
Universitat de Barcelona using HP 5988A (CI, NH3),
VG-Quattro (FAB, NBA) and Voyager DE-RP (Maldi-
TOF) spectrometers. IR spectra were taken on a Nicolet
Impact 400 using KBr pellets.
3.2. Preparation of the compounds
Compounds [Pt2Me4(l-SMe2)2] (1) [18] and
[PtCl2(dmso)2] (10) [19] were prepared as reported.
3.2.1. Synthetic procedure for the ligands
9-(Me2NCH2CH2N@CH)C14H9 (2a) was obtained as
a yellow oil from the reaction of phenanthrene-9-alde-
hyde (1 g, 4.8 mmol) and the equimolar amount (427
mg) of N,N-dimethylethylenediamine in toluene (20 ml).
The mixture was stirred for 1 h and dried over Na2SO4.
The solvent was removed in a rotary evaporator to yield
a yellow oil. Yield: 1.25 g (93%). IR: m(CH@N) ¼ 1642
cmꢀ1. 1H NMR (500 MHz, acetone-d6): d ¼ 2:29 [s, Ha],
3
3
2.68 [t, J(H–H) ¼ 6.0, Hb], 3.85 [t, J(H–H) ¼ 6.0, Hc],
7.67 [td, 3J(H–H) ¼ 8.0, 4J(H–H) ¼ 1.2, H2], 7.69 [td,
3J(H–H) ¼ 8.0, 4J(H–H) ¼ 1.2, H7], 7.73 [td, 3J(H–
H) ¼ 8.0, 4J(H–H) ¼ 1.2, H6], 7.75 [td, 3J(H–H) ¼ 8.0,
4J(H–H) ¼ 1.2, H3], 8.05 [dd, 3J(H–H) ¼ 7.0, 4J(H–
H) ¼ 1.2, H1], 8.51 [s, H10], 8.82 [d, J(H–H) ¼ 8.0, H4],
3
8.87 [dd, J(H–H) ¼ 8.0, J(H–H) ¼ 1.2, H5], 9.41 [dd,
3J(H–H) ¼ 8.0, 4J(H–H) ¼ 1.2, H8], 8.97 [s, Hd]. 13C
NMR (75 MHz, CDCl3): d ¼ 45:9 [Ca], {60.2, 60.9, Cb,
Cc}, {122.5, 122.9, 125.2, 126.7, 126.8, 127.0, 127.8,
129.4, 130.6, CHAr}, {128.2, 129.0, 129.8, 130.3, 131.0,
CAr}, 167.7 [Cd]. MS-CI (NH3, m=z): 277 [M + H]þ.
9-(Me2NCH2CH2N@CH)C14H9 (2b) was obtained as
a red oil using the same procedure than for 2a from
3
4
anthracene-9-aldehyde. Yield: 1.14
1
g
(85%). IR:
m(CH@N) ¼ 1643 cmꢀ 1. H NMR (500 MHz, acetone-
3
d6): d ¼ 2:39 [s, Ha], 2.87 [t, J(H–H) ¼ 6.0, Hb], 4.08 [t,
3J(H–H) ¼ 6.0, Hc], 7.50 [td, 3J(H–H) ¼ 7.5, 4J(H–
H) ¼ 1.5, H2], 7.52 [td, 3J(H–H) ¼ 7.5, 4J(H–H) ¼ 1.5,
3
4
H3], 7.54 [td, J(H–H) ¼ 9.0, J(H–H) ¼ 1.5, H7], 7.55

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M. Crespo, E. Evangelio / Journal of Organometallic Chemistry 689 (2004) 1956–1964
3
4
3
[td, J(H–H) ¼ 6.5, J(H–H) ¼ 1.5, H6], 8.03 [dd, J(H–
127.2, 127.9, 130.11, CHAr}, {128.44, 129.0, 130.4,
130.7, 131.1, CAr}, 161.0 [2J(Pt–C) ¼ 92, Cf ]. 195Pt NMR
(54 MHz, CDCl3): d ¼ ꢀ3432 [s]. MS-FAB (+) (NBA,
m=z): 486 [M–Me]þ, 471 [M–2Me]þ. Anal. Found: C,
49.9; H, 5.2; N, 5.5. Calc. for C21H26N2Pt: C, 50.29; H,
5.23; N, 5.59%.
H) ¼ 6.5, J(H–H) ¼ 1.5, H5], 8.04 [dd, J(H–H) ¼ 7.5,
4
3
4J(H–H) ¼ 1.5, H4], 8.50 [s, H10], 8.53 [dd, 3J(H–
H) ¼ 7.5, J(H–H) ¼ 1.5, H1], 8.55 [dd, J(H–H) ¼ 9.0,
4J(H–H) ¼ 1.5, H8], 9.46 [s, Hd]. 13C NMR (50 MHz,
CDCl3): d ¼ 45:8 [Ca], {60.0, 61.1, Cb, Cc}, {124.9 [2C],
125.1 [2C], 126.5 [2C], 128.7 [2C], 129.0 [C10], CHAr},
{123.5 [C9], 129.8 [2C], 131.2 [2C], CAr}, 161.0 [Cd]. MS-
CI (NH3, m=z): 277 [M + H]þ.
4
3
[PtMe2{9-(Me2NCH2CH2NCH)C14H9}] (3b). Yield:
137 mg (78%). 1H NMR (500 MHz, acetone-d6):
d ¼ ꢀ0:93 [s, J(Pt–H) ¼ 93, Mea], 0.19 [s, J(Pt–H) ¼
86, Meb], 2.80 [s, 3J(Pt–H) ¼ 20, Hc], 3.00 [t, 3J(H–
H) ¼ 6.0, Hd], 4.41 [td, 3J(H–H) ¼ 6.0, He], 7.49 [t, 3J(H–
H) ¼ 7.0, 4J(H–H) ¼ 1.0, H2], 7.50 [td, 3J(H–H) ¼ 7.0,
4J(H–H) ¼ 1.0, H3], 7.54 [td, 3J(H–H) ¼ 9.0, 4J(H–
H) ¼ 1.0, H7], 7.55 [td, 3J(H–H) ¼ 6.0, 4J(H–H) ¼ 1.0,
2
2
9-(C6H5CH2N@CH)C14H9 (2c) was obtained as a
white solid from of phenanthrene-9-aldehyde (500 mg,
2.42 mmol) and the equimolar amount (260 mg) of
benzylamine using an analogous procedure than for 2a
and 2b. Yield: 530 mg (74%). IR: m(CH@N) ¼ 1641
cmꢀ1. H NMR (200 MHz, CDCl3): d ¼ 4:96 [s, Ha],
H6], 8.08 [dd, J(H–H) ¼ 6.0, J(H–H) ¼ 1.0, H5], 8.10
1
3
4
3
3
4
3
{7.20–7.50 [m, 5H], 7.59–7.77 [m, 4H], 7.92 [dd, J(H–
[dd, J(H–H) ¼ 7.0, J(H–H) ¼ 1.0, H4], 8.30 [dd, J(H–
H) ¼ 7.0, 1H], 8.15 [s, H10], 8.62–8.74 [m, 2H], 9.09 [m,
1H], aromatics}, 9.02 [s, Hb]. 13C NMR (50 MHz,
CDCl3): d ¼ 66:1 [Ca], {122.5, 122.9, 125.3, 126.7, 126.8,
126.9, 126.8, 127.1, 127.9, 128.5, 129.4, 131.2, CHAr},
162.1 [Cb]. MS-CI (NH3, m=z): 296 [M + H]þ.
H) ¼ 7.0, J(H–H) ¼ 1.0, H1], 8.32 [dd, J(H–H) ¼ 9.0,
4J(H–H) ¼ 1.0, H8], 8.64 [s, H10], 10.12 [s, 3J(Pt–
H) ¼ 54, Hf ]. 13C NMR (62.5 MHz, CDCl3): d ¼ ꢀ26:6
[Mea], )17.6 [Meb], 48.8 [Cc], 65.9 [Cd], 66.0 [Ce], {125.7
[2C], 125.8 [2C], 126.0 [2C], 128.6 [C10], 128.8 [2C],
CHAr}, {126.7 [C9], 128.4 [2C], 131.7 [2C], CAr}, 161.5
[Cf ]. 195Pt NMR (54 MHz, CDCl3): d ¼ ꢀ3458 [s]. MS-
FAB (+) (NBA, m=z): 486 [M–Me]þ, 471 [M–2Me]þ.
Anal. Found: C, 48.6; H, 5.4; N, 5.4. Calc. for
C21H26N2Pt Æ H2O: C, 48.55; H, 5.43; N, 5.39%.
4
3
9-(C6H5CH2N@CH)C14H9 (2d) was obtained as a
yellow solid using the same procedure than for 2c from
anthracene-9-aldehyde. Yield: 600 mg (84%). IR:
m(CH@N) ¼ 1635 cmꢀ1. H NMR (200 MHz, CDCl3):
1
d ¼ 5:20 [s, Ha], {7.29–7.43 [m, 3H], 7.45–7.56 [m, 6H],
8.08–8.14 [m, 2H], 8.65 [s, 1H], 8.73–8.75 [m, 2H], aro-
matics}, 9.72 [s, Hb]. 13C NMR (50 MHz, CDCl3):
d ¼ 67.2 [Ca], {126.0 [2C], 126.2 [2C], 127.6 [2C], 127.8,
129.1 [2C], 129.4 [2C], 129.8 [2C], 130.4, CHAr}, {131.1
[2C], 132.4 [2C], 141.0, CAr}, 161.8 [Cb]. MS-CI (NH3,
m=z): 296 [M + H]þ.
Compounds 4a/4a0 and 4b were obtained by refluxing
during 2 h (4a/4a0) or 3 h (4b) a toluene solution (20 ml)
containing, respectively, 3a (118 mg, 0.24 mmol) or 3b
(95 mg, 0.2 mmol). The solvent was removed in a rotary
evaporator and the red residue was washed with ether
(3 · 2 ml) to yield light brown (4a/4a0) or dark red (4b)
solids which were dried in vacuum.
3.2.2. Synthetic procedure for the platinum compounds
Compounds 3 were obtained by adding a solution of
the corresponding imine (96 mg, 0.348 mmol) in acetone
(10 ml) to a solution of compound [Pt2Me4(l-SMe2)2]
(1) (100 mg, 0.174 mmol) in acetone (10 ml). The mix-
ture was stirred for 30 min at room temperature, and the
solvent was removed in a rotary evaporator. The yellow
(3a) or orange (3b) solids were washed with ether
(3 · 2 ml) and dried in vacuum. [PtMe2{9-(Me2NCH2-
CH2NCH)C14H9}] (3a). Yield: 157 mg (90%). 1H NMR
(500 MHz, acetone-d6): d ¼ ꢀ0:06 [s, 2J(Pt–H) ¼ 94,
Mea], 0.52 [s, 2J(Pt–H) ¼ 88, Meb], 2.95 [s, 3J(Pt–
[PtMe{9-(Me2NCH2CH2NCH)C14H8}] (4a/4a0). Yi-
1
eld: 90 mg (79%). H NMR (500 MHz): 4a ¼ 1.34 [s,
2J(Pt–H) ¼ 72, Mea], 2.74 [s, 3J(Pt–H) ¼ 14, Hb], 3.15 [t,
3J(H–H) ¼ 6.5, Hc], 4.02 [t, 3J(H–H) ¼ 5.5, Hd], 7.42 [dd,
4
3J(H–H) ¼ 8.0, J(H–H) ¼ 1.0, H7], 7.43–7.47 [m, H2],
7.55 [td, 3J(H–H) ¼ 7.5, 4J(H–H) ¼ 1.0, H3], 7.61 [td,
3J(H–H) ¼ 7.0, 4J(H–H) ¼ 1.0, H6], 8.47 [d, 3J(H–
H) ¼ 8.0, H4], 8.59 [d, 3J(H–H) ¼ 8.0, H5], 8.63 [d, 3J(H–
H) ¼ 8.0, H8], 8.91 [td, 3J(H–H) ¼ 7.0, H1], 9.43 [s,
3J(Pt–H) ¼ 59, He]. 4a0 d ¼ 0:91 [s, 2J(Pt–H) ¼ 77, Mea],
3
3
2.72 [t, J(H–H) ¼ 6.0, Hc], 2.80 [s, J(Pt–H) ¼ 18, Hb],
3
3.96 [t, J(H–H) ¼ 6.5, Hd], 7.35–7.45 [m, H3, H6], 7.78
H) ¼ 25, Hc], 2.98 [t, J(H–H) ¼ 6.0, Hd], 4.34 [t, J(H–
[s, H10], 7.81 [d, 3J(H–H) ¼ 7.5, H2], 7.92 [dd, 3J(H–
3
3
H) ¼ 6.0, He], 7.67 [td, 3J(H–H) ¼ 8.0, 4J(H–H) ¼ 1.0,
H) ¼ 8.5, J(H–H) ¼ 1.0, H1], 8.09 [dd, J(H–H) ¼ 7.5,
4
3
H2], 7.71 [td, J(H–H) ¼ 8.0, J(H–H) ¼ 1.0, H7], 7.73
4J(H–H) ¼ 1.0, H4], 8.35 [d, 3J(H–H) ¼ 8.0, H5], 8.53
3
4
3
4
3
3
4
3
[td, J(H–H) ¼ 8.0, J(H–H) ¼ 1.0, H6], 7.78 [td, J(H–
[dd, J(H–H) ¼ 8.8, J(H–H) ¼ 1.0, H7], 8.72 [s, J(Pt–
H) ¼ 8.0, 4J(H–H) ¼ 1.0, H3], 8.17 [d, 3J(H–H) ¼ 8.0,
H) ¼ 37, He]. 13C NMR (100 MHz, CDCl3): d ¼ 0:21
0
0
0
H1], 8.31 [dd, J(H–H) ¼ 8.0, J(H–H) ¼ 1.0, H8], 8.94
[Ca], 1.24 [Ca ], 48.6 [Cb], 49.4 [Cb0 ], 52.7 [Cc], 60.1 [Cc ],
3
4
0
0
3
3
4
[d, J(H–H) ¼ 8.0, H4], 9.01 [dd, J(H–H) ¼ 8.0, J(H–
65.2 [Cd ],0 68.6 [Cd], {119.2 [C5 ], 122.1 [m, C1 , C4],
0
H) ¼ 1.0, H5], 9.53 [s, H10], 10.04 [s, J(Pt–H) ¼ 49, Hf ].
122.8 [C10 ], 123.5–123.7 [4s, C8, C5, C7 , C1], 124.0,
3
13C NMR (62.5 MHz, CDCl3): d ¼ )24.8 [Ca, 1J(Pt–
125.6, 126.1, 126.7, 127.0,0 128.1 [C3], 128.7 [C6], 129.2
0
C) ¼ 1158], )18.4 [Cb, J(Pt–C) ¼ 912], 49.5 [Cc], {65.3,
[C2 ], CHAr}, 157.7 [s, Ce ], 165.2 [s, Ce]. 195Pt NMR
1
65.2, Cd, Ce}, {122.6, 123.4, 123.5, 126.8, 126.9, 127.0,
(54 MHz, CDCl3): d ¼ ꢀ3218 [s, 4a0], )3421 [s, 4a].

M. Crespo, E. Evangelio / Journal of Organometallic Chemistry 689 (2004) 1956–1964
1963
MS-FAB (+) (NBA, m=z): 485 [M]þ, 470 [M–Me]þ
Anal. Found: C, 48.9; H, 5.0; N, 5.3. Calc. for
C20H22N2Pt: C, 49.48; H, 4.57; N, 5.77%.
[C10], 141.4 [C7], {125.9, 129.1, 133.0, 136.0, CAr}, 157.4
[Cd]. 195Pt NMR (54 MHz, CDCl3): d ¼ ꢀ2944 [s]. MS-
FAB(+) (NBA, m=z): 505 [M]þ, 470 [M–Cl]þ. Anal.
Found: C, 44.6; H, 4.0; N, 4.9. Calc. for C19H19ClN2Pt:
C, 45.11; H, 3.79; N, 5.54%.
[PtMe{9-(Me2NCH2CH2NCH)C14H8}] (4b). Yield:
1
74 mg (80%). H NMR (500 MHz, CDCl3): d ¼ 1:07 [s,
2J(Pt–H) ¼ 76, Mea], 2.91 [t, 3J(H–H) ¼ 6.0, Hc], 2.92 [s,
3J(Pt–H) ¼ 17, Hb], 4.31 [t, 3J(H–H) ¼ 6.0, Hd], 7.32 [dd,
3J(H–H) ¼ 7.5, 4J(H–H) ¼ 1.0, H6], 7.43 [dd, 3J(H–
[PtCl{9-(Me2NCH2CH2NCH)C14H8}] (5b). Yield: 60
mg (58%). 1H NMR (400 MHz, CDCl3): d ¼ 2:76
3
3
[t, J(H–H) ¼ 6.0, Hb], 2.98 [s, J(Pt–H) ¼ 12, Ha], 4.27
4
3
3
3
H) ¼ 6.5, J(H–H) ¼ 1.0, H3], 7.59 [ddd, J(H–H) ¼ 9.0,
3J(H–H) ¼ 6.5, 4J(H–H) ¼ 1.5, H2], 7.74 [d, 3J(H–
H) ¼ 8.0, H5], 8.04 [d, 3J(H–H) ¼ 8.0, H4], 8.26 [dd,
3J(H–H) ¼ 7.0, 4J(H–H) ¼ 1.0, H7], 8.41 [d, 3J(H–
[t, J(H–H) ¼ 6.0, Hc], 7.42 [t, J(H–H) ¼ 8.0, H6], 7.46
[td, 3J(H–H) ¼ 8.0, 4J(H–H) ¼ 1.0, H3], 7.62 [t, 3J(H–
3
4
H) ¼ 8.0, H2], 7.77 [dd, J(H–H) ¼ 8.0, J(H–H) ¼ 1.0,
H5], 8.02 [d, 3J(H–H) ¼ 8.0, H4], 8.27 [d, 3J(H–H) ¼ 8.0,
H1], 8.67 [s, H10], 8.86 [dd, 3J(H–H) ¼ 8.0, 4J(H–
H) ¼ 1.0, 3J(Pt–H) ¼ 57, H7], 9.64 [s, 3J(Pt–H) ¼ 119,
Hd]. 13C NMR (75 MHz, CDCl3): d ¼ 49:7 [Ca], 63.4
[Cc] 64.6 [Cb], 123.8 [C1], 125.4 [C6], 125.9 [C3], 128.0
[C5], 129.4 [C2], 129.5 [C4], 138.8 [C10] 144.2 [C7], 150.3
[Cd]. 195Pt NMR (54 MHz, CDCl3): d ¼ ꢀ2891 [s]. MS-
FAB(+) (NBA, m=z): 505 [M]þ, 470 [M–Cl]þ. Anal.
Found: C, 39.5; H, 4.5; N, 5.2. Calc. for
C19H19ClN2Pt Æ 4H2O: C, 39.48; H, 4.71; N, 4.85%.
Compounds 6 were obtained when methyl iodide (0.5
ml) was added to a stirred solution of 4a/4a0 or 4b (52
mg, 0.11 mmol) in acetone (20 ml). Continuous stirring
was maintained during 30 min. The solvent was re-
moved in the rotary evaporator and the residue was
washed with hexane and the yellow (4a/4a0) or orange
(4b) solid was dried in vacuum.
H) ¼ 9.0, H1], 8.67 [s, H10], 10.04 [s, J(Pt–H) ¼ 40, He].
3
13C NMR (75 MHz, CDCl3): d ¼ ꢀ3:8 [1J(Pt–C) ¼ 854,
Ca], 49.3 [Cb], 61.4 [Cc], 65.1 [Cd], 121.8 [C1], 124.0 [C3],
125.4 [C6], 126.4 [C5], 127.4 [C2], 129.7 [C4], 137.1 [C10],
140.8 [C7], {124.8, 125.9, 129.2, 130.0, 132.48, 133.50,
CAr}, 150.1 [Ce]. 195Pt NMR (54 MHz, CDCl3):
d ¼ ꢀ3078 [s]. MS-FAB (+) (NBA, m=z): 485 [M]þ, 470
[M–Me]þ. Anal. Found: C, 46.5; H, 5.3; N, 5.2. Calc. for
C20H22N2Pt Æ 2H2O: C, 46.06; H, 5.03; N, 5.37%.
Compounds 3a0 and 3b0 were obtained from reaction
of cis-[PtCl2(dmso)2] (10) (150 mg, 0.36 mol) with the
equimolecular amount (98 mg) of the corresponding
imine in dry methanol. The mixture was refluxed during
4 h, and the insoluble orange solids were filtered and
dried in vacuo.
[PtCl2{9-(Me2NCH2CH2NCH)C14H9}] (3a0). Yield:
200 mg (97%). IR m(CH@N) ¼ 1650 cmꢀ1. MS-MALDI
(m=z): 505.0 [M–Cl]þ, 468.0 [M–2Cl]þ. Anal. Found: C,
42.1; H, 4.1; N, 5.0. Calc. for C19H20Cl2N2Pt: C, 42.08;
H, 3.72; N, 5.16%.
[PtCl2{9-(Me2NCH2CH2NCH)C14H9}] (3b0). Yield:
185 mg (90%). IR m(CH@N) ¼ 1623 cmꢀ1. MS-MALDI
(m=z): 505.0 [M–Cl]þ, 468.0 [M–2Cl]þ. Anal. Found: C,
42.2; H, 4.0; N, 5.0. Calc. for C19H20Cl2N2Pt: C, 42.08;
H, 3.72; N, 5.16%.
[PtMe2I{9-(Me2NCH2CH2NCH)C14H8}]
(6a/6a0).
Yield: 55 mg (82%). 1H NMR (500 MHz, CDCl3):
2
2
d ¼ 0:77 [s, J(Pt–H) ¼ 71, Mea], 0.98 [s, J(Pt–H) ¼ 71,
0
Mea ], 1.44 [s, 2J(Pt–H) ¼ 65, Meb], 1.64 [s, 2J(Pt–
0
H) ¼ 59, Meb ], {2.49 [s, 3J(Pt–H) ¼ 16, 3H], 2.52 [s,
3J(Pt–H) ¼ 15, 3H], 3.13 [s, 0 J(Pt–H) ¼ 12, 3H], 3.24 [s,
3
3J(Pt–H) ¼ 11, 3H], Hc, Hc }, {2.67 [m, 1H], 3.72 [td,
2J(H–H) ¼ 15, J(H–H) ¼ 4.0, 1H], Hd}, {2.99 [m, 1H],
3
0
4.27 [td, J(H–H) ¼ 10, J(H–H) ¼ 5.0, 1H], Hd }, {4.01
2
3
Compounds 5 were obtained when acetylchloride (0.5
ml) was slowly added to a stirred solution of 4a/4a0 or 4b
(100 mg) in a 1:1 mixture of dichloromethane and
methanol (20 ml). Continuous stirring was maintained
during 15 min and the solvents were removed. Crystal-
lisation of the obtained residues in dichloromethane/
hexane afforded yellow compounds, which were dried in
vacuum.
[m, 1H], 4.15 [m, 1H], He}, {4.08 [m, 1H], 4.11 [m, 1H],
0
He }, {7.39 [t, J(H–H) ¼ 8.0, 1H], 7.49–7.57 [m, 3H],
3
7.61–7.69 [m, 3H], 7.82 [d, 3J(H–H) ¼ 7.0, 1H], 7.83 [dd,
0
3J(H–H) ¼ 7.0, J(H–H) ¼ 1.0, 1H], 7.88 [s, H10 ], 8.07
[m, 1H], 8.33 [d, 3J(H–H) ¼ 8.0, 1H], 8.53 [d, 3J(H–
H) ¼ 8.0, 1H], 8.60 [m, 2H], 8.71 [m, 1H], aromatics},
4
0
8.57 [s, Hf ], 9.42 [s, J(Pt–H) ¼ 48, Hf ]. 130 C NMR (100
3
MHz, CDCl3): d ¼ ꢀ3:5 [Mea], 2.1 [Mea ], 10.6 [Meb],
0
0
[PtCl{9-(Me2NCH2CH2NCH)C14H8}] (5a0). Yield:
12.1 [Meb ], {46.4, 47.2, 52.7, 54.5, Ccc }, {52.1, 59.2,
0
0
1
40 mg (38%). H NMR (500 MHz, CDCl3): d ¼ 2:63 [s,
64.1, 68.3 Cdd ee }, {120.1, 122.2, 123.0, 123.5, 123.6,
125.5, 126.5, 126.9, 127.2, 127.3, 129.1, 129.7, 129.8,
3
3J(H–H) ¼ 6.0, Hb], 2.94 [s, J(Pt–H) ¼ 14, Ha], 3.91 [t,
0
3J(H–H) ¼ 6.0, Hc], 7.44 [s, H10], 7.47 [m, H3, H6], 7.58
134.8, 136.1, 141.0, CHAr}, 162.8 [Cf ], 167.1 [Cf ]. 195Pt
3
4
3
[dd, J(H–H) ¼ 7.0, J(H–H) ¼ 1, H2], 7.71 [dd, J(H–
NMR (54 MHz, CDCl3): d ¼ ꢀ2429 [s]; )2524 [s]. MS-
FAB(+) (NBA, m=z): 500 [M–I]þ, 485 [M–I–Me]þ.
Anal. Found: C, 40.8; H, 4.4; N, 4.3. Calc. for
C21H25IN2Pt: C, 40.20; H, 4.02; N, 4.46%.
H) ¼ 7.0, J(H–H) ¼ 1.0, H1], 8.43 [dd, J(H–H) ¼ 8.0,
4
3
4J(H–H) ¼ 1.0, H4], 8.65 [d, 3J(H–H) ¼ 8.0, H5], 8.83
3
4
3
[dd, J(H–H) ¼ 7.0, J(H–H) ¼ 1.0, H7], 8.09 [s, J(Pt–
H) ¼ 117, Hd]. 13C NMR (75 MHz, CDCl3): d ¼ 49:7
[Ca], 63.2 [Cb] 63.3 [Cc], 120.3 [C4], 123.5 [C5], 126.0 [C3
or C6], 126.4 [C3 or C6], 129.1 [C2], 129.5 [C1], 139.2
[PtMe2I{9-(Me2NCH2CH2NCH)C14H8}] (6b). Yield:
60 mg (90%). 1H NMR (400 MHz, CDCl3): d ¼ 1:20 [s,
2
2J(Pt–H) ¼ 72, Mea], 1.47 [s, J(Pt–H) ¼ 65, Meb], {2.59

1964
M. Crespo, E. Evangelio / Journal of Organometallic Chemistry 689 (2004) 1956–1964
3
3
[s, J(Pt–H) ¼ 13, 3H], 3.31 [s, J(Pt–H) ¼ 10, 3H], Hc},
ꢀ
[3] C. Anderson, M. Crespo, M. Font-Bardıa, A. Klein, X. Solans, J.
Organomet. Chem. 601 (2000) 22.
{2.76 [m, 1H], 3.73 [m, 1H], Hd}, {4.22 [m, 1H], 4.39 [m,
[4] C. Anderson, M. Crespo, J. Organomet. Chem. 689 (2004) 1496.
[5] (a) E. Wehman, G. van Koten, J.T.B.H. Jastrzebski, H. Ossor, M.
Pfeffer, J. Chem. Soc., Dalton Trans. (1988) 2975;
(b) M. Pfeffer, N. Sutter-Beydoun, A. De Cian, J. Fischer, J.
Organomet. Chem. 453 (1993) 139;
1H], He}, {7.31 [t, J(H–H) ¼ 7.8, 1H], 7.47 [t, J(H–
3
3
H) ¼ 7.4, 1H], 7.58 [t, J(H–H) ¼ 8.0, 1H], H2, H3, H6},
3
{7.62 [d, 3J(H–H) ¼ 8.0, 1H], 7.87 [d, 3J(H–H) ¼ 8.0,
2J(Pt–H) ¼ 63, 1H], 7.99 [d, 3J(H–H) ¼ 8.0, 1H], 8.39 [d,
3J(H–H) ¼ 8.0, 1H], H1, H4, H5, H7}, 8.61 [s, H10],
(c) E. Wehman, G. van Koten, C.T. Knaap, H. Ossor, M. Pfeffer,
A.L. Spek, Inorg. Chem. 27 (1988) 4409;
aromatics}, 9.70 [s, J(Pt–H) ¼ 32, Hf ]. 13C NMR (100
3
(d) I.G. Phillips, P.J. Steel, J. Organomet. Chem. 410 (1991) 247;
(e) L. Kind, A.J. Klaus, P. Rys, V. Gramlich, Helv. Chim. Acta
81 (1998) 307.
MHz, CDCl3): d ¼ 1:9 [1J(Pt–C) ¼ 670, Mea], 12.13
[1J(Pt–C) ¼ 678, Meb], {47.3, 54.7, Cc}, {60.9,Ce}, {64.3,
Cd}, {121.9, 127.4, 130.1, 137.6, C1, C4, C5, C7}, {124.8,
126.0 [2J(Pt–C) ¼ 66], 128.4, C2, C3, C6}, 138.6 [C10],
{123.7, 128.5, 130.2, 132.3, 134.3, 134.9, CAr}, 156.0
[Cd]. 195Pt NMR (54 MHz, CDCl3): d ¼ ꢀ2433 [s]. MS-
FAB(+) (NBA, m=z): 500 [M–I]þ, 485 [M–I–Me]þ, 470
[M–I–2Me]þ. Anal. Found: C, 39.1; H, 4.2; N, 4.3. Calc.
for C21H25IN2Pt Æ H2O: C, 39.08; H, 4.22; N, 4.34%.
ꢀ ꢀ
[6] M. Crespo, M. Font-Bardıa, S. Perez, X. Solans, J. Organomet.
Chem. 642 (2002) 171.
[7] (a) C.M. Anderson, M. Crespo, M.C. Jennings, A.J. Lough, G.
Ferguson, R.J. Puddephatt, Organometallics 10 (1991) 2672;
ꢀ
(b) M. Crespo, M. Martinez, J. Sales, X. Solans, M. Font-Bardıa,
Organometallics 11 (1992) 1288;
(c) M. Crespo, C. Grande, A. Klein, J. Chem. Soc., Dalton Trans.
(1999) 1629.
[8] (a) G. Minghetti, M.A. Cinellu, G. Chelucci, S. Gladiali, F.
Demartin, M. Manassero, J. Organomet. Chem. 307 (1986) 107;
(b) R. Annunziata, S. Cenini, F. Demartin, G. Palmisano, S.
Tollari, J. Organomet. Chem. 496 (1995) C(1);
(c) G. Minghetti, A. Doppiu, S. Stoccoro, A. Zucca, M.A.
Cinellu, M. Manassero, M. Sansoni, Eur. J. Inorg. Chem. (2002)
431;
Acknowledgements
This work was supported by the Ministerio de Cien-
ꢀ
cia y Tecnologıa (Project: BQU2003-00906/50% FED-
ER) and by the Comissionat per a Universitats i Recerca
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