Synthesis and reactivity of cyclometallated platinum (II) compounds containing [C,N,N′] terdentate ligands: Crystal structures of [PtCl{(CH3)2N(CH2)3NCH(4-ClC 6H3)}], [PtCl{(CH3)2N(CH 2)3NCH(2-ClC6H3)}]

Article abstract of DOI:10.1016/j.jorganchem.2005.06.038

The reaction of compound cis-[PtCl₂(dmso)₂] with ligands RCHN(CH₂)₃NMe₂ (1a-1h) in which R is a phenyl group containing substituents such as Cl, F, Me, NO₂ and MeO produced compounds [PtCl₂{(CH₃)₂N(CH ₂)₃NCHR}] (2), as mixtures of Z and E isomers. When treated with an equimolar amount of sodium acetate in refluxing methanol compounds 2 gave cyclometallated platinum compounds 3 containing a terdentate [C,N,N′] ligand. The obtained compounds were fully characterized including structure determinations for compounds 3a, 3b and 3e. The effects of the substituents in the regioselectivity of the cyclometallation reaction and the reactivity of 3a and 3b with mono and bidentate phosphines were also studied.

Full text of DOI:10.1016/j.jorganchem.2005.06.038

Journal of Organometallic Chemistry 690 (2005) 4309–4318
www.elsevier.com/locate/jorganchem
Synthesis and reactivity of cyclometallated platinum (II)
compounds containing [C,N,N0] terdentate ligands:
Crystal structures of [PtCl{(CH3)2N(CH2)3NCH(4-ClC6H3)}],
[PtCl{(CH3)2N(CH2)3NCH(2-ClC6H3)}] and
[PtCl{(CH3)2N(CH2)3NCH(3-(CH3)C6H3)}]
a
a,
a
Alejandro Capape , Margarita Crespo *, Jaume Granell ,
´
`
b
b
´
Merce Font-Bardıa , Xavier Solans
a
`
Departament de Quı´mica Inorganica, Universitat de Barcelona, Diagonal 647, 08028 Barcelona, Spain
`
b
´
`
Departament de CristalÆlografia, Mineralogı´a i Diposits Minerals, Universitat de Barcelona, Martı i Franques s/n, 08028 Barcelona, Spain
Received 22 April 2005; received in revised form 15 June 2005; accepted 16 June 2005
Available online 10 August 2005
Abstract
The reaction of compound cis-[PtCl2(dmso)2] with ligands RCHN(CH2)3NMe2 (1a–1h) in which R is a phenyl group containing
substituents such as Cl, F, Me, NO2 and MeO produced compounds [PtCl2{(CH3)2N(CH2)3NCHR}] (2), as mixtures of Z and E
isomers. When treated with an equimolar amount of sodium acetate in refluxing methanol compounds 2 gave cyclometallated plat-
inum compounds 3 containing a terdentate [C,N,N0] ligand. The obtained compounds were fully characterized including structure
determinations for compounds 3a, 3b and 3e. The effects of the substituents in the regioselectivity of the cyclometallation reaction
and the reactivity of 3a and 3b with mono and bidentate phosphines were also studied.
ꢀ 2005 Elsevier B.V. All rights reserved.
Keywords: Platinum; Cyclometallation; Nitrogen ligands
1. Introduction
In this work, the reactions of ligands RCHN(CH2)3-
NMe2 (R being a substituted aryl ring) with cis-
[PtCl2(dmso)2] are reported. Analogous potentially
terdentate imines RCHN(CH2)2NMe2 have been
reported to produce intramolecular C–H bond activa-
tion via oxidative addition at platinum substrates such
as [Pt(dba)2] [3], [Pt2Me4(l-SMe2)2] [4] or [PtMe2(cod)]
[5]. Compound [Pt(l-Cl)(g3-2Me-C3H4)]2 has also been
used for the synthesis of terdentate cycloplatinated
derivatives [6]. The recent progress in using the platinum
(II) complex cis-[PtCl2(dmso)2] as an electrophilic cyclo-
metalating agent [7] can be attributed to its easy synthe-
sis and high stability. In addition, [N,N0] coordination
compounds can be isolated as a prior step to the
Cyclometallated compounds, in particular those de-
rived from nitrogen ligands, have been a topic of interest
in the last years as a consequence of the wide range of
their potential applications in many areas [1]. Although
this field has been widely studied for bidentate [C,N] li-
gands, there are less examples of the cyclometallation of
potentially terdentate [C,N,N0] ligands, which benefit
from a second N-donor atom [2].
*
Corresponding author. Tel.: +34934039132; fax: +34934907725.
E-mail address: margarita.crespo@qi.ub.es (M. Crespo).
0022-328X/$ - see front matter ꢀ 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2005.06.038

4310
A. Capape´ et al. / Journal of Organometallic Chemistry 690 (2005) 4309–4318
cyclometallation process, thus improving the overall
yield. As reported in the literature, [7d,7e] such coordi-
nation compounds can be readily converted into cyclo-
platinated derivatives via C–H activation when
refluxed for several hours in a donor solvent in the pres-
ence of an external base such as sodium acetate.
The ligands selected in the present study contain sub-
stituents of different nature in the aryl group (Cl, F, Me,
NO2, MeO) and thus should allow us to clarify the influ-
ence of stereo-electronic effects of the substituents in
both the reactivity and the regioselectivity of the C–H
bond activation at platinum.
The reaction of the imines with cis-[PtCl2(dmso)2] in
refluxing methanol gave the corresponding coordination
compounds [PtCl2{(CH3)2N(CH2)3NCHR}] (2). As
noted in Scheme 1, a mixture of two isomers corre-
sponding to the two possible conformations (Z and E)
around the C@N bond was obtained. Generally, the Z
isomer was the most abundant (for imines 1f and 1g it
was the only which could be isolated and characterised)
and in the specific case of imine 1a the two isomers could
be obtained separately. These isomers display striking
differences in their spectral features. The 1H NMR
shows among other peculiarities an anisotropic effect
in both the methylene and NMe2 protons in the Z iso-
mer, and a strong deshielding effect in the imine proton
of the E isomer (d = 9.26–9.54 ppm) caused by plati-
num. For both isomers evidence of coordination of the
two nitrogen atoms to platinum is obtained from the
fact that both methylamino and imine protons are cou-
pled to 195Pt. The J(H–Pt) values for the imine proton
are higher for the Z (ca. 120 Hz) than for the E isomers
(ca. 60 Hz). Furthermore, the nature of the compounds
in which the imine acts as a bidentate [N,N0] ligand was
confirmed by FAB mass spectra in all cases and elemen-
tal analysis except for 2f and 2g which could not be ob-
tained in an analytically pure form. A slight decrease of
the wave-numbers in the imine bond stretching peaks
was observed in the IR spectra.
2. Results and discussion
2.1. Reactions of the imines with cis-[PtCl2(dmso)2]
The N-(substituted benzylidene)-N0,N0-dimethyl-1,3-
propanediamines RCHN(CH2)3NMe2 (1a–h) were ob-
tained from the condensation reaction between
Me2N(CH2)3NH2 and the corresponding aldehyde un-
1
der the usual conditions [3,8–10]. In the H NMR spec-
tra a signal (ca. 8–9 ppm) corresponding to the imine
proton is displayed. IR data are consistent with the for-
mation of a C@N bond, showing intense peaks around
1650 cmꢀ1
.
c,c'
d,d'
b,b'
R2
R4
R2
Ha
a
5
b
d
R3
R4
R2
R4
N
NMe2
cis-[PtCl2(dmso)2]
Z
N
NMe2
c
6
Pt
c
R3
e,e'
e
+
b
d
Cl
Cl
6
R3
6
5
E
N
NMe2
Pt
1a: R4=Cl R2,R3,R6=H
e
5
Ha
Cl
Cl
1b: R2=Cl R3,R4,R6=H
1c: R3=Cl R2,R4,R6=H
1d: R3=F R2,R4,R6=H
1e: R3=Me R2,R4,R6=H
1f: R2,R3,R4,R6=H
2a: R4=Cl R2,R3=H
2f: R2,R3,R4=H
2g: R4=NO2 R2,R3=H
2a': R4=Cl R2,R3=H
2b: R2=Cl R3,R4=H
2c: R3=Cl R2,R4=H
2d: R3=F R2,R4=H
2e: R3=Me R2,R4=H
2h: R3,R4= MeO R2=H
1g: R4=NO2 R2,R3,R6=H
1h: R3,R4= MeO R2,R6=H
R2
a
NaAcO
R3
b
4a: R4=Cl R2,R3=H
4b: R2=Cl R3,R4=H
N
3a: R4=Cl R2,R3=H
Pt
c
R4
R2
3b: R2=Cl R3,R4=H
3c: R3=Cl R2,R4=H
3d: R3=F R2,R4=H
3e: R3=Me R2,R4=H
3f: R2,R3,R4=H
5
Cl
PPh3
dppe
Ph3P
f,g,h
d
a
R3
R4
NMe2
e
b
N
Cl
a
Pt
c
3
5
Cl
3g: R4=NO2 R2,R3=H
3h: R3,R4= MeO R2=H
b
Me2N
5b
Cl
N
d
e
c
d
5
Pt
4
PPh2
g
Ph2P
h
NMe2
e
f
Scheme 1.

A. Capape´ et al. / Journal of Organometallic Chemistry 690 (2005) 4309–4318
4311
The terdentate [C,N,N0] cyclometallated compounds
H
were obtained from the equimolar reaction of the coor-
dination compounds and sodium acetate as auxiliary
base in refluxing methanol. The process involves the
activation of a C–H bond and the formal release of
N
NMe2
Cl
Pt
Cl
R3
1
2c: R3 = Cl, R4 = H
2d: R3 = F, R4 = H
2e: R3 = Me, R4 = H
2h: R3,R4 = MeO
R4
HCl which is promoted in the presence of a base. H
NMR, along with other characterisation tools, con-
firmed ortho-metallation of the imine and formation of
1
a fused [6,5,6]-tricyclic system. In the H NMR, J(H–
Chart 1. The two possible metallation sites for asymmetric ligands.
Pt) values for the imine proton (ca. 140 Hz) are higher
than those observed for compounds 2 and a new signal
also coupled to 195Pt appears next to the imine proton
and is assigned to the aromatic proton adjacent to the
metallated position. The 195Pt NMR spectra (3a, 3b,
3f and 3h) show only one signal, the position of which
is consistent with the nature of the ligands bound to
platinum [11]. The values indicate a downfield shift in
the sequence 3f < 3h < 3b ꢁ 3a which is consistent with
increasing deshielding of the platinum nucleus on
changing the substituents (MeO, H or Cl) in the aryl
group. 13C NMR spectra for compounds 3b, 3f and
3h confirm the cyclometallation process since only three
(3b), four (3f) and two (3h) resonances corresponding to
aromatic C–H appear; in addition, for 3b the metallated
carbon C(6) appears as a downfield shifted signal with a
large coupling constant to 195Pt (J(C–Pt) = 1019 Hz).
FAB spectra show two intense signals corresponding
to M and M ꢀ X fragments, and in some cases weak
signals corresponding to dinuclear species 2M and
2M ꢀ X. Following the tendency of coordination com-
pounds, the m(C@N) peaks in the IR spectra have smal-
ler values than their precursors. That would be in
agreement with a weakening of the imine bond due to
the platinum and/or a delocalization effect within the
metallacycle. All compounds were characterized by ana-
lytical and spectroscopic techniques, and 3a, 3b and 3e
were characterized crystallographically as well. Com-
pound 3b was also synthesized following the previously
reported procedure using [Pt(dba)2] (dba = dibenzylide-
neacetone) as metallating agent and imine 2,6-
Cl2C6H3CHN(CH2)3NMe2. Yield and purity were
remarkably poorer than those observed for the method
described in the present work.
solubility of the cyclometallated compounds or confor-
mational effects could play an important role.
On the other hand, the fairly good experimental re-
sults obtained for the 2-chlorosubstituted ligand (1b)
can be related to the N@CHꢂ ꢂ ꢂCl interaction which rein-
forces the planarity of the ArC@N fragment [12] and in-
creases the stability of the corresponding compound 3b.
As shown in Chart 1, cyclometallation of 3-R substi-
tuted imines can give two different metallated isomers,
depending whether metallation takes place at position
2 or position 6 of the phenyl ring. We performed reac-
tions with ligands containing 3-Cl (1c), 3-F (1d), 3-Me
(1e) and 3,4-MeO (1h) substituted phenyl ring in order
to investigate if the steric and/or electronic effects play
a significant role in the regioselectivity of the reaction.
Experimental results point to a major influence of the
steric hindrance of the substituents, since cycloplatina-
tion of ligands 1c, 1e and 1h produced only a single iso-
mer in which cyclometallation took place at the less
hindered site (position 6) regardless of the electronic
effects caused by each substituent. Only for the small flu-
oro substituent, activation was achieved at the two non-
equivalent positions leading to a mixture of two isomers
in a 2.5 : 1 ratio, the major isomer corresponding to met-
allation at the less hindered position. Additional evi-
dence was obtained from the 19F NMR since coupling
to 195Pt was observed for the signal corresponding to
the minor isomer.
2.2. Reactions with phosphines
The position and nature of the substituents in the aryl
ring can either determine or favor the carbon position in
which the electrophilic attack takes place. For example,
imine with 4-chloro-substituted aryl ring was easily met-
allated, producing with higher yields bright red crystals
that were fully characterised. Imines with 4-nitro-substi-
tuted and unsubstituted aryl rings, however, gave in
comparison poor results, leading to low yields and
unpurified products. All the experimental results here re-
ported cannot be fully understood taking only into ac-
count the electronic effect of the substituents; a
concerted mechanism via a tetra-centered transition
state [7e], along with other factors such as the relative
As shown in previous works [13], the reaction of
cyclometallated compounds with mono or bidentate
phosphines can result in the cleavage of the metallacy-
cles, leading to bidentate [C,N] or even monodentate
[C] systems. In order to analyse the reactivity of the
cyclometallated compounds in front of phosphines, the
reaction of 3a and 3b with triphenylphosphine and 1,
2-bisdiphenylphosphinoethane (dppe) were studied and
the results are shown in Scheme 1.
In compounds 4a and 4b obtained upon reaction with
triphenylphosphine the imine behaves as a [C,N] biden-
tate ligand and the square-planar coordination of plati-
num (II) is completed with a phosphine and a halide

4312
A. Capape´ et al. / Journal of Organometallic Chemistry 690 (2005) 4309–4318
1
ligand. In the H NMR spectra, no platinum satellites
are observed for the dimethylamino group, thus ruling
out the possibility of penta-coordination of the plati-
num. The trans arrangement of the phosphine and the
imine is expected in agreement with the transphobia ef-
fect [14], and experimental evidence is obtained from
the value of J(P–Pt) and the observed coupling of the
imine to the phosphorous in trans.
Compound 5b obtained upon reaction of 3b with
dppe contains the chelated diphosphine and the imine
as a bidentate [C,N] ligand. The 31P NMR spectrum
shows two sets of resonances due to two non-equivalent
phosphorus atoms, both coupled to platinum. A peak
corresponding to the complex cation was obtained in
the FAB mass spectrum. The formation of compound
5b clearly shows the high stability of the metallacycle
which is resistant to cleavage even when reacted with
chelating diphosphine.
Fig. 2. Molecular structure of compound 3b.
2.3. Crystal structures
Suitable crystals of compounds 3a, 3b and 3e (Figs.
1–3, respectively) were grown from acetone solution.
All crystal structures are composed of discrete molecules
separated by Van der Waals distances. Selected molecu-
lar dimensions, listed in Table 1, confirm the geometries
predicted from spectroscopic data.
In spite of the presence of different substituents (para-
chloro (3a), ortho-chloro (3b), meta-methyl (3e)), the
three structures lack of significant differences among
them. The three compounds consist of a fused [6,5,6] tri-
cyclic system containing a five-membered metallacycle, a
chelate ring with two nitrogen atoms coordinated to
platinum and the ortho-metallated phenyl group. The
square-planar coordination environment of the metal,
adopted by most Pt(II) compounds, is completed by a
chlorine atom. For 3e, the molecular structure provides
decisive evidence of the fact that metallation takes place
regioselectively at the less hindered position. As shown
in Table 1, bond lengths and angles are well within the
Fig. 3. Molecular structure of compound 3e.
range of values obtained for analogous compounds
[3,5,7]. Most bond angles at platinum are close to the
ideal value of 90ꢁ, and the smallest angles correspond
to the metallacycle (79.6(12)ꢁ (3a); 81.1(3)ꢁ (3b);
80.73(19)ꢁ (3e)). The chelate angle N(1)–Pt–N(2) is
greater (95.2(8)ꢁ (3a); 97.3(3)ꢁ (3b); 95.00(18)ꢁ (3e)) than
for analogous compounds derived from N,N-dimethyle-
thylenediamine [3,5]. The imine C@N bond lengths lie in
the usual range, and Pt–amine distances are larger than
platinum–imine distances consistent with the weaker
ligating ability of amines for platinum. The Pt–amine
distances are greater than those observed for com-
pounds derived from N,N-dimethylethylenediamines
[3,5]. The chelate ring presents a strong deviation in its
planarity caused by the propyl moiety as reported for
analogous compounds [7d,10]. The metallacycle atoms
adopt a practically planar arrangement, as shown by
the sum of their internal bond angles which is close to
540ꢁ [15]. The metallacycle is nearly coplanar with the
coordination plane, the dihedral angle between the mean
planes ranging from 3.90ꢁ (3e) to 5.90ꢁ (3b).
Intramolecular distances were measured and the va-
lue obtained for N@CHꢂ ꢂ ꢂCl in compound 3b
˚
(3.143(10) A) confirms the interaction suggested above.
Fig. 1. Molecular structure of compound 3a.

A. Capape´ et al. / Journal of Organometallic Chemistry 690 (2005) 4309–4318
4313
Table 1
Selected bond lengths (A) and angles (ꢁ) with estimated standard deviations
˚
3a
3b
3e
Pt–N(1)
Pt–C(1)
Pt–N(2)
Pt–Cl(1)
N(2)–C(7)
C(7)–C(6)
C(6)–C(1)
2.180(9)
1.955(15)
2.092(13)
2.240(4)
1.23(2)
Pt–N(1)
Pt–C(1)
Pt–N(2)
Pt–Cl(2)
N(1)–C(7)
C(7)–C(6)
C(6)–C(1)
1.981(7)
1.985(8)
2.170(8)
2.289(2)
1.267(12)
1.430(12)
1.419(11)
Pt–C(1)
Pt–N(1)
Pt–N(2)
Pt–Cl
N(1)–C(8)
C(6)–C(8)
C(1)–C(6)
1.959(5)
1.986(4)
2.186(5)
2.306(2)
1.282(6)
1.423(7)
1.388(6)
1.47(2)
1.47(4)
C(1)–Pt–N(2)
N(2)–Pt–N(1)
C(1)–Pt–Cl(1)
N(1)–Pt–Cl(1)
79.6(12)
95.2(8)
93.7(12)
91.7(8)
N(1)–Pt–C(1)
N(1)–Pt–N(2)
C(1)–Pt–Cl(2)
N(2)–Pt–Cl(2)
81.1(3)
97.3(3)
92.5(3)
89.02(18)
N(1)–Pt–C(1)
N(1)–Pt–N(2)
C(1)–Pt–Cl
80.73(19)
95.00(18)
93.74(16)
90.40(16)
N(2)–Pt–Cl
Total:a
360.2
359.92
359.87
N(2)–Pt–C(1)
C(7)–N(2)–Pt
C(7)–C(6)–C(1)
C(6)–C(1)–Pt
N(2)–C(7)–C(6)
79.6(12)
116.8(10)
112.0(12)
114.6(18)
116.9(13)
N(1)–Pt–C(1)
C(7)–N(1)–Pt
C(7)–C(6)–C(1)
C(6)–C(1)–Pt
N(1)–C(7)–C(6)
81.1(3)
115.9(6)
113.4(7)
111.6(6)
117.1(7)
C(1)–Pt–N(1)
C(8)–N(1)–Pt
C(6)–C(1)–Pt
C(1)–C(6)–C(8)
N(1)–C(8)–C(6)
80.73(19)
114.9(3)
114.0(3)
112.8(4)
117.4(4)
Total:b
539.9
539.1
539.83
a
Sum of angles in the coordination environment of the platinum atom.
Sum of internal angles of the metallacycle.
b
In addition, short distances C(2)-H(2)ꢂ ꢂ ꢂCl (3a,
ligand and (ii) intramolecular C–H bond activation in
the presence of a base. Isomerization of the ligand to
the adequate conformation around the C@N bond has
been reported to be a key step of the C–H bond activa-
tion process [7d,7e] and occurs more readily for the
more flexible propyl derivatives which are obtained as
a mixture of (Z) and (E) conformers than for the ethyl-
ene analogues which isomerizes only in the presence of a
base [7e]. In addition a pre-equilibrium dechelation pro-
cess is needed for the C–H activation to occur [8] and
this should be easier for the propylene than for the eth-
ylene amines assuming that a greater platinum–amine
distance, as obtained from crystallographic data of com-
pounds 3, also apply to coordination compounds de-
rived from propyleneamine. Given the advantageous
features of the propyl system, a study of regioselectivity
could also be realised for several 3-substituted ligands
(1c, 1d, 1e and 1h) and allow us to conclude that steric
effects play a decisive role in the selectivity of the C–H
bond activation.
˚
˚
˚
3.266(15) A; 3b, 3.250(10) A; 3e, 3.26(10) A) suggest a
weak intramolecular interaction similar to those re-
ported for analogous palladium compounds [12].
˚
In relation to intermolecular interactions, a ca. 3.6 A
distance was observed between the aromatic rings of 3e.
That might suggest p–p interactions within the aromatic
moieties, as reported previously in other works with
platinum cyclometallated compounds [16].
3. Conclusions
Although several platinum substrates, such as cis-
[PtCl2(dmso)2], [Pt(dba)2] and [Pt(l-Cl)(g3-2Me-
C3H4)]2 under different reaction conditions were initially
investigated in order to optimize the synthesis of cyclo-
metallated platinum compounds, the best yields and the
most easily purified metallacycles were those obtained
using cis-[PtCl2(dmso)2]. Indeed, the reaction of cis-
[PtCl2(dmso)2] with N-(substituted benzylidene)-N0,N0-
dimethyl-1,3-propanediamines allows the synthesis of
compounds in which the imine behaves as [N,N0] ligand
which are precursors of new cyclometallated platinum
(II) compounds containing a terdentate [C,N,N0] ligand.
The latter react with phosphines to yield compounds in
which the imine acts as a bidentate [C,N] ligand.
4. Experimental
4.1. General
The solvents were purified and distilled by standard
methods. Methanol (dry, max. 0.005H2O) was pur-
chased from Panreac.
Mass spectra were performed by the Servei dꢀEspec-
trometria de Masses de la Universitat de Barcelona.
The general picture of the process leading to [C,N,N0]
cyclometallated compounds is analogous to that de-
scribed for N-benzylidene-N0,N0-dimethyl-ethanediam-
ines which consists of: (i) coordination of the bidentate

4314
A. Capape´ et al. / Journal of Organometallic Chemistry 690 (2005) 4309–4318
NMR spectra were performed at the Unitat de NMR
dꢀAlt Camp de la Universitat de Barcelona. Microanal-
and 0.217 g (0.97 mmol) of imine 1b, using the proce-
dure reported for 2a. Yield 43%. IR: m(CH@N) =
yses were performed by the Servei de Recursos Cientıfics
1626.7, 1619.3, 1611.8 cmꢀ1 1H NMR (250 MHz,
;
´
i Tecnics de la Universitat Rovira i Virgili de Tarragona.
CDCl3): isomer Z d 10.79 [m, H6], 9.04 [s, 3J(Pt–
`
IR spectra were recorded in Nicolet 520, Thermo-
Nicolet 5700 and Thermo-Nicolet Avatar 330 spectrofo-
tometers, using KBr pellets for solid samples and NaCl
support for liquid samples.
H) = 117.2, 1H, Ha], 7.58 [m, 2H, H3,5], 7.46 [m, 2H,
0
H4], 4.99 [m, 1H, Hb], 4.25 [m, 1H, Hb ], 3.20 [m,
0
1H, Hd], 2.99 [s, 3H, He], 2.90 [s, 3H, He0 ], 2.76 [m,
0
1H, Hd ], 2.41 [m, 1H, Hc], 2.00 [m, 1H, Hc ]; isomer E
d 9.38 [s, 3J(Pt–H) = 59.9, 1H, Ha ], 7.48 [dd 4J(H–
H) = 1.75, 3J(H–H) = 6.4, H8], 7.47 [m, 1H, H4 or 5],
FAB mass spectra were carried out in VG-Quattro
(with a 3-nitrobenzyl alcohol matrix) and Voyager
DE-RP (with a dithranol matrix) spectrometers. 1H,
13C, 31P, 19F and 195Pt NMR spectra were recorded by
using Varian Gemini-200 (1H, 200 MHz), Bruker
DRX-250 (1H, 250 MHz; 31P, 101 MHz; 195Pt,
54 MHz), Varian Unity-300 (1H, 300 MHz; NOESY;
13C, 75 MHz), Mercury-400 (1H, 400 MHz; 13C,
100.6 MHz; 19F, 376 MHz; NOESY), Inova-500 (1H,
500 MHz) and Bruker DMX-500 (1H, 500 MHz; COSY)
spectrometers, and referenced to SiMe4 (1H, 13C),
P(OMe)3 in (CD3)2CO (31P) and H2PtCl6 in D2O
4
3
7.39 [td, J(H–H) = 2.4, J(H–H) = 7, 1H, H4 or 5], 7.29
[d, 3J(H–H) = 7.2, 1H, H3], 3.92 [td, 4J(H–H) =1.5,
3J(H–H) = 6.75, 3J(Pt–H) = 35, 2H, Hb], 3.01 [s,
3J(Pt–H) = 33.2, He], 2.70 [m, 2H, Hd], 2.14 [m, 2H,
Hc]. FAB-MS, m/z: 532.90 [M ꢀ Cl + dmso]+, 455
[M ꢀ Cl]+, 419 [M ꢀ 2Cl]+. Anal. Calc.: C, 29.36; H,
3.68; N, 5.62. Found: C, 29.5; H: 3.5; N: 5.7.
[PtCl2{(CH3)2N(CH2)3NCH(3-ClC6H4)}] (2c) was
obtained from 0.320 g (0.75 mmol) of cis-[PtCl2(dmso)2]
and 0.168 g (0.75 mmol) of imine 1c, using the proce-
dure reported for 2a. Yield 34%. IR: m(CH@N) =
(
195Pt). d values are given in ppm and J values in Hz
1
(s = singulet; d = doblet; t = triplet; q = quadruplet;
qi = quintuplet; m = multiplet; b = broad).
1629.3 cmꢀ1; H NMR (250 MHz, CDCl3): isomer Z d
9.94 [d, 3J(H–H) = 7.6, 1H, H6], 8.50 [s, 3J(Pt–
H) = 107, 1H, Ha], 8.47 [t, 4J(H–H) = 1.8, 1H, H2],
4.2. Preparation of the compounds
7.6–7.4 [m, 2H, H4,5], 4.99 [m, 1H, Hb], 4.17 [m, 1H,
0
Hb ], 3.20 [bm, 1H, Hd], 2.98 [s, 3H, He], 2.96 [s, 3H,
0
0
[PtCl2(dmso)2] was prepared as reported elsewhere
[17]. Ligands 1a–1h were prepared under the usual con-
ditions reported in the literature [3,8–10] (see supple-
mentary material).
He ], 2.69 [m, 1H, Hd ], 2.40 [m, 1H, Hc], 1.96 [m, 1H,
0
Hc ]; isomer E d 9.31 [s, J(Pt–H) = 60, 1H, Ha], 7.64
[dt, 3J(H–H) = 8.8, 4J(H–H) = 1.2, 1H, H6], 7.42 [t,
4J(H–H) = 1.75, 1H, H2], 4.11 [td, 3J(H–H) = 6.5,
3
4J(H–H) = 1.6, J(Pt–H) = 56.0, 2H, Hb], 3.01 [s, 6H,
3
4.2.1. Preparation of the coordination compounds
[PtCl2{(CH3)2N(CH2)3NCH(4-ClC6H4)}]
He], 2.66 [m, 2H, Hd], 2.23 [m, 2H, Hc]; non-assigned
3
(2a,2a0)
protons: 7.64 [d, J(H–H) = 8.8, 1H, H4Z or 4E], 7.57 [t,
3
was obtained from 0.316 g (0.7 mmol) of cis-
[PtCl2(dmso)2] and 0.169 g (0.7 mmol) of imine 1a which
were allowed to react in refluxing methanol (30 ml) for
4 h. The solvent was removed in a rotary evaporator
and the residue was treated with methanol–dichloro-
methane, yielding a yellow solid which was filtered in
3J(H–H) = 8.0, 1H, H5Z or 5E], 7.54 [d, J(H–H) = 8.8,
1H, H4Z or 4E], 7.46 [t, J(H–H) = 8.0, 1H, H5Z or 5E].
3
FAB-MS, m/z: 568.96 [M ꢀ 2Cl + 2dmso]+, 532.97
[M ꢀ Cl + dmso]+, 452.97 [M ꢀ Cl]+, 418.01 [M ꢀ
2Cl]+. Anal. Calc.: C, 29.25; H, 3.73; N, 5.56. Found:
C, 29.5; H, 3.73; N, 5.7.
1
vacuum. Yield 72%. IR: m(CH@N) = 1625.3 cmꢀ1; H
[PtCl2{(CH3)2N(CH2)3NCH(3-FC6H4)}] (2d) was
obtained from 0.353 g (0.84 mmol) of cis-[PtCl2(dmso)2]
and 0.174 g (0.84 mmol) of imine 1d, using the procedure
3
NMR (250 MHz, CDCl3): isomer Z d 9.24 [d, J(H–
3
H) = 8.4, 2H, H2,6], 8.50 [s, J(Pt–H) = 120, 1H, Ha],
7.55 [d, 3J(H–H)0 = 8.4, 2H, H3,5], 4.90 [m, 1H, Hb],
4.15 [m, 1H, Hb ], 3.20 [m, 1H, Hd], 2.97 [s, 3J(Pt–
reported for 2a. Yield 85%. IR: m(CH@N) = 1632.1 cmꢀ1
;
1H NMR (250 MHz, CDCl3): isomer Z d 9.25 [d, 3J(H–
H) = 7.6, 1H, H6], 8.79 [dt, 3J(F–H) = 9.2, 4J(H–
0
3
H) = 34.5, 3H, He], 2.83 [s, J(Pt–H) = 28.5, 3H, He ],
0
0
2.73 [m, 1H, Hd ], 2.38 [m, 1H, Hc], 1.95 [m, 1H, Hc ];
H) = 1.75, 1H, H2], 8.53 [s, J(Pt–H) = 112, 1H, Ha],
3
isomer E d 9.30 [s, 3J(Pt–H) = 61, 1H, Ha], 7.56 [d,
7.58 [dt, J(H–H) = 8, J(F–H) = 5.6, 1H, H4], 7.38 [dt,
3
4
3J(H–H) = 8.6, 2H, H2,6], 7.48 [d, J(H–H) = 8.6, 2H,
3J(H–H) = 8.2, J(F–H) = 2.54, 1H, H5], 4.96 [m, 1H,
3
4
0
H3,5], 4.10 [td, 3J(H–H) = 5, 4J(H–H) = 1.8, 3J(Pt–
Hb], 4.11 [m, 1H, Hb ], 3.20 [m, 1H,0 H8], 3.01 [m, 1H,
0
H) = 34, 2H, Hb], 3.00 [s, J(Pt–H) = 30, 6H, He], 2.63
H9], 2.98 [m, 1H,0H9 ], 2.72 [m, 1H, H8 ], 2.40 [m, 1H, H7],
3
[m, 3J(H–H) = 5, 3J(Pt–H) = 34, 2H, Hd], 2.23 [m,
3J(H–H) = 5.5, 2H, Hc]. FAB-MS, m/z: 455 [M ꢀ Cl]+,
417 [M ꢀ 2Cl]+. Anal. Calc.: C, 30.07; H, 3.57; N, 6.14.
Found: 29.5; H: 3.5; N: 5.7.
1.96 [m, 1H, H7 ]; isomer E d 9.54 [s, J(Pt–H) = 45.3,
3
1H, H5], 7.54-7.48 [m, 3H, H1,2,3], 7.15 [dt, 3J(F–H) = 9,
4J(H–H) = 1.75, 1H, H4], 4.49 [td, 3J(H–H) = 6.4,
4J(H–H) = 1.2, 2H, H6], 2.86 [s, 6H, H9], 2.72 [m, 2H,
H8], 2.24 [m, 2H, H7]. 19F NMR (376.481 MHz, CDCl3);
isomer Z: ꢀ110.06 [dd, 3J(F–H) = 8.0, 3J(F–H) = 14.6],
[PtCl2{(CH3)2N(CH2)3NCH(2-ClC6H4)}] (2b) was
obtained from 0.408 g (0.97 mmol) of cis-[PtCl2(dmso)2]

A. Capape´ et al. / Journal of Organometallic Chemistry 690 (2005) 4309–4318
4315
3
3
3
ꢀ110.83 [dd, J(F–H) = 8.0, J(F–H) = 14.6]; isomer E:
ꢀ117.77 [m], ꢀ121.27 [m]. FAB-MS, m/z: 516.07
H) = 2, 1H, H6], 6.95 [d, J(H–H) = 8.4, 1H, H5], 4.80
[m, 1H, Hb], 4.16 [s, 3H, 0H3], 3.97 [s, 3H, H4], 2.97 [s,
[M ꢀ Cl + dmso]+,
439.04
[M ꢀ Cl]+,
401.04
3H, He], 2.80 [s, 3H, He ], 2.69 [m, 1H, Hd] 2.44 [m,
0
[M ꢀ 2Cl]+. Anal. Calc.: C, 27.92; H, 3.42; N, 5.56.
1H, Hc], 1.94 [m, 1H, Hc ]. FAB-MS, m/z: 559.14
Found: C, 27.5; H, 3.4; N, 4.8.
[M ꢀ Cl + dmso]+,
479.07
[M ꢀ Cl]+,
443.09
[PtCl2{(CH3)2N(CH2)3NCH(3-(CH3)C6H4)}]
(2e)
[M ꢀ 2Cl]+. Anal. Calc. for C14H22N2Cl2O2Pt Æ H2O:
C, 31.47; H, 4.53; N, 5.24. Found: C, 31.4; H, 4.5; N,
4.6.
was obtained from 0.363 g (0.86 mmol) of cis-
[PtCl2(dmso)2] and 0.176 g (0.86 mmol) of imine 1e,
using the procedure reported for 2a. Yield 39%. IR:
m(CH@N) = 1621.6 cmꢀ1; 1H NMR (250 MHz, CDCl3):
isomer Z d 9.64 [d, 3J(H–H) = 7.2, 1H, H6], 8.55 [s, 1H,
4.2.2. Preparation of cyclometallated compounds
[PtCl{(CH3)2N(CH2)3NCH(4-ClC6H3)}] (3a) was ob-
tained from 0.100 g (0.2 mmol) of compound 2a and
0.017 g (0.2 mmol) of sodium acetate which were al-
lowed to react in refluxing methanol for 12 h. The sol-
vent was removed using a rotary evaporator, and the
residue was treated with dichloromethane–methanol.
The precipitated red crystals were washed with diethyl
ether and filtered in vacuum. Yield 50%. IR:
m(CH@N) = 1598.8 cmꢀ1; 1H NMR (500 MHz, CDCl3):
d 8.29 [s, 3J(Pt–H) = 142.5, 1H, Ha], 7.98 [d, 4J(H–
H) = 2, 3J(Pt–H) = 44, 1H, H5], 7.02 [d, 3J(H–
H) = 8.4, 1H, H2], 6.98 [d, 3J(H–H) = 8.4, 1H, H3],
3.85 [td,3J(H–H) = 5, 3J(Pt–H) = 35, 4J(H–H) = 1.5,
2H, Hb], 2.82 [m, 2H, Hd], 2.81 [s, 3J(Pt–H) = 14.5,
H2], 8.49 [s, 3J(Pt–H) = 120, 1H, Ha], 7.55–7.45 [m,
0
2H, H4,5], 4.92 [m, 1H, Hb], 4.15 [m, 1H, Hb ], 3.60
0
[m, 1H, Hd], 3.21 [m, 1H, Hd ], 3.01 [s, 3H, He], 2.71
0
[m, 1H, Hc], 2.41 [s, 3H, H3], 1.94 [m, 1H, Hc ]; isomer
3
E d 9.26 [s, J(Pt–H) = 60, 1H, Ha], 8.90 [s, 1H, H2],
7.40-7.30 [m, 2H, H4,5,6], 4.13 [td, 3J(H–H) = 6.4,
4J(H–H) = 1.6, 2H, Hb], 2.65 [m, 2H, Hd], 2.41 [s, 3H,
H3], 2.22 [m, 2H, Hc]; non-assigned protons: 2.97 [s,
0
0
3H, He Z or eE], 2.84 [s, 3H, He Z or eE]. FAB-MS, m/z:
549.11 [M ꢀ 2Cl + 2dmso]+, 513.10 [M ꢀ Cl + dmso]+,
434.04 [M ꢀ Cl]+, 397.06 [M ꢀ 2Cl]+. Anal. Calc.: C,
30.28; H, 3.99; N, 5.04. Found: C, 30.0; H, 4.2; N, 5.1.
[PtCl2{(CH3)2N(CH2)3NCH(C6H5)}] (2f) was ob-
tained from 0.391 g (0.93 mmol) of cis-[PtCl2(dmso)2]
and 0.177 g (0.93 mmol) of imine 1f, using the procedure
reported for 2a. Yield 50%. IR: m(CH@N) =
6H, He], 2.02 [qi, J(H–H) = 5, 2H, Hc]. 195Pt NMR
(54 MHz, CDCl3): ꢀ3510.97 [s]. MALDI-MS, m/z:
454.53 [M]+, 416.58 [M ꢀ Cl]+. Anal. Calc.: C, 31.78;
H, 3.56; N, 6.18. Found: C, 31.0; H, 3.8; N, 6.2.
3
1
1625.6 cmꢀ1; H NMR (250 MHz, CDCl3): d 9.28 [d,
3J(H–H) = 7.3, 2H, H2,6], 8.52 [s, J(Pt–H) = 120, 1H,
[PtCl{(CH3)2N(CH2)3NCH(2-ClC6H3)}] (3b) was
obtained from 0.072 g (0.15 mmol) of compound 2b
and 0.013 g (0.15 mmol) of sodium acetate using the
procedure reported for 3a. Yield 66%. IR:
m(CH@N) = 1589.8 cmꢀ1; 1H NMR (250 MHz, CDCl3):
3
Ha], 7.68 [t, 3J(H–H) = 7.75, 1H, H4], 7.58 [t, 3J(H–
H)0= 7.5, 2H, H3,5], 4.94 [m, 1H, Hb], 4.13 [m, 1H,
0
Hb ], 2.97 [s, 3H, He], 2.83 [s, 3H, He ], 3.3-2.7 [m, 2H,
0
0
Hd,d ], 2.40 [m, 1H, Hc], 1.95 [m, 1H, Hc ]. FAB-MS,
m/z: 535.08 [M ꢀ 2Cl + 2dmso] 499.08 [M ꢀ Cl +
dmso]+, 420.03 [M ꢀ Cl]+, 383.02 [M ꢀ 2Cl]+.
d 8.79 [t,4J(H–H) = 1.5, J(Pt–H) = 140, 1H, Ha], 7.93
3
[dd, 3J(H–H) = 7.75, 4J(H–H) = 0.75, 3J(Pt–H) = 44,
1H, H5], 7.10 [t, 3J(H–H) = 7.75, 1H, H4], 6.93 [dd,
3J(H–H) = 7.75, 4J(H–H) = 0.75, 1H, H3], 3.91
[td,3J(H–H) = 5, 3J(Pt–H) = 35, 4J(H–H) = 1.5, 2H,
Hb], 2.88 [m, 2H, Hd], 2.84 [s, 3J(Pt–H) = 14.5, 6 H,
He], 2.03 [qi, 3J(H–H) = 5, 2H, Hc]. 13C NMR
(75 MHz, CDCl3): d 174.19 [2J(C–Pt) = 93, Ca], 144.26
[1J(C–Pt) = 1019, C6], 141.93 [C2], 133.01 [2J(C–
Pt) = 56.5, C5], 132.52 [2J(C–Pt) = 51.0, C4], 131.30
[2J(C–Pt) = 50.0, C1], 123.68 [C3], {64.00, 58.28 [ J(C–
Pt) = 39.0], 50.13, Cb, Cc, Cd}, 27.18 [2J(C–Pt) = 30.8,
Ce]. 195Pt NMR (54 MHz, CDCl3): ꢀ3519.10 [s]. MAL-
DI-MS, m/z: 453.9 [M]+, 418 [M ꢀ Cl]+. Anal. Calc.: C,
31.78; H, 3.56; N, 6.18. Found: C, 31.2; H, 3.6; N, 6.1.
[PtCl{(CH3)2N(CH2)3NCH(3-ClC6H3)}] (3c) was
obtained from 0.045 g (0.1 mmol) of compound 2c and
0.007 g (0.1 mmol) of sodium acetate using the
procedure reported for 3a. Yield 52%. IR:
m(CH@N) = 1593.9 cmꢀ1; 1H NMR (250 MHz, CDCl3):
d 8.38 [s, 3J(Pt–H) = 141.2, 1H, Ha], 7.99 [d, 3J(H–
H) = 8.4, 3J(Pt–H) = 39, 1H, H5], 7.23 [s, 1H, H2],
7.17 [m, H4], 3.92 [t, 3J(H–H) = 4.8, 3J(Pt–H) = 35,
[PtCl2{(CH3)2N(CH2)3NCH(4-(NO2)C6H4)}]
(2g)
was obtained from 0.250 g (0.59 mmol) of cis-
[PtCl2(dmso)2] and 0.140 g (0.59 mmol) of imine 1g,
using the procedure reported for 2a. Yield 49%. IR:
m(CH@N) = 1625.3 cmꢀ1; 1H NMR (250 MHz, CDCl3):
d 9.42 [d, 3J(H–H) = 8.7, 2H, H2,6], 8.77 [s, 3J(Pt–
H) = 117, 1H, Ha], 8.39 [d, J(H–H) = 8.8, 2H, H3,5],
3
4.98 [m, 3J(H–H)0 = 7.3, 1H, Hb], 4.29 [m, 3J(H–
H)0= 7.25, 1H, Hb ], 3.24 [m, 1H, Hd], 4.29 [m, 1H,
0
Hd ], 2.99 [s, 3H, He], 2.89 [s, 3H, He ], 2.42 [m, 1H,
0
Hc], 1.98 [m, 1H, Hc ]. FAB-MS, m/z: 465.04 [M ꢀ Cl]+,
428.02 [M ꢀ 2Cl]+. Anal. Calc. for C12H17N3Cl2O2Pt Æ
H2O: C, 27.75; H, 3.68; N, 8.09. Found: C, 27.6; H,
3.4; N, 7.9.
[PtCl2{(CH3)2N(CH2)3NCH(3,4-(MeO)2C6H3)}] (2h)
was obtained from 0.259 g (0.61 mmol) of
[PtCl2(dmso)2] and 0.154 g (0.61 mmol) of imine 1g,
using the procedure reported for 2a. Yield 49%. IR:
m(CH@N) = 1611.6 cmꢀ1; 1H NMR (250 MHz, CDCl3):
d 10.42 [d, 4J(H–H) = 1.6, 1H, H2], 8.33 [s, 3J(Pt–
H) = 119.4, 1H, Ha], 7.83 [dd, 3J(H–H) = 8.4, 4J(H–

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A. Capape´ et al. / Journal of Organometallic Chemistry 690 (2005) 4309–4318
1
2H, Hb], 2.97 [m, 2H, Hd], 2.85 [m, 6H, He], 2.05 [m, 1H,
Hc]. Anal. Calc.: for C12H16N2Cl2PtÆCH2Cl2: C, 28.95;
H, 3.36; N, 5.19. Found: C, 28.6; H, 3.5; N, 4.2.
1595.3 cmꢀ1; H NMR (250 MHz, CDCl3): d 8.83 [d,
4J(H–H) = 2.25, 3J(Pt–H) = 42.3, 1H, H5], 8.58 [s,
3J(Pt–H) = 140, 1H, Ha], 7.85 [dd, 3J(H–H) = 8.5,
3
[PtCl{(CH3)2N(CH2)3NCH(3-FC6H3)}] (3d) was ob-
tained from 0.100 g (0.21 mmol) of compound 2d and
0.017 g (0.21 mmol) of sodium acetate using the proce-
dure reported for 3a. Yield 25%. IR: m(CH@N) =
4J(H–H) = 2.25, 1H, H3], 7.40 [d, J(H–H) = 8.25, 1H,
H2], 4.00 [td, J(H–H) = 5.50, J(H–H) = 1.75, J(Pt–
3
4
3
H) = 17.3, 2H, Hb], 2.98 [m, 2H, Hd], 2.86 [s, J(Pt–
3
H) = 15, 6H, He], 2.08 [m, 3J(H–H) = 4.75, 2H, Hc].
FAB-MS, m/z: 466.08 [M]+, 428.05 [M ꢀ Cl]+. Anal.
Calc. for C12H16N3ClO2Pt Æ H2O: C, 29.86; H, 3.75; N,
8.70. Found: C, 29.7; H, 3.4; N, 8.5.
1
1595.8 cmꢀ1; H NMR (250 MHz, CDCl3): major iso-
mer: d 8.37 [s, 3J(Pt–H) = 141.5, 1H, Ha], 7.98 [dd
3J(H–H) = 8, 4J(H–F) = 6, 3J(Pt–H) = 39, 1H, H5],
7.0-6.9 [m, 1H, H2,4], 3.92 [t, 3J(H–H) = 4.5, 3J(Pt–
H) = 37, 2H, Hb], 2.86 [m, 2H, Hd], 2.85 [s, 3J(Pt–
[PtCl{(CH3)2N(CH2)3NCH(3,4-(MeO)2C6H2)}] (3h)
was obtained from 0.124 g (0.24 mmol) of compound
2h and 0.020 g (0.24 mmol) of sodium acetate using
the procedure reported for 3a. Yield 32%. IR:
m(CH@N) = 1592.6 cmꢀ1; 1H NMR (400 MHz, CDCl3):
d 8.17[t, 4J(H–H) = 1.2, 3J(Pt–H) = 142.4, 1H, Ha],
3
H) = 14.5, 6H, He], 2.02 [qi, J(H–H) = 5.0, 2H, Hc];
minor isomer: d 8.46 [d, 4J(H–H) = 1.37, 3J(Pt–
3
H) = 137, 1H, Ha], 7.16 [d, J(H–H) = 7.23, 1H, H2],
6.9 [m, 1H, H3], 6.81 [dd, 3J(H–H) = 8.4, 3J(H–
F) = 10, 1H, H4], 3.86 [m, 2H, Hb] 2.96 [s, 6H, He],
2.86 [m, 2H, Hd], 2.0 [m, Hc]. 19F NMR (376.481 MHz,
CDCl3): major isomer: ꢀ121.25 [dd, 3J(F–H) = 8.66,
3J(F–H) = 9.06]; minor isomer: ꢀ93.91 [dd, 3J(F–
7.59[s, J(Pt–H) = 44, 1H, H5], 6.84 [s, J(Pt–H) = 6.2,
1H, H2], 3.97 [s, 3H, H3], 3.83 [m, 2H, Hb], 3.80 [s 3H,
H4], 2.84 [s, 3J(Pt–H) = 14.4, 6H, He], 2.85 [m, 2H,
Hd], 1.99 [q, 3J(H–H) = 5.2, 2H, Hc]. 13C NMR
(100.6 MHz, CDCl3): d 175.46 [Ca], 151.10 [C4], 145.72
[C3], 136.90 [C6], 136.02 [C1], 116.71 [2J(Pt–C) = 67.4,
C5], 110.04 [3J(Pt–C) = 40.4, C2], {56.06, 55.99, CMeO},
{64.25, 57.40 [2J(Pt–C) = 37.4], 50.11, Cb, Cc, Cd}, 27.43
[Ce]. 195Pt NMR (54 MHz, CDCl3): ꢀ3567.00 [s]. FAB-
MS, m/z: 479.9 [M]+, 442.9 [M ꢀ Cl]+. Anal. Calc.: C,
35.04; H, 4.41; N, 5.84. Found: C, 35.3; H, 4.9; N, 5.8.
3
4
4
3
H) = 10, J(F–H) = 5.9, J(Pt–F) = 75]. Anal. Calc.: C,
32.92; H, 3.68; N, 6.40. Found: C, 32.6; H, 2.5; N, 6.2.
[PtCl{(CH3)2N(CH2)3NCH(3-(CH3)C6H3)}] (3e) was
obtained from 0.100 g (0.21 mmol) of compound 2e and
0.017 g (0.21 mmol) of sodium acetate using the proce-
dure reported for 3a. Yield 22%. IR: m(CH@N) =
1601.8 cmꢀ1 1H NMR (250 MHz, CDCl3): 8.24 [s,
;
3J(Pt–H) = 143.6, 1H, Ha], 7.85 [d, 3J(H–H) = 8,
3J(Pt–H) = 38, 1H, H5], 7.05 [s, 1H, H2], 6.98, [d,
3J(H–H) = 7, 1H, H4], 3.84 [t, 3J(H–H) = 5, 3J(Pt–
H) = 36, 2H, Hb], 2.8 [bm, 8H, Hd,e], 2.23 [s, 3H, H3],
1.98 [m, 2H, Hc].
[PtCl{(CH3)2N(CH2)3NCHC6H4}] (3f) was obtained
from 0.100 g (0.22 mmol) of compound 2f and 0.020 g
(0.22 mmol) of sodium acetate using the procedure re-
4.2.3. Preparation of phosphine derivatives
[PtCl{(CH3)2N(CH2)3NCH(4-ClC6H3)}(PPh3)] (4a)
was obtained from 0.035 g (0.08 mmol) of compound
3a and 0.020 g (0.08 mmol) of triphenylphosphine,
which were allowed to react in acetone at room temper-
ature for 4 h. The residue was washed with hexane and
dried in vacuum. Yield 98%. IR: m(CH@N) =
ported for 3a. Yield 37%. IR: m(CH@N) = 1593.5 cmꢀ1
;
1618.0 cmꢀ1; H NMR (250 MHz, CDCl3): d 8.84 [d,
1
1H NMR (250 MHz, CDCl3): d 8.34 [t, 4J(H–H) = 1.25,
3J(Pt–H) = 142, 1H, Ha], 7.60 [d, 3J(H–H) = 7.45,
4J(P–H) = 9.4, 3J(Pt–H) = 100, 1H, Ha], 7.73 [m,
3J(H–H) = 9, 3J(P–H) = 12, 6H, Hf ], 7.4–7.3 [m,
3
4
3
3
3J(Pt–H) = 40,1H, H5], 7.25 [dd, J(H–H) = 7.2, J(H–
Hg,h], 7.18 [d, J(H–H) = 7.9, 1H, H2], 6.88 [d, J(H–
H) = 1.25, 1H, H2], 7.16 [td, 3J(H–H) = 7.5,
H) = 6.8, 1H, H3], 6.4 [s, J(Pt–H) = 56, 1H, H5], 4.12
3
4J(H–H) = 1.2, 1H, H3 or 4], 6.98 [td, 3J(H–H) = 7.4,
[m, 3J(H–H) = 5.25, 2H, Hb], 2.42 [t, 3J(H–H) = 6.8,
4J(H–H) = 1.25, 1H, H3
4], 3.88 [td, 3J(H–H) = 5,
2H, Hd], 2.26 [s, 6H, He], 2.10 [m, J(H–H) = 6.7, 2H,
or
3
3
4J(H–H) = 1.5, J(Pt–H) = 35.2, 2H, Hb], 2.86 [m, 2H,
Hd], 2.84 [s, 3J(Pt–H) = 14, 6H, He], 2.01 [q, 3J(H–
H) = 5.2, 2H, Hc]. 13C NMR (100.6 MHz, CDCl3): d
176.60 [Ca], 144.66 [C6], 141.96 [C1], 134.70 [C4],
131.09 [2J(Pt–C) = 44.1, C5], 127.15 [3J(Pt–C) = 32.0,
C2], 123.50 [C3], {64.17, 57.96 [2J(Pt–C) = 39.0], 50.06,
Cb, Cc, Cd}, 27.32 [Ce]. 195Pt NMR (54 MHz, CDCl3):
ꢀ3581.21 [s]. FAB-MS, m/z: 419.33 [M]+, 383.35
[M ꢀ Cl]+. Anal. Calc. for C12H17N2ClPt Æ H2O: C,
32.91; H, 4.37; N, 6.40. Found: C, 33.2; H, 4.4; N, 6.7.
[PtCl{(CH3)2N(CH2)3NCH(4-(NO2)C6H3)}] (3g) was
obtained from 0.050 g (0.1 mmol) of compound 2g and
0.009 g (0.1 mmol) of sodium acetate using the proce-
dure reported for 3a. Yield 44%. IR: m(CH@N) =
Hc]. 31P NMR (101 MHz): 21.36 [s, 1J(P–
d
Pt) = 4132.8]. FAB-MS, m/z: 716.8 [M]+, 681.0
[M ꢀ Cl]+.
[PtCl{(CH3)2N(CH2)3NCH(2-ClC6H3)}(PPh3)] (4b)
was obtained from 0.035 g (0.08 mmol) of compound
3b and 0.020 g (0.08 mmol) of triphenylphosphine,
which were allowed to react in acetone at room temper-
ature for 4 h. The residue was washed with hexane and
dried in vacuum. Yield 44%. IR: m(CH@N) =
1
1610.6 cmꢀ1; H NMR (400 MHz, CDCl3): d 8.85 [d,
4J(P–H) = 9.5, 3J(Pt–H) = 95, Ha], 7.72 [ddd, 3J(H–
H) = 8.2, 4J(H–H) = 1.75, 3J(P–H) = 11.8, 5H, Hf],
7.5-7.3 [m, Hg,h], 6.83 [dd, 3J(H–H) = 7.75, 4J(H–
H) = 1.25, 1H, H3], 6.48 [t, 3J(H–H) = 7.6, H4], 6.37

A. Capape´ et al. / Journal of Organometallic Chemistry 690 (2005) 4309–4318
4317
Table 2
Crystallographic and refinement data
Compound 3a
Compound 3b
Compound 3e
Empirical formula
Molecular weight
Temperature (K)
C12H16Cl2N2Pt
454.26
293(2)
C12H16Cl2N2Pt
454.26
293(2)
C13H19ClN2Pt
433.84
293(2)
˚
Wavelength (A)
0.71073
0.71073
0.71073
Crystal system, space group
Unit cell dimensions
Monoclinic, P21
Monoclinic, P21/n
Orthorhombic, Pbca
˚
a (A)
6.231(5)
11.603(3)
9.721(3)
90
94.3(10)
90
701.1(6)
2; 2.152
6.4940(10)
11.398(10)
18.7880(10)
90
100.640(10)
90
1366.8(12)
4; 2.208
10.670(10)
11.282(18)
22.96(4)
90
90
90
2764(7)
8; 2.085
10.326
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
3
˚
Volume (A )
Z; calculated density (Mg mꢀ3
)
Absorption coefficient (mmꢀ1
F(000)
)
10.368
428
10.636
856
1648
Crystal size (mm)
H range for data collection (ꢁ)
Limiting indices
Reflections collected/unique [R(int)]
Completeness to h
Refinement method
0.1 · 0.1 · 0.2
2.10–29.96
0.1 · 0.1 · 0.2
3.65–35.90
0.1 · 0.1 · 0.2
2.61–33.48
ꢀ8 6 h 6 8.0 6 k 6 16.0 6 l 6 13
2085/2085 [0.0918]
97.7% (h = 29.99)
Full-matrix least-squares on F2
2085/1/148
ꢀ8 6 h 6 8.0 6 k 6 15.0 6 l 6 27
0 6 h 6 16.0 6 k 6 17.0 6 l 6 35
4327/4327 [0.0825]
–
Full-matrix least-squares on F2
4327/0/155
6801/2699 [0.0453]
–
Full-matrix least-squares on F2
2699/0/154
Data/restraints/parameters
Goodness-of-fit on F2
1.057
1.144
1.212
Final R indices [I > 2r(I)]
R indices (all data)
Absolute structure parameter
R1 = 0.0482, wR2 = 0.1171
R1 = 0.0566, wR2 = 0.1217
0.08(3)
0.989 and ꢀ0.868
R1 = 0.0436, wR2 = 0.1352
R1 = 0.0497, wR2 = 0.1494
–
0.884 and ꢀ0.765
R1 = 0.0348, wR2 = 0.0885
R1 = 0.0452, wR2 = 0.0959
0.00019(11)
0.832 and ꢀ0.818
ꢀ3
˚
Largest diff. peak and hole (e A
)
3
4
3
[dd, J(H–H) = 8.0, J(H–H) = 2.4, J(Pt–H) = 49, 1H,
H5], 4.15 [m, 3J(H–H) = 4.5, 2H, Hb], 2.50 [t, 3J(H–
H) = 6.25, 2H, Hd], 2.34 [s, 6H, He], 2.17 [m, 2H, Hc].
31P NMR (101 MHz): d 21.36 [s, 1J(P–Pt) = 4132.8].
FAB-MS, m/z: 717.6 [M]+, 681.6 [M ꢀ Cl]+.
tized Mo Ka radiation. The structures were solved
by using SHELXS program [18], and refined by full-ma-
trix least-squares method with SHELX 97 computer pro-
gram using 2085 reflections (very negative intensities
were not assumed). Further details are given in
Table 2.
[Pt{(CH3)2N(CH2)3NCH(2-ClC6H3)}{PPh2(CH2)2-
PPh2}]Cl (5b) was obtained from 0.030 g (0.07 mmol)
of compound 3b and 0.026 g (0.07 mmol) of triphenyl-
phosphine, which were allowed to react in acetone at
room temperature for 4 h. The residue was washed
with hexane and filtered in vacuum. Yield 44%. IR:
4.3.2. Data Collection, structure solution and refinement
for 3b and 3e
Prismatic crystals were selected and mounted on a
MAR345 diffractometer with an image plate detector.
Intensities were collected with graphite monochroma-
tized Mo Ka radiation. The structures were solved
using SHELXS program [18], and refined by full-matrix
least-squares method with SHELX97 computer program
using 2699 (3b) and 4327 (3e) reflections (very negative
intensities were not assumed). Further details are given
in Table 2.
m(CH@N) = 1600.9 cmꢀ1
;
1H
NMR
(400 MHz,
3
3
CDCl3): d 9.18 [d, J(P–H) = 7.6, J(Pt–H) = 90, 4H,
Ha], 7.89 [d, J(P–H) = 12.0, J(H–H) = 7.0, 4H, Hh],
6.98 [d, 3J(H–H) = 7.6, H4], 6.79 [td, 3J(H–H) = 8.0,
4J(H–H) = 1.76, 1H, H3], 6.67 [m, H5], 3.75 [bm, 2H,
3
3
Hb]. 31P NMR (101 MHz):
d
46.68 [s, 1J(P–
Pt) = 1906.21, PA], 39.96 [s, 1J(P–Pt) = 3605.95, PB].
FAB-MS, m/z: 816.86 [M ꢀ Cl]+.
4.3. X-ray structure analysis
Acknowledgments
4.3.1. Data Collection, structure solution and refinement
for 3a
This work was supported by the Ministerio de
´
A prismatic crystal was selected and mounted on
an Enraf-Nonious CAD4 four circle diffractometer.
Intensities were collected with graphite monochroma-
Ciencia y Tecnologıa (project: BQU2003-00906/50%
FEDER) and by the Comissionat per a Universitats
i Recerca (project: 2001SGR-00054).

4318
A. Capape´ et al. / Journal of Organometallic Chemistry 690 (2005) 4309–4318
[4] M. Crespo, E. Evangelio, J. Organomet. Chem. 689 (2004)
1956.
Appendix A. Supplementary data
´
[5] J.M. Vila, M.T. Pereira, J.M. Ortigueira, D. Lata, M. Lopez-
The preparation and spectroscopic data (IR, 1H
NMR) of compounds 1a–1h (3 pages).
´
´
Torres, J.J. Fernandez, A. Fernandez, H. Adams, J.Organomet.
Chem. 566 (1998) 93.
The crystallographic data of compounds 3a, 3b and3e
have been deposited with the Cambridge Crystallo-
graphic Data Centre, CCDC Nos. 268978, 268979 and
268980, respectively. Copies of this information may be
obtained free of charge from The Director, CCDC, 12
Union Road, Cambridge CB2 1EZ, UK (fax: +44 1223
336033; e-mail: deposit@ccdc.cam.ac.uk or www: http://
www.ccdc.cam.ac.uk).
[6] J. Bravo, C. Cativiela, R. Navarro, E.P. Urriolabeitia, J.
Organomet. Chem. 650 (2002) 157.
[7] (a) P.R.R. Ranatunge-Bandarage, B.H. Robinson, J. Simpson,
Organometallics 13 (1994) 500;
(b) Y.J. Wu, L. Ding, H.X. Wang, Y.H. Liu, H.Z. Yuan, X.A.
Mao, J. Organomet. Chem. 535 (1997) 49;
(c) A.D. Ryabov, I.M. Panyashkina, V.A. Polyakov, A. Fisher,
Organometallics 21 (2002) 1633;
´
´
´
(d) S. Perez, C. Lopez, A. Caubet, X. Solans, M. Font-Bardıa,
New J. Chem. 27 (2003) 975;
Supplementary data associated with this article can
be found, in the online version at doi:10.1016/
j.jorganchem.2005.06.038.
´
´
(e) M. Crespo, M. Font-Bardıa, J. Granell, M. Martınez, X.
Solans, J. Chem. Soc., Dalton Trans. (2003) 3763.
´
´
[8] I. Favier, M. Gomez, J. Granell, M. Martınez, X. Solans, M.
Font-Bard´ıa, Dalton Trans. (2005) 123.
[9] M.V. Diurno, O. Mazzoni, G. Correale, I.G. Monterrey, A.
Calignano, G. La Rana, A. Bolognese, Il Farmaco 54 (1999)
579.
References
´
´
´
´
[10] A. Fernandez, P. Urıa, J.J. Fernandez, M. Lopez-Torres, A.
´
´
´
Suarez, D. Vazquez-Garcıa, M.T. Pereira, J.M. Vila, J. Organo-
[1] (a) A.D. Ryabov, Synthesis (1985) 233;
(b) A.D. Ryabov, Chem. Rev. 90 (1990) 403;
(c) J. Dupont, M. Pfeffer, J. Spencer, Eur. J. Inorg. Chem. (2001)
1917;
met. Chem. 620 (2001) 8.
[11] P.S. Pregosin, Coord. Chem. Rev. 44 (1982) 247.
[12] (a) J. Albert, J. Granell, J. Mınguez, G. Muller, D. Sainz, P.
´
Valerga, Organometallics 16 (1997) 3561;
(b) M. Crespo, C. Grande, A. Klein, M. Font-Bardıa, X. Solans,
(d) P. Espinet, M.A. Esteruelas, L.A. Oro, J.L. Serrano, E. Sola,
Coord. Chem. Rev. 117 (1992) 215;
´
J. Organomet. Chem. 563 (1998) 179.
[13] M. Crespo, J. Granell, X. Solans, M. Font-Bardıa, J. Organomet.
´
´
(e) C. Navarro-Ranninger, I. Lopez-Solera, J.M. Perez, J.R.
Masaguer, C. Alonso, Appl. Organomet. Chem. 7 (1993) 57.
[2] (a) C.R. Baar, H.A. Jenkins, J.J. Vittal, G.P.A. Yap, R.J.
Puddephatt, Organometallics 17 (1998) 2805;
´
Chem. 681 (2003) 143.
´
[14] J. Vicente, J.A. Arcas, E. Martınez-Viviente, P.G. Jones, Organo-
metallics 21 (2002) 4454.
[15] H.F. Klein, S. Camadanli, R. Beck, D. Leukel, U. Flo¨rke, Angew.
Chem. Int. Ed. 44 (2005) 975.
[16] W. Lu, M.C.W. Chan, K.K. Cheung, C.M. Che, Organometallics
20 (2001) 2477.
[17] J.H. Price, A.N. Williamson, R.F. Schramm, B.B. Wayland,
Inorg. Chem. 11 (1972) 1280.
[18] G.M. Sheldrick, SHELXS97, a Computer Program for Crystal
Structure Determination, University of Go¨ttingen, Germany,
1997.
(b) C.R. Baar, G.S. Hill, J.J. Vittal, R.J. Puddephatt, Organo-
metallics 17 (1998) 32;
(c) C.M. Anderson, M. Crespo, M.C. Jennings, A.J. Lough, G.
Ferguson, R.J. Puddephatt, Organometallics 10 (1991) 2672;
(d) A. Zucca, S. Stoccoro, M.A. Cinellu, G. Minghetti, M.
Manassero, M. Sansoni, Eur. J. Inorg. Chem. (2002) 3336;
(e) A. Doppiu, M.A. Cinellu, G. Minghetti, S. Stoccoro, A. Zucca,
M. Manassero, M. Sansoni, Eur. J. Inorg. Chem. (2000) 2555.
´
[3] M. Crespo, J. Granell, X. Solans, M. Font-Bardıa, Organomet-
allics 21 (2002) 5140.