Reactions of [C,N,N′]-cyclometallated platinum compounds with phosphines: Transphobia and effect of the chloro substituents. Crystal structure of [PtCl(3,5-C6H2Cl2CHNCH 2CH2NMe2)(PPh3)2]

Article abstract of DOI:10.1016/S0022-328X(03)00593-X

The reaction of [C,N,N′]-cyclometallated platinum compounds [PtX(C₆H_4-nCl_nCHNCH₂ CH₂NMe₂)] (1a-1g) with triphenylphosphine gave either [C,N]-cyclometallated compounds [PtX(C₆ H_4-nCl_nCHNCH₂CH₂ NMe₂)PPh₃] (2), in which PPh₃ is trans to the imine nitrogen, or compounds [PtX(C₆ H_4-nCl_nCHNCH₂CH₂ NMe₂)(PPh₃)₂] (4), with cleavage of the metallacycle. The stereochemistry of compounds 2 is the expected one according to the transphobia effect, while formation of compounds 4 takes place only when there is a chlorine atom adjacent to the metallated carbon. An ionic compound 3 has also been obtained using the chelate diphosphine 1,2-bis(diphenylphosphino)ethane. All compounds have been fully characterised including a structure determination for [PtCl(3,5-C₆H₂Cl₂CHNCH₂ CH₂NMe₂)(PPh₃)₂] (4f).

Full text of DOI:10.1016/S0022-328X(03)00593-X

Journal of Organometallic Chemistry 681 (2003) 143ꢁ149
/
www.elsevier.com/locate/jorganchem
Reactions of [C,N,N?]-cyclometallated platinum compounds with
phosphines: transphobia and effect of the chloro substituents
Crystal structure of [PtCl(3,5-C6H2Cl2CHNCH2CH2NMe2)(PPh3)2]
Margarita Crespo a,*, Jaume Granell a, Xavier Solans b, Merce` Font-Bardia b
a Departament de Qu´ımica Inorga`nica, Universitat de Barcelona, Diagonal 647, 08028 Barcelona, Spain
b Departament de Cristallografia, Mineralogia i Dipo`sits Minerals, Universitat de Barcelona, Mart´ı i Franque`s s/n, 08028 Barcelona, Spain
Received 7 May 2003; received in revised form 13 June 2003; accepted 19 June 2003
Abstract
The reaction of [C,N,N?]-cyclometallated platinum compounds [PtX(C6H4ꢀnClnCHNCH2CH2NMe2)] (1aꢁ1g) with triphenyl-
/
phosphine gave either [C,N]-cyclometallated compounds [PtX(C6H4ꢀnClnCHNCH2CH2NMe2)PPh3] (2), in which PPh3 is trans to
the imine nitrogen, or compounds [PtX(C6H4ꢀnClnCHNCH2CH2NMe2)(PPh3)2] (4), with cleavage of the metallacycle. The
stereochemistry of compounds 2 is the expected one according to the transphobia effect, while formation of compounds 4 takes place
only when there is a chlorine atom adjacent to the metallated carbon. An ionic compound 3 has also been obtained using the chelate
diphosphine 1,2-bis(diphenylphosphino)ethane. All compounds have been fully characterised including a structure determination
for [PtCl(3,5-C6H2Cl2CHNCH2CH2NMe2)(PPh3)2] (4f).
# 2003 Elsevier B.V. All rights reserved.
Keywords: Platinum; Cyclometallated compounds; Phosphines; N-donor ligands
1. Introduction
proposed to explain the increasing phobia of being
mutually trans of the following pair of ligands: X-
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
palladium and platinum metallacycles with nitrogen
donors, which can be stabilised as monomers (Figure a
of Chart I) using ligands such as tertiary phosphines [2].
donor/Y-donor (X,Yꢂ
C-donor, X-donor (Xꢂ
P-donorBC-donor/C-donor [3]. In addition, the trans
/
halogen, N-donor, P-donor)#
/
/
halogen, N-donor)BC-donor/
/
/
choice concept has been recently proposed as the effect
according to which the most stable complex is that
having the softest and the hardest ligands in trans
positions [4]. Both transphobia and trans choice con-
cepts can be related to the previously reported anti-
symbiotic effect which indicates that two soft ligands in
mutually trans positions will have a desestabilising effect
when attached to a class b metal [5].
There is a lot of information available about these
reactions in palladium complexes, but in contrast
platinum compounds have been less studied and present
some exceptions to these rules since kinetically con-
trolled reactions are not rare in platinum chemistry [4].
On the other hand, depending on the nature of the
cycle and the basicity of the nitrogen donor, cleavage of
The regioselectivity of the reaction between cyclome-
tallated dinuclear complexes and Lewis bases has been
extensively studied and the term transphobia has been
* Corresponding author. Tel.:
907725.
E-mail address: margarita.crespo@qi.ub.es (M. Crespo).
ꢃ
/
34-934-021273; fax:
ꢃ/34-934-
the metalÃ
/
nitrogen bond may be achieved in the
reaction of palladacycles with monodentate phosphines
0022-328X/03/$ - see front matter # 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0022-328X(03)00593-X

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M. Crespo et al. / Journal of Organometallic Chemistry 681 (2003) 143ꢁ149
/
[6]. Moreover, steric crowding in the coordination
sphere of the metal has been shown to favour the
cleavage of metallacycles upon reaction with triphenyl-
phosphine. In particular, the presence of a fluorine [7] or
spectra, no platinum satellites are observed for the
dimethylamino group, thus ruling out the possibility of
pentacoordination of the platinum. The imine group
appears as a doublet due to coupling to 31P and also
shows platinum satellites, which confirms both coordi-
nation of the imine nitrogen to platinum and a trans
arrangement of this atom and the phosphine ligand. For
2a and 2e, the methylene resonances appear as broad
unresolved signals. The 1H- and 31P-NMR spectra of 2e
recorded at lower temperatures showed the presence of
two compounds with coordinated triphenylphosphine in
nearly (1:1) ratio for which the structures in Scheme 2
are deduced [11]. The conductivity observed for com-
pound 2e in acetone is consistent with the proposed
equilibrium between a neutral and an ionic compound.
Moreover, the FAB mass spectrum of 2e does not show
the molecular peak but a peak corresponding to the loss
of the chloro ligand.
a chlorine [8] atom in the position adjacent to the MÃ
/
C(aryl) bond seems to be decisive. In such cases, the
newly entering phosphine replaces the nitrogen atom,
leading either to a trans or a cis arrangement of both
phosphines, as depicted in structures b and c of Chart I.
This paper analyses the reactions of triphenylpho-
sphine with cyclometallated platinum compounds of
general formula [PtX(C6H4ꢀnClnCHNCH2CH2NMe2)]
recently reported [9]. These compounds contain a
terdentate [C,N,N?] ligand and may upon reactions
with phosphines, lead to either bidentate [C,N] or
monodentate [C] systems. Both the influence of the
chlorine substituents in the tendency of the metallacycle
to open up and the stereochemistry of the obtained
compounds will be analysed. It should be noted that
these ligands direct the entering phosphine to a position
trans to the carbon atom, and that this is not the most
favoured arrangement according to the previously
mentioned models.
The reaction of compound 2e with 1 mol of PPh3 was
1
monitored by H- and 31P-NMR, and no evidence of
coordination of a second phosphine with cleavage of the
metallacycle was obtained. However, several changes in
the spectra took place in the presence of free phosphine.
The methylene resonances appear as well-resolved
triplets, the phosphorus resonance is very broad and
the imine proton is now a singlet coupled to 195Pt but
not to phosphorus. These results are consistent with a
fast exchange between coordinated and free phosphine,
as proposed for analogous palladium compounds (see
Scheme 3) [12].
2. Results and discussion
2.1. Reactions with phosphines
The reactions of 1aꢁ1f with phosphines were carried
/
out in acetone at room temperature and produced the
compounds depicted in Scheme 1.
Since both palladium(II) [13] and platinum(II) [14]
metallacycles are easily cleaved with diphosphines due
to the chelating nature of these ligands, the reaction of
1e with 1,2-bis(diphenylphosphino)ethane (dppe) was
also studied. Examples in which the formation of either
compounds containing a bridging diphosphine [15] or
ionic compounds with a chelate diphosphine [16] is
favoured over cleavage of the metallacycles have also
been reported in the literature. Upon reaction with
dppe, compound 1e gave a light yellow solid which was
characterised by FAB-MS, 1H-, 31P- and 195Pt-NMR
The reactions of 1a, 1c, 1d and 1e with triphenylpho-
sphine gave compounds 2, in which the imine behaves as
a [C,N] bidentate ligand and the square-planar coordi-
nation of platinum(II) is completed with a phosphine
and a halide ligand. Spectral characterisation of these
compounds indicates that the phosphine is trans to
nitrogen in agreement with the transphobia effect
described above [3]. Therefore, initial displacement of
the NMe2 moiety by the phosphine ligand is followed by
isomerisation to the more stable isomer. Compounds 2
are yellow solids, which were characterised by elemental
analyses, FAB-MS, and 1H-, 31P- and 195Pt-NMR
1
spectra. The H-NMR spectrum suggests that the imine
behaves as a [C,N] ligand since no platinum satellites are
observed for the dimethylamino group, while the imine
resonance consists of a doublet due to coupling to the
phosphorus in trans position and also shows platinum
satellites. The 31P-NMR spectrum shows two sets of
resonances due to two non-equivalent phosphorus
spectra. The J(PÃ
/
Pt) values observed in both 31P- and
195Pt-NMR spectra suggest the presence of a PPh3
coordinated to platinum and the obtained values (2a:
4042 Hz, 2c: 4080 Hz, 2d: 4120 Hz and 2e: 4159 Hz)
support the trans arrangement of phosphorus and
nitrogen indicated above. The 195Pt-NMR spectra
show a doublet, due to coupling with one phosphorous
atom, the position of which is consistent with the nature
of the ligands bound to platinum(II) [10]. The d(195Pt)
values indicate a downfield shift on increasing the
chlorination of the aryl ring which is consistent with
atoms, both coupled to platinum. The values of J(PÃ
Pt) which were confirmed by 195Pt-NMR are consistent
with the presence of a N-donor (J(PÃPt)ꢂ3635 Hz)
and a C-donor (J(PÃPt)ꢂ1876 Hz) trans to the
phosphorus atoms. The spectral characterisation and
/
/
/
/
/
the conductivity observed in acetone (Lꢂ
98 Vꢀ1 cm2
/
molꢀ1) are consistent with an ionic nature for cyclome-
tallated compound 3e as depicted in Scheme 1. A peak
1
deshielding of the platinum nucleus. In the H-NMR

M. Crespo et al. / Journal of Organometallic Chemistry 681 (2003) 143ꢁ
/149
145
Scheme 1.
formation of an ionic compound with dissociation of the
chloro ligand clearly shows the high stability of the
metallacycle which is resistant to cleavage even when
reacted with chelating diphosphines.
Compounds 1b, 1f and 1g which contain a chloro
substituent in position 5 gave under reaction condi-
tions similar to those reported for the reactions of
1a with triphenylphosphine,
a
1:1 mixture of
(4)
[PtCl(C6H4ꢀnClnCHÄNCH2CH2NMe2)(PPh3)2]
/
Scheme 2.
and starting platinum material [17]. Compounds 4,
best obtained from reaction of the corresponding
compound 1 with two equivalents of PPh3, are white
solids. They were characterised by elemental analyses,
1H-, 31P- and 195Pt-NMR spectra, and compound 4f was
corresponding to the complex cation was obtained in the
FAB mass spectrum. Compound 3e could not be
isolated in a pure form due to decomposition processes
during attempted crystallisation in several solvents. The
Scheme 3.

146
M. Crespo et al. / Journal of Organometallic Chemistry 681 (2003) 143ꢁ149
/
also characterised by 13C-NMR and X-ray crystal
structure determination. Both dimethylamine and imine
protons lack platinum satellites, indicating that the
imine is acting as a monodentate ligand through the
aryl carbon. Only one signal is observed in the 31P-
Table 1
˚
Selected bond lengths (A) and angles (8) for compound 4f with
estimated standard deviations
˚
Bond length (A)
PtÃ
PtÃ
PtÃ
PtÃ
Cl(2)Ã
Cl(3)Ã
C(2)Ã
N(1)Ã
N(2)Ã
N(2)Ã
N(2)Ã
N(1)Ã
C(8)Ã
/
C(1)
P(1)
P(2)
Cl(1)
2.023(4)
/
2.3092(11)
2.3106(10)
2.3767(11)
1.737(4)
NMR spectra and the coupling constant J(PÃ
/
Pt)
deduced from both 31P and 195Pt spectra is in the range
expected for mutually trans phosphines [18]. The 195Pt-
NMR spectra consist of a triplet due to coupling with
two mutually trans phosphorus atom. The d(195Pt)
values move to high field when compared to compounds
2 in agreement with replacement of a N-donor for a P-
donor in the coordination sphere of platinum [10].
/
/
/C(4)
/C(6)
1.717(4)
/C(7)
1.524(5)
/C(7)
1.191(6)
/C(10)
1.444(10)
1.449(9)
/C(9)
/C(11)
1.481(12)
1.474(8)
/C(8)
/C(9)
1.531(11)
2.2. Crystal structure of compound 4f
Bond angle (8)
C(1)Ã
C(1)Ã
P(1)ÃPtÃ
P(2)ÃPtÃ
/
PtÃ
/
P(1)
89.66(11)
89.31(11)
91.14(4)
89.85(4)
Suitable crystals were obtained upon addition of
diethylether to an acetone solution of 4f followed by
slow evaporation. The crystal structure is composed of
discrete molecules separated by van der Waals interac-
tions. A view of the molecule is shown in Fig. 1. Selected
bond lengths and angles are given in Table 1. The crystal
structure confirms the square-planar coordination
around platinum, completed with two mutually trans
PPh3 ligands, a chloro and a monodentate [C] ligand, as
well as the presence of a chlorine atom (Cl5) adjacent to
/
PtÃ
/P(2)
/
/Cl(1)
/
/Cl(1)
the metallated carbon in the aryl group. Bond lengths
and angles are well within the range of values obtained
for analogous compounds [16]. As observed for square-
planar aryl complexes of platinum(II), the metallated
Fig. 1. Molecular structure of compound 4f.

M. Crespo et al. / Journal of Organometallic Chemistry 681 (2003) 143ꢁ
/149
147
phenyl ring is nearly perpendicular to the coordination
plane, the dihedral angle being 91.858.
In conclusion, the five-membered endo platinacycles
are very stable as is shown in the reaction of 1e with
dppe. However, this type of metallacycle can be easily
cleaved provided that a chloro substituent is present in a
Br], 457 [PtPPh3]. Anal. Found: C, 49.0; H, 4.5; N, 3.9.
Calc. for C29H30BrN2PPt: C, 48.88; H, 4.24; N, 3.93%.
Compound [PtCl(2,3-C6H2Cl2CHNCH2CH2NMe2)-
PPh3] (2c) was obtained as a yellow solid by an
analogous procedure using 50 mg (1.1ꢄ
compound 1e and 28 mg (1.1ꢄ
10ꢀ4 mol) of PPh3.
Yield 60 mg (75%). 1H-NMR (200 MHz, CDCl3): d 2.32
/
10ꢀ4 mol) of
/
position adjacent to the PtÃ/C bond. As previously
reported for analogous systems [6,7], the cleavage of
the metallacycle relieves the steric crowding in the
coordination sphere of platinum. On the other hand,
the stereochemistry of all the new platinum compounds
containing triphenylphosphine is in agreement with the
transphobia effect, in spite of the fact that the [C,N,N?]
ligand directs the entering phosphine to a position trans
to the carbon atom that is not the most favoured
arrangement according to this model.
(s, Ha), 2.89 (m, Hb), 4.25 (m, Hc), 6.36 (d, J(HH)ꢂ
Hz, J(HÃPt)ꢂ
55 Hz, 1H, H5), 6.58 (d, J(HH)ꢂ
1H, H4), 7.43 (m), 7.65 (m) PPh3, 8.82 (d, J(HÃ
P)ꢂ
Hz, J(HÃPt)ꢂ
CDCl3): d 22.0 (s, J(PÃ
NMR (54 MHz, CDCl3): d ꢀ
/
8
/
/
/
8 Hz,
/
/
9
/
/
95 Hz, Hd) ppm. 31P-NMR (101 MHz,
/
Pt)ꢂ
/
4080 Hz) ppm. 195Pt-
/
4155 (d, J(PÃ
/
Pt)ꢂ4080
/
Hz) ppm. Anal. Found: C, 47.2; H, 3.8; N, 3.9. Calc. for
C29H28Cl3N2PPt: C, 47.26; H, 3.83; N, 3.80%.
Compound
PPh3] (2d) was obtained as a yellow solid by an
analogous procedure using 60 mg (1.4ꢄ
10ꢀ4 mol) of
compound 1e and 35 mg (1.4ꢄ
10ꢀ4 mol) of PPh3.
Yield 76 mg (80%). 1H-NMR (200 MHz, CDCl3): d 2.32
(s, Ha), 2.89 (t, J(HÃ 6 Hz, Hb), 4.25 (m, Hc), 6.36
H)ꢂ
(m, J(HÃPt)ꢂ 8 Hz,
55 Hz, 1H, H5), 6.45 (t, J(HH)ꢂ
1H, H4), 6.82 (d, J(HH)ꢂ8 Hz, 1H, H3), 7.43 (m), 7.65
(m) PPh3, 8.82 (d, J(HÃP)ꢂ9 Hz, J(HÃPt)ꢂ95 Hz,
Hd) ppm. 31P-NMR (101 MHz, CDCl3): d 21.50 (s,
J(PÃPt)ꢂ
4140 Hz) ppm. 195Pt-NMR (54 MHz,
CDCl3): d ꢀ4166 (d, J(PÃPt)ꢂ4120 Hz) ppm. FAB-
MS, m/z: 666 [MÃCl]. Anal. Found. C, 49.1; H, 4.0; N,
[PtCl(2-C6H3ClCHNCH2CH2NMe2)-
/
/
3. Experimental
/
/
3.1. General
/
/
/
/
Mass and NMR spectra were performed by the
Serveis Cient´ıfico-Te`cnics de la Universitat de Barce-
lona. Microanalyses were performed by the Institut de
Qu´ımica Bio-orga`nica de Barcelona (Consejo Superior
de Investigaciones Cient´ıficas).
/
/
/
/
/
/
/
/
/
/
FAB mass spectra were carried out in a VG-Quattro
spectrometer with 3-nitrobenzyl alcohol matrix. 1H-,
13C-, 31P- and 195Pt-NMR spectra were recorded by
using Varian Gemini 200 (1H, 200 MHz), Varian
XL300FT (13C, 75.4 MHz) and Bruker 250 (31P, 101.2
MHz; 195Pt, 54 MHz) spectrometers, and referenced to
SiMe4 (1H, 13C), H3PO4 (31P) and H2PtCl6 in D2O
4.0. Calc. for C29H29Cl2N2PPt: C, 49.58; H, 4.16; N,
3.99%.
Compound
(2e) was obtained as a yellow solid by an analogous
procedure using 50 mg (1.2ꢄ
10ꢀ4 mol) of compound
1e and 32 mg (1.2ꢄ
10ꢀ4 mol) of PPh3. Yield 60 mg
(73%). 1H-NMR (200 MHz, CDCl3): d 2.43 (s, Ha), 2.89
(t, J(HÃH)ꢂ H)ꢂ6 Hz, J(HÃ
6 Hz, Hb), 4.25 (t, J(HÃ
Pt)ꢂ
27 Hz, Hc), 6.51 (m, 2H), 6.89 (m, 2H) H2ꢁ5, 7.43
(m), 7.64 (m) PPh3; 8.66 (d, J(HÃP)ꢂ10 Hz, J(HÃ
Pt)ꢂ
91 Hz, Hd) ppm. 31P-NMR (101 MHz, CDCl3):
d 24.21 (s, J(PÃPt)ꢂ
4159 Hz) ppm. 195Pt-NMR (54
MHz, CDCl3): d ꢀ4221 (d, br, J(PÃPt) ca. 4200 Hz)
ppm. L (10ꢀ3 M in acetone): 26.2 Vꢀ1 cm2 molꢀ1
FAB-MS, m/z: 632 [MÃCl]. Anal. Found: C, 49.0; H,
4.4; N, 4.0. Calc. for C29H30ClN2PPt×2H2O: C, 49.47;
H, 4.87; N, 3.98%.
Compound [Pt(C6H4CHNCH2CH2NMe2)dppe]Cl
(3e) was obtained as a light yellow solid by an analogous
procedure using 25 mg (6.2ꢄ
10ꢀ5 mol) of compound
1e and 25 mg (6.3ꢄ
10ꢀ5 mol) of dppe. Yield 40 mg
(81%). 1H-NMR (200 MHz, CDCl3): d 2.04 (s, Ha), 1.93
(m, 2H), 2.45ꢁ
2.53 (m, 4H), 3.59 (m, 2H) Hb,c,e,f, 6.84
(m, 1H), 7.09 (m, 1H), 7.60 (m), 7.90 (m) aromatics, 8.63
(d, J(HÃP)ꢂ8 Hz, J(HÃPt)ꢂ
87 Hz, Hd) ppm. 31P-
NMR (101 MHz, CDCl3): d 42.72 (s, J(PÃPt)ꢂ3635
Hz, Pb), 50.24 (s, J(PÃ 1876 Hz, Pa) ppm. 195Pt-
Pt)ꢂ
NMR (54 MHz, CDCl3): d ꢀ Pt)ꢂ
4673 (dd, J(PbÃ
[PtCl(C6H4CHNCH2CH2NMe2)PPh3]
/
/
(
195Pt). d values are given in ppm and J values in Hz.
/
/
/
/
/
/
3.2. Preparation of the compounds
/
/
/
/
Compounds 1 were prepared as previously reported
[9].
/
/
/
/
Compound
(2a) was obtained from 50 mg (1.1ꢄ
compound 1a and 29 mg (1.1ꢄ
10ꢀ4 mol) of PPh3
[PtBr(C6H4CHNCH2CH2NMe2)PPh3]
.
/
10ꢀ4 mol) of
/
/
/
which were allowed to react in acetone (20 ml) at room
temperature for 2 h. The solvent was removed in a
rotary evaporator and the residue was washed with
hexane and dried in vacuo. Yield 60 mg (76%). 1H-
NMR (200 MHz, CDCl3): d 2.27 (s, Ha), 3.15 (m, Hb),
/
/
4.43 (m, Hc), 6.26 (d, J(HÃ
H5), 6.53 (t, J(HÃ
H)ꢂ7 Hz), 6.90 (t, J(HÃ
H3, H4, 7.34ꢁ 7.77 (m) PPh3 and H2, 8.77
7.45 (m), 7.72ꢁ
(d, J(HÃP)ꢂ6 Hz, J(HÃPt)ꢂ
94 Hz, Hd) ppm. 31P-
NMR (101 MHz, CDCl3): d 24.35 (s, J(PÃPt)ꢂ4042
Hz) ppm. 195Pt-NMR (54 MHz, CDCl3): d ꢀ
4227 (d,
br, J(PÃPt) ca. 4000 Hz) ppm. FAB-MS, m/z: 632 [MÃ
/
H)ꢂ
/
7 Hz, J(HÃ
/
Pt)ꢂ
/
50 Hz,
/
/
/
H)ꢂ
/7 Hz)
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/

148
M. Crespo et al. / Journal of Organometallic Chemistry 681 (2003) 143ꢁ149
/
3628 Hz, J(PaÃ
acetone): 98 Vꢀ1 cm2 molꢀ1. FAB-MS, m/z: 768 [MÃ
Cl].
Compound [PtCl(C6Cl4CHNCH2CH2NMe2)(PPh3)2]
(4b) was obtained as a white solid by an analogous
procedure using 50 mg (9.2ꢄ
10ꢀ5 mol) of compound
1b and 48 mg (1.8ꢄ
10ꢀ4 mol) of PPh3. Yield 70 mg
(71%). 1H-NMR (200 MHz, CDCl3): d 2.10 (s, Ha), 1.97
(t, J(HÃH)ꢂ H)ꢂ
7 Hz, Hb), 3.57 (t, J(HÃ 7 Hz, Hc),
7.39 (m), 7.77 (m) PPh3, 8.27 (s, Hd) ppm. 31P-NMR
(101 MHz, CDCl3): d 19.33 (s, J(PÃPt)ꢂ3052 Hz)
ppm. 195Pt-NMR (54 MHz, CDCl3): d ꢀ
4214 (t, J(PÃ
Pt)ꢂ3054 Hz) ppm. FAB-MS, m/z: 1065 [M], 998 [MÃ
2Cl], 961 [MÃ3Cl], 803 [MÃPPh3], 769 [MÃPPh3ÃCl],
718 [Pt(PPh3)2]. Anal. Found: C, 49.2; H, 4.1; N, 2.5.
Calc. for C47H41Cl5N2P2Pt×4H2O: C, 49.51; H, 4.33; N,
2.46%.
/
Pt)ꢂ
1876 Hz) ppm. L (10ꢀ3 M in
/
Table 2
Crystallographic and refinement data for compound 4f
/
Empirical formula
Formula weight
Temperature (K)
C
47H43Cl3N2P2Pt×0.5C3H6O
/
1028.25
293(2)
˚
Wavelength (A)
0.71069
triclinic, P1
/
¯
Crystal system, space group
Unit cell dimensions
/
˚
a (A)
12.1960(10)
13.4760(10)
16.6550(10)
92.03
/
/
/
/
˚
b (A)
˚
c (A)
a (8)
b (8)
g (8)
/
/
106.63
114.79
/
/
/
/
3
˚
V (A ); Z
2342.8(3); 2
1.458
3.269
dcalcd (Mg mꢀ3
)
/
/
/
/
Abs coefficient (mmꢀ1
F(0 0 0)
)
1028
/
Reflections coll./unique
Data/restraint/parameters
GOF on F2
11 307/7339 [Rint
7339/0/509
1.060
ꢂ/0.0235]
Compound [PtCl(3,5-C6H2Cl2CHNCH2CH2NMe2)-
(PPh3)2] (4f) was obtained as a white solid by an
R1 (I ꢀ
wR2 (all data)
Peak and hole (e A
/
2s(I))
0.0313
0.0902
analogous procedure using 50 mg (1.0ꢄ
compound 1f and 54 mg (2.1ꢄ
10ꢀ4 mol) of PPh3. Yield
74 mg (71%). H-NMR (200 MHz, CDCl3): d 2.32 (s,
Ha), 2.37 (m, Hb), 3.39 (t, J(HÃ 7 Hz, Hc), 6.18 (d,
H)ꢂ
J(HÃH)ꢂ2 Hz, 1H), 7.06 (d, J(HÃH)ꢂ
2 Hz, 1H) H2,
H4, 7.26ꢁ 7.60 (m) PPh3, 9.33 (s, Hd)
7.38 (m), 7.54ꢁ
ppm. 13C-NMR (75 MHz, CDCl3): d 45.42 (s, Ca), 58.77
(s), 59.59 (s) Cc, Cb, 123.88 (s, J(CÃ
Pt)ꢂ53 Hz), 141.36
(s) C2, C4, 127.93 (s), 130.49 (s), 134.57 (s) PPh3, 165.64
(s, J(PtÃC)ꢂ
90 Hz, Cd) ppm. 31P-NMR (101 MHz,
CDCl3): d 22.05 (s, J(PÃPt)ꢂ
2921 Hz) ppm. 195Pt-
NMR (54 MHz, CDCl3): d ꢀ4295 (t, J(PÃPt)ꢂ2930
Hz) ppm. FAB-MS, m/z: 997 [M], 735 [MÃPPh3], 718
[Pt(PPh3)2], 700 [MÃPPh3ÃCl]. Anal. Found: C, 56.5; H,
/
10ꢀ4 mol) of
ꢀ3
˚
)
0.977 and ꢀ0.736
/
/
1
/
/
/
/
/
/
puter program [19] using 7339 reflections (very negative
intensities were not assumed). The function minimised
/
/
2
2 2
was awjjFoj ꢀ
/
jFcj j , where wꢂ
/
[s2(I)ꢃ
/
(0.0584P)2ꢃ
/
/
/
1.3536P]ꢀ1 and Pꢂ
/
(jFoj ꢃ2jFcj )/3. f, f? and f?? were
/
2
2
taken from International Tables of X-ray Crystallogra-
phy [20]. All hydrogen atoms were computed and
refined using a riding model with an isotropic tempera-
ture factor equal to 1.2 times the equivalent temperature
factor of the atom to which they are linked. Further
details are given in Table 2.
/
/
/
/
/
/
/
/
/
/
4.5; N, 2.1. Calc. for C47H43Cl3N2P2Pt: C, 56.49; H,
4.34; N, 2.80%.
3.3. X-ray structure analysis
4. Supplementary material
3.3.1. Data collection
A prismatic crystal was selected and mounted on a
MAR345 diffractometer with an image plate detector.
Unit cell parameters were determined from automatic
The crystallographic data of compound 4f have been
deposited with the Cambridge Crystallographic Data
Centre, CCDC No. 206995. Copies of this information
may be obtained free of charge from The Director,
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK
centering of 11 247 reflections (38B
by least-squares method. Intensities were collected with
graphite monochromatised MoꢁKa radiation. 11 307
reflections were measured in the range 2.688Bu B
28.938, 7339 of which were non-equivalent by symmetry
(Rint (on I)ꢂ0.023) and 6425 reflections were assumed
as observed applying the condition I ꢀ2s(I). Lorentz
/
u B
/
318) and refined
/
(Fax: ꢃ44-1223-336033; e-mail: deposit@ccdc.cam.ac.
/
/
/
uk or www: http://www.ccdc.cam.ac.uk).
/
/
polarisation and absorption corrections were made.
Further details are given in Table 2.
Acknowledgements
This work was supported by the Ministerio de Ciencia
y Tecnolog´ıa (project: BQU2000-0652) and by the
Comissionat per a Universitats i Recerca (project:
2001SGR-00054).
3.3.2. Structure solution and refinement
The structure was solved by Patterson synthesis using
SHELXS computer program [19] and refined by the full-
matrix least-squares method, with the SHELXL97 com-

M. Crespo et al. / Journal of Organometallic Chemistry 681 (2003) 143ꢁ
/149
149
[11] NMR data obtained at 228 K in CDCl3 solution: 31P-NMR: d
23.1 (Jꢂ4223 Hz) ppm, 2e; 23.3 (Jꢂ
3946 Hz) ppm, 2e?. 1H-
NMR d 2.26 (6H), 3.31 (2H), 4.48 (2H), 8.97 (1H, Jꢂ90 Hz)
75 Hz)
References
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[17] Compound 1g is the minor isomer obtained when [Pt(dba)2]
reacted with 2,3,6-Cl3C6H2CHNCH2CH2NMe2 (see Ref. [9]). In
this case, the reaction with triphenylphosphine has been carried
out with the mixture of isomers 1c and 1g to afford 2c and 4g,
respectively. NMR data for 4g: 1H-NMR (200 MHz, CDCl3): d
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2.23 (s, Ha), 2.89 (m, J(HÃ
J(HÃH)ꢂ8 Hz, 1H), 6.35 (d, J(HÃ
7.38 (m), 7.54ꢁ
7.60 (m) PPh3, 8.50 (s, Hd) ppm. 31P-NMR (101
MHz, CDCl3): d 18.20 (s, J(PÃPt)ꢂ3054 Hz) ppm.
/
H)ꢂ
/
6 Hz, Hb), 4.27 (m, Hc), 6.10 (d,
(b) M. Crespo, X. Solans, M. Font-Bard´ıa, Organometallics 14
(1995) 355;
/
/
/
H)ꢂ
/
8 Hz, 1H) H3, H4, 7.26ꢁ
/
/
(c) J. Albert, J. Granell, R. Moragas, J. Sales, M. Font-Bard´ıa, X.
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/
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Structure Determination, University of Gottingen, Germany,
¨
1997.
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/