Compound [PtPh2(SMe2)2] as a Versatile Metalating Agent in the Preparation of New Types of [C,N,N′] Cyclometalated Platinum Compounds

Article abstract of DOI:10.1021/om030674t

The reactions of [PtPh₂(SMe₂)₂] (1) with ligands RCH=NCH₂CH₂NMe₂ (R = C ₆H₅ (2a), 2-BrC₆H₄ (2b), 2,6-Cl ₂C₆H₃ (2c), 2-ClC₆H₄ (2d), and C₆F₆ (2e)) produced compounds [PtPh ₂{Me₂NCH₂CH₂NCHR}] (3). Compounds 3 led to formation of three different types of [C,N,N′] platinum compounds, including platinum(II) compounds with a seven-membered metallacycle. The reactions of the cyclometalated compounds with triphenylphosphine were also studied.

Full text of DOI:10.1021/om030674t

1708
Organometallics 2004, 23, 1708-1713
Com p ou n d [P tP h 2(SMe2)2] a s a Ver sa tile Meta la tin g
Agen t in th e P r ep a r a tion of New Typ es of [C,N,N′]
Cyclom eta la ted P la tin u m Com p ou n d s
Margarita Crespo,*,† Merce` Font-Bardia,‡ and Xavier Solans‡
Departament de Quı´mica Inorga`nica, Universitat de Barcelona, Diagonal 647,
08028 Barcelona, Spain, and Departament de Cristal‚lografia, Mineralogia i Dipo`sits
Minerals, Universitat de Barcelona, Mart´ı i Franque`s s/ n, 08028 Barcelona, Spain
Received November 26, 2003
The reactions of [PtPh2(SMe2)2] (1) with ligands RCHdNCH2CH2NMe2 (R ) C6H5 (2a ),
2-BrC6H4 (2b), 2,6-Cl2C6H3 (2c), 2-ClC6H4 (2d ), and C6F5 (2e)) produced compounds
[PtPh2{Me2NCH2CH2NCHR}] (3). Compounds 3 led to formation of three different types of
[C,N,N′] platinum compounds, including platinum(II) compounds with a seven-membered
metallacycle. The reactions of the cyclometalated compounds with triphenylphosphine were
also studied.
Cyclometalated compounds containing nitrogen ligands
pounds.13-17 The present paper deals with the reactions
of potentially terdentate [C,N,N′] ligands RCHdNCH2-
CH2NMe2 (R ) C6H5, 2-BrC6H4, 2,6-Cl2C6H3, 2-ClC6H4,
and C6F5) with platinum substrate [PtPh2(SMe2)2] in
order to compare the results with those obtained for
[C,N] ligands,16 as well as with those reported when [Pt2-
Me4(µ-SMe2)2]3 was used as starting material.
The reaction of [PtPh2(SMe2)2] with C6H5CHdNCH2-
CH2NMe2 (2a ) in toluene at room temperature produced
compound [PtPh2(Me2NCH2CH2NCHC6H5)] (3a ) con-
taining a bidentate [N,N′] ligand. Cyclometalation of the
coordinated ligand 2a was not observed at room tem-
perature; however, when a toluene solution of compound
3a was refluxed for several hours, the cyclometalated
platinum(II) compound [PtPh(Me2NCH2CH2NCHC6H4)]
(4a ) containing a terdentate [C,N,N′] ligand was ob-
tained in fair yield.
have been widely studied due to their potential applica-
tions in several areas such as organic synthesis, homo-
geneous catalysis, and the design of new materials with
interesting properties.1 In recent years, in addition to
classical bidentate [C,N] systems, interest has been
focused on cyclometalated platinum compounds con-
taining [C,N,N′]2-8 or [N,C,N]9-12 terdentate monoan-
ionic ligands.
Diarylplatinum(II) complexes containing readily dis-
placed dialkylsulfide ligands have been extensively used
as precursors of several types of platinum com-
* Corresponding
margarita.crespo@qi.ub.es.
† Departament de Qu´ımica Inorga`nica.
author.
Fax:
934907725.
E-mail:
‡ Departament de Cristal‚lografia, Mineralogia i Dipo`sits Minerals.
(1) (a) Ryabov, A. D. Synthesis 1985, 233. (b) Dupont, J .; Pfeffer,
M.; Spencer, J . Eur. J . Inorg. Chem. 2001, 1917. (c) Espinet, P.;
Esteruelas, M. A.; Oro, L. A.; Serrano, J . L.; Sola, E. Coord. Chem.
Rev. 1992, 117, 215. (d) Maestri, M.; Deuschel-Cornioley, C.; von
Zelewsky, A. Coord. Chem. Rev. 1991, 111, 117. (e) Albrecht, M.; Lutz,
M.; Spek, A. L.; van Koten, G. Nature 2000, 406, 970. (f) Guillena, G.;
Rodriguez, G.; Albrecht, M.; van Koten, G. Chem. Eur. J . 2002, 8 (23),
5368.
The reaction of [PtPh2(SMe2)2] (1) with 2-BrC6H4CHd
NCH2CH2NMe2 (2b ) in toluene at room temperature
produced the cyclometalated [C,N,N′] platinum(IV)
complex [PtBrPh2(Me2NCH2CH2NCHC6H4)] (5b), which
indicates that oxidative addition of C-Br is fast, in
agreement with the higher reactivity of C-Br versus
C-H bonds.18 Intermediate coordination compound
[PtPh2{Me2NCH2CH2NCH(2-BrC6H4)}] (3b) could be
(2) (a) Baar, C. R.; J enkins, H. A.; Vittal, J . J .; Yap, G. P. A.;
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X. J . Chem. Soc., Dalton Trans. 2003, 3763.
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Nicolo´, F.; Del Zotto, A. Eur. J . Inorg. Chem. 2002, 629. (b) Casado
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10.1021/om030674t CCC: $27.50 © 2004 American Chemical Society
Publication on Web 02/27/2004

[PtPh2(SMe2)2] as a Versatile Metalating Agent
Organometallics, Vol. 23, No. 8, 2004 1709
Sch em e 1
dergo reductive elimination of biaryl,12,20 no evidence
of reductive elimination of biphenyl from 5b to yield a
platinum(II) compound was observed.
for 2 h 3c and 3d gave, respectively, compounds [PtCl-
(Me2NCH2CH2NCHC6ClH3C6H4)] (6c) and [PtCl(Me2-
NCH2CH2NCHC6H4C6H4)] (6d ), depicted in Scheme 1,
which represent a new class of [C,N,N′] cyclometalated
platinum(II) compound containing a seven-membered
metallacycle. In view of these results, the behavior of
the compound [PtBrPh2(Me2NCH2CH2NCHC6H4)] (5b)
in refluxing toluene was also studied, but no compound
with a spectral pattern analogous to that of compounds
6 was detected. The failure to transform 5b into a seven-
membered metallacycle can be related to the low
tendency of the chelate dinitrogen ligand to dissociate
and produce the required vacant site in the coordination
sphere of the platinum.
The reactions of [PtPh2(SMe2)2] with ligands 2,6-
Cl2C6H3CHdNCH2CH2NMe2 (2c), 2-ClC6H4CHdNCH2-
CH2NMe2 (2d ), and C6F5CHdNCH2CH2NMe2 (2e) in
toluene gave coordination compounds 3c, 3d , and 3e,
in which the ligand behaves as bidentate [N,N′] ligands.
A 2D-NOESY NMR was carried out for 3e, and the
presence of a cross-peak signal between the imine (Hd)
and the methylene (Hc) protons supports a trans ar-
rangement (E configuration)21 across the CdN bond, as
observed in the structure determination carried out for
3a (see below).
Intramolecular activation of C-Cl or C-F bonds was
not observed at room temperature, in agreement with
their lower reactivity when compared to C-Br bonds.
Therefore, toluene solutions of compounds 3c-e were
refluxed for several hours. For 3e, formation of the
corresponding platinum(IV) cyclometalated compound
was not observed. The lack of reactivity of the C-F
bond, which has been however activated upon reaction
of ligand 2e with platinum substrate [Pt2Me4(µ-SMe2)2],22
can be related to the combined effects of the inertness
of the C-F bond23 and the unfavorable steric effects of
the phenyl groups. In contrast, upon refluxing in toluene
All compounds were characterized by elemental analy-
ses, FAB mass spectra, and NMR spectroscopies, and
compounds 3a and 4a were also characterized crystal-
lographically. In the 1H NMR spectra, the dimethyl-
amino protons and the imine proton are coupled to
platinum, thus confirming coordination of both nitrogen
atoms to platinum. For compounds 6, the large value
of J (H-Pt) for the imine (149 Hz) is consistent with the
presence of a chloro ligand trans to the imine. The {1H-
13C}-heterocorrelation spectra of 3a , 4a , 5b, 6c, and 6d
showed respectively 9, 7, 10, 7, and 8 cross-peaks in the
aromatic region. These results are consistent with the
(19) Resonances at δ ) 2.65 [s, J (Pt-H) ) 21, NMe2] and δ ) 8.98
[s, J (Pt-H) ) 41, CHN] were assigned to 3b. Other resonances could
not be assigned due to overlapping with those of 2b and 5b.
(20) Anderson, G. K. In Comprehensive Organometallics Chemistry,
2nd ed., Puddephatt, R. J ., Ed.; Pergamon Press: New York, 1995;
Vol. 9, Chapter 8, p 431.
(22) (a) Anderson, C. M.; Crespo, M.; Ferguson, G.; Lough, A. J .;
Puddephatt, R. J . Organometallics 1992, 11, 1177. (b) Lo´pez, O.;
Crespo, M.; Font-Bard´ıa, M.; Solans, X. Organometallics 1997, 16,
1233.
(23) (a) Burdeniuc, J .; J edlicka, B.; Crabtree, R. H. Chem. Ber. Recl.
1997, 130, 145. (b) Bosque, R.; Clot, E.; Fantacci, S.; Maseras, F.;
Eisenstein, O.; Perutz, R. N.; Renkema, K. B.; Caulton, K. G. J . Am.
Chem. Soc. 1998, 120, 12634.
(21) Z/E conformations have been assigned not taking into account
the platinum coordination to the imine nitrogen.

1710 Organometallics, Vol. 23, No. 8, 2004
Crespo et al.
Sch em e 2
proposed structures, in particular with the nonequiva-
lence of the two η1-phenyl ligand in 3a and 5b. The 195Pt
resonances are in the expected range for the corre-
sponding set of ligands and oxidation state of the
platinum center. Complete NMR data and the {1H-
13C}-heterocorrelation spectrum of 6c (Figure S1) are
given in the Supporting Information.
creases significantly from compounds 8 (J (P-Pt) ca.
1800 Hz), in which the triphenylphosphine is trans to
the metalated ring, to compounds 9 (J (P-Pt) ca. 4300
Hz), in which the triphenylphosphine is trans to the
imine. Consistently, the imine proton appears as a
singlet for compounds 8 and as a doublet due to coupling
with 31P for compounds 9.
The obtained geometries for 7a (PPh3 trans to the
metalated carbon) and for 9c and 9d (PPh3 trans to the
imine) are in good agreement with the transphobia26
and the trans-choice27 models.
The reaction of compound 5b with triphenylphosphine
under the conditions reported for compounds 4 and 6
led to nearly quantitative recovery of the initial com-
pound 5b, indicating a high stability of the terdentate
[C,N,N′] platinum(IV) compound. When this reaction
was followed by 1H and 31P NMR in solution, formation
The reactions of the new cyclometalated compounds
(4a , 5b, 6c, and 6d ) with triphenylphosphine were
studied in order to analyze the lability of the dimethyl-
amino group as well as the stability of the metalla-
cycles.24,25
The reaction of 4a with an equimolecular amount of
PPh3 carried out in acetone at room temperature
produced compound [PtPh(Me2NCH2CH2NCHC6H4)-
(PPh3)] (7a ), in which the triphenylphosphine replaces
the dimethylamino group. As shown in Scheme 2, a
similar reaction for compounds 6c and 6d produces
respectively compounds [PtCl(Me2NCH2CH2NCHC6-
ClH3C6H4)(PPh3)] (8c) and [PtCl(Me2NCH2CH2NCHC6-
H4C6H4)(PPh3)] (8d ), which isomerize in solution to yield
within a few hours compounds 9c and 9d . In contrast,
isomerization was not observed for 7a . Cyclometalated
[C,N] compounds 7, 8, and 9 do not react further with
phosphine, which indicates that the corresponding met-
allacycles are not cleaved.
Compounds 8c and 8d were characterized by NMR
in solution, and compounds 7a , 9c, and 9d were
characterized by elemental analyses, FAB mass spectra,
and NMR spectroscopies. Compound 9c was also char-
acterized crystallographically. The value of the coupling
J (P-Pt) observed in 31P and 195Pt NMR spectra in-
of the expected platinum(IV) compound 10b in a 30%
28
yield was observed within 1 h.
After 24 h, the
intensity of the NMR signals corresponding to 10b
decreased, while new signals corresponding to a plati-
num(II) compound with one triphenylphosphine ligand
appeared and were tentatively assigned to 8b (relative
amounts 8b:10b ) 2:1). After 48 h, according to 31P
NMR, unreacted 5b was still the major component (ca.
70%), and, in addition to 8b, very minor resonances
corresponding to a compound with two mutually trans
PPh3 ligands (11b) were observed. These results support
the suggestion that a vacant site in the coordination
sphere of platinum is required for the process leading
to seven-membered metallacycles. This process takes
place for 5b only in the presence of PPh3, which induces
the dissociation of the dimethylamino arm of the ter-
(24) (a) Albert, J .; Go´mez, M.; Granell, J .; Sales, J .; Solans, X.
Organometallics 1990, 9, 1405. (b) Albert, J .; Granell, J .; Moragas, R.;
Sales, J .; Font-Bardia, M.; Solans, X. J . Organomet. Chem. 1995, 494,
95.
(25) (a) Crespo, M.; Solans, X.; Font-Bard´ıa, M. Organometallics
1995, 14, 355. (b) Crespo, M.; Granell, J .; Solans, X.; Font-Bard´ıa, M.
J . Organomet. Chem. 2003, 681, 143.
(26) Vicente, J .; Abad, J . A.; Mart´ınez-Viviente, E.; J ones, P. G.
Organometallics 2002, 21, 4454.
(27) Cuevas, J . V.; Garc´ıa-Herbosa, G.; Miguel, D.; Mun˜oz, A. Inorg.
Chem. Commun. 2002, 5, 340.
(28) Anderson, C.; Crespo, M.; Font-Bard´ıa, M.; Klein, A.; Solans,
X. J . Organomet. Chem. 2000, 601, 22.

[PtPh2(SMe2)2] as a Versatile Metalating Agent
Organometallics, Vol. 23, No. 8, 2004 1711
F igu r e 1. Molecular structure of compound 3a .
F igu r e 3. Molecular structure of compound 9c.
C(11). The dihedral angle between the mean planes of
the metallacycle and the coordination plane is 22.20°,
and the phenyl ligand is tilted from the coordination
plane by 81.68°.
For 9c, a nonplanar seven-membered metallacycle in
which the two phenyl rings are tilted 52.30(2)° from
each other results from bidentate [C,N] coordination.
The triphenylphosphine is trans to the imine group, and
the uncoordinated NMe2 moiety points away from the
platinum center.
Bond lengths and angles are well within the range of
values obtained for analogous compounds. In particular,
the Pt-C bonds are in the range of values found for
other aryl complexes of platinum(II)13,17b and the Pt-
amine distances are larger than platinum-imine dis-
tances, consistent with the weaker ligating ability of
amines for platinum.3,7,22 Most bond angles at platinum
are close to the ideal value of 90°, and the smallest
angles correspond to N(2)-Pt-N(1) (81.3(3)° for 3a and
81.0(2)° for 4a ) and to the metallacycle (C(11)-Pt-N(2)
) 81.46(18)° for 4a and C(1)-Pt-N(1) ) 84.23(13)° for
9c).
Con clu sion s. In conclusion, compound [PtPh2(SMe2)2],
although less reactive than [Pt2Me4(µ-SMe2)2] toward
intramolecular activation of C-X bonds, has been shown
to be an excellent metal precursor for the synthesis of
three different types of cyclometalated compounds. As
previously reported for the chemistry of dimethylplati-
num analogues,3 a concerted mechanism, involving prior
dissociation of the dimethylamino group of the inter-
mediate 3, is suggested for intramolecular C-X bond
activation. As shown in Scheme 3, for X ) Br platinum-
(IV) compound 5 is obtained upon coordination of the
NMe2 moiety, while for X ) H, compound 4 is formed
along with reductive elimination of benzene. The more
drastic conditions required for activation of the C-Cl
bond along with the vacant site in the coordination
sphere of platinum facilitate the process leading to
compounds 6. As described for compound [PtBrPh2(Ph-
CH2NCHC6H4)(SMe2)],16 the process consists of reduc-
tive elimination to form a biaryl coordinated through
the imine to platinum(II), followed by C-H activation
F igu r e 2. Molecular structure of compound 4a .
dentate ligand and favors the formation of the corre-
sponding compound 8. A similar result has been de-
scribed for compound [PtBrPh2(PhCH2NCHC6H4)-
(SMe2)],16 in which prior dissociation of the SMe2 ligand
is required for the formation of a seven-membered
metallacycle.
Cr ysta l Str u ctu r es. Suitable crystals of compounds
3a and 4a were grown from acetone solution. Crystals
of 9c were obtained upon slow difusion of hexane into
an acetone solution of the compound. The crystal
structures are composed of discrete molecules separated
by van der Waals distances. The structures are shown
in Figures 1, 2, and 3, and selected molecular dimen-
sions are listed in Table 1. The molecular structures
confirm the geometries predicted from spectroscopic
data.
For 3a , the imine is coordinated through both nitro-
gen atoms to platinum and adopts an E configuration,
the torsion angle C(4)-N(2)-C(5)-C(6) being 172.39°.
The phenyl ligands are tilted from the coordination
plane by 87.30° (Ph trans to imine) and 48.27° (Ph trans
to amine), being rotated by 82.75° to each other.
For 4a a fused [5,5,6] tricyclic system containing a
five-membered metallacycle, a chelate ring with two
nitrogen atoms, and the phenyl group results from
terdentate [C,N,N′] coordination of the ligand. The
metallacycle contains the imine functionality and is
approximately planar; the largest deviation from the
mean plane defined by the five atoms is -0.0240 Å for

1712 Organometallics, Vol. 23, No. 8, 2004
Crespo et al.
Ta ble 1. Selected Bon d Len gth s (Å) a n d An gles (d eg) for Com p ou n d s 3a , 4a , a n d 9c w ith Estim a ted
Sta n d a r d Devia tion s
compound 3a
compound 4a
compound 9c
Pt-C(12)
Pt-C(18)
Pt-N(2)
Pt-N(1)
C(12)-Pt-C(18)
C(18)-Pt-N(2)
C(12)-Pt-N(1)
N(2)-Pt-N(1)
1.977(11)
1.992(8)
2.145(8)
2.178(8)
88.2(4)
97.5(4)
93.0(3)
81.3(3)
Pt-C(11)
Pt-C(12)
Pt-N(2)
Pt-N(1)
C(11)-Pt-C(12)
C(11)-Pt-N(2)
C(12)-Pt-N(1)
N(2)-Pt-N(1)
1.986(6)
2.009(4)
2.016(4)
2.139(6)
98.36(18)
81.46(18)
99.1(2)
Pt-C(1)
Pt-Cl(1)
Pt-N(1)
Pt-P(1)
C(1)-Pt-N(1)
C(1)-Pt-P(1)
N(1)-Pt-Cl(1)
P(1)-Pt-Cl(1)
1.996(3)
2.3980(9)
2.071(3)
2.2347(10)
84.23(13)
94.42(11)
86.04(8)
81.0(2)
95.32(3)
Sch em e 3
de Barcelona using Varian Gemini 200 (1H, 200 MHz), Varian
XL300FT (13C, 75.4 MHz; 19F, 282.2 MHz), Varian Mercury
400 (1H-13C ghsqc; 1H, 400 MHz; 13C, 100.6 MHz), and Bruker
250 (31P, 101.25 MHz; 195Pt, 54 MHz) spectrometers, and
referenced to SiMe4 (1H, 13C), CCl3F (19F), H3PO4 (31P), and
H2PtCl6 in D2O (195Pt). δ values are given in ppm and J values
in Hz.
and reductive elimination of benzene to yield the final
compound. The reactions of the obtained cyclometalated
compounds with triphenylphosphine confirm the stabil-
ity of both five- and seven-membered platinacycles.
Exp er im en ta l Section
P r ep a r a tion of th e Com p ou n d s. Compounds [PtPh2-
(SMe2)2] (1)29 and 2a -d 3 were prepared as reported.
[P tP h 2(Me2NCH2CH2NCHC6H5)] (3a ) was obtained from
0.100 g (2.1 × 10-4 mol) of [PtPh2(SMe2)2] (1) and 0.037 g (2.1
× 10-4 mol) of ligand C6H5CHNCH2CH2NMe2 (1a ) in 25 mL
of toluene. The mixture was stirred at room temperature for
4 h, the solvent was evaporated in vacuo, and the remaining
Gen er a l P r oced u r es. Microanalyses were performed at
the Servei de Recursos Cient´ıfics i Te`cnics de la Universitat
Rovira i Virgili. FAB-mass spectra were performed at the
Servei d’Espectrometria de Masses de la Universitat de
Barcelona in a VG-Quattro spectrometer with 3-nitrobenzyl
1
alcohol matrix. H, 13C, 19F, 31P, and 195Pt NMR spectra were
recorded at the Unitat de RMN d’Alt Camp de la Universitat

[PtPh2(SMe2)2] as a Versatile Metalating Agent
Organometallics, Vol. 23, No. 8, 2004 1713
Ta ble 2. Cr ysta llogr a p h ic a n d Refin em en t Da ta for Com p ou n d s 3a , 4a , a n d 9c
3a
4a
9c
formula
C
23H26N2Pt
C17H20N2Pt
447.44
C35H33Cl2N2PPt‚0.5C3H6O6OH6O
807.63
fw
525.55
temp, K
wavelength, Å
cryst syst
space group
a, Å
293(2)
0.71069
monoclinic
P21/c
7.0430(10)
19.0655(16)
15.1942(15)
92.377(11)
2038.5(4); 4
1.712
293(2)
293(2)
0.71069
monoclinic
P21/c
14.5590(10)
7.7300(10)
15.0750(10)
114.29(10)
1546.4(2); 4
1.922
0.71073
monoclinic
P21/c
12.7770(10)
13.3150(10)
21.2780(10)
98.953(10)
3575.8(4); 4
1.500
b, Å
c, Å
â, deg
V, Å3; Z
d(calcd), Mg/m3
abs coeff, mm-1
F(000)
6.891
1024
9.065
856
4.146
1600
rflns collctd/unique
no. of data/restraints/params
GOF on F2
R1(I>2σ(I))
wR2 (all data)
peak and hole, e‚Å-3
16 358/2421
2421/0/235
1.164
15 370/4381
4381/0/169
1.030
40 579/11 442
11 442/0/426
1.205
0.0366
0.0380
0.0435
0.1252
0.675 and -0.910
0.0964
0.647 and -0.606
0.0963
1.127 and -1,137
residue was treated with diethyl ether to yield a white solid.
Yield: 70 mg (63%). Anal. Found: C, 52.9; H, 5.0; N, 5.1. Calc
for C23H26N2Pt: C, 52.56; H, 4.99; N, 5.33. FAB-MS, m/z: 525
[M], 448 [M - Ph], 371 [M - 2Ph].
acetone was evaporated in vacuo, and the remaining residue
was treated with diethyl ether to yield a white solid. Yield:
60 mg (69%). Anal. Found: C, 59.4; H, 5.4; N, 3.8. Calc for
C35H35N2PPt: C, 59.23; H, 4.97; N, 3.95. FAB-MS, m/z: 709
[M], 632 [M - Ph].
[P tP h 2{Me2NCH2CH2NCH(2,6-Cl2C6H3)}] (3c), [P tP h 2-
{Me2NCH2CH2NCH(2-ClC6H4)}] (3d), and [P tP h 2(Me2NCH2-
CH2NCHC6F 5)] (3e) were obtained as yellow solids using an
analogous procedure from 2c, 2d , and 2e, respectively. 3c:
Yield 70 mg (56%). Anal. Found: C, 46.8; H, 4.4; N, 4.6. Calc
for C23H24Cl2N2Pt: C, 46.47; H, 4.07; N, 4.71. FAB-MS, m/z:
593 [M], 558 [M - Cl], 516 [M - Ph], 481 [M - Cl - Ph]. 3d :
Yield 75 mg (64%). Anal. Found: C, 49.4; H, 4.5; N, 4.9. Calc
for C23H25ClN2Pt: C, 49.33; H, 4.50; N, 5.00. FAB-MS, m/z: 524
[M - Cl], 370 [M - Cl - 2Ph]. 3e: Yield 75 mg (64%). Anal.
Found: C, 44.5; H, 3.7; N, 4.3. Calc for C23H21F5N2Pt: C, 44.88;
H, 3.44; N, 4.55. FAB-MS, m/z: 615 [M]; 461 [M - 2Ph].
[P tP h (Me2NCH2CH2NCHC6H4)] (4a ) was obtained by
refluxing during 6 h a toluene solution (20 mL) containing
0.040 g (7.6 × 10-5 mol) of compound 3a . The solution was
filtered to remove a metallic residue, the solvent was evapo-
rated in vacuo, and the remaining residue was treated with
diethyl ether to yield a dark orange solid, which was recrystal-
lized in dichloromethane-hexane and dried in vacuo. Yield:
25 mg (73%). Anal. Found: C, 45.3; H, 4.5; N, 5.9. Calc for
[P t Cl(Me2NCH2CH 2NCH C6ClH3C6H 4)(P P h 3)] (9c) and
[P tCl(Me2NCH2CH2NCHC6H4C6H4)(P P h 3)] (9d ) were simi-
larly prepared from 50 mg of 6c or 6d and an equimolecular
amount of PPh3. 9c: Yield 40 mg (55%). Anal. Found: C, 53.6;
H, 4.5; N, 3.6. Calc for C35H33Cl2N2PPt: C, 53.99; H, 4.27; N,
3.60. FAB-MS, m/z: 778 [M], 743 [M - Cl]. 9d : Yield 35 mg
(47%). Anal. Found: C, 56.1; H, 4.7; N, 3.9. Calc for C35H34
-
ClN2PPt: C, 56.49; H, 4.61; N, 3.76. FAB-MS, m/z: 708 [M -
Cl].
[P t Cl(Me2NCH2CH 2NCH C6ClH3C6H 4)(P P h 3)] (8c) and
[P tCl(Me2NCH2CH2NCHC6H4C6H4)(P P h 3)] (8d ) were char-
acterized by NMR in solution: 10 mg of the corresponding
compound 6 was dissolved in 0.7 mL of CDCl3 in a NMR tube,
and an equimolar amount of PPh3 was added. 1H and 31P NMR
spectra were taken immediately after. A similar procedure was
followed to monitor by NMR the reaction of [PtBr(Ph)2(Me2-
NCH2CH2NCHC6H4)] (5b) with triphenylphosphine, and spec-
tra were taken at regular times until no further changes were
observed.
C
17H20N2Pt: C, 45.63; H, 4.51; N, 6.26. FAB-MS, m/z: 447 [M],
X-r a y Str u ctu r e An a lysis (3a , 4a , a n d 9c). Prismatic
crystals were selected and mounted on a MAR345 diffracto-
meter with an image plate detector. Intensities were collected
with graphite-monochromatized Mo KR radiation. The struc-
tures were solved by direct methods using the SHELXS
computer program30 and refined by the full-matrix least-
squares method, with the SHELXL97 computer program using
2421 (3a ), 4381 (4a ), and 11 442 (9c) reflections (very negative
intensities were not assumed). Further details are given in
Table 2.
370 [M - Ph].
[P tBr P h 2(Me2NCH2CH2NCHC6H4)] (5b) was obtained
from 0.100 g (2.1 × 10-4 mol) of [PtPh2(SMe2)2] (1) and 0.054
g (2.1 × 10-4 mol) of ligand 2-BrC6H4CHNCH2CH2NMe2 (2b)
in 25 mL of toluene. The mixture was stirred at room
temperature for 4 h, the solvent was evaporated in vacuo, and
the remaining residue was treated with diethyl ether to yield
a white solid. Yield: 80 mg (62%). Anal. Found: C, 45.5; H,
4.1; N, 4.6. Calc for C23H25BrN2Pt: C, 45.70; H, 4.17; N, 4.63.
FAB-MS, m/z: 524 [M - Br], 447 [M - Br - Ph], 370 [M - Br
- 2Ph].
Ack n ow led gm en t. This work was supported by the
Ministerio de Ciencia y Tecnolog´ıa (project: BQU2003-
00906/50% FEDER) and by the Comissionat per a
Universitats i Recerca (project: 2001SGR-00054).
Su p p or tin g In for m a tion Ava ila ble: Complete NMR
data (1H, 13C, 19F, 31P, and 195Pt) for compounds 3, 4, 5, 6, 7, 8,
9, and 10, Figure S1, and tables giving all bond lengths and
angles, refined and calculated atomic coordinates, and aniso-
tropic thermal parameters for 3a , 4a , and 9c. This material
is available free of charge via the Internet at http://pubs.acs.org.
[P tCl(Me2NCH2CH2NCHC6ClH3C6H4)] (6c) was obtained
from 0.060 g (1.00 × 10-4 mol) of compound 3c in refluxing
toluene for 2 h. The solvent was evaporated in vacuo, and the
remaining residue was treated with diethyl ether to yield a
light yellow solid. Yield: 35 mg (67%). Anal. Found: C, 39.3;
H, 3.6; N, 5.2. Calc for C17H18Cl2N2Pt: C, 39.55; H, 3.51; N,
5.43. FAB-MS, m/z: 515 [M], 480 [M - Cl].
[P t Cl(Me2NCH2CH2NCHC6H4C6H4)] (6d ) was similarly
prepared from 0.060 g (1.07 × 10-4 mol) of compound 3d .
Yield: 23 mg (44%). Anal. Found: C, 42.1; H, 4.1; N, 5.5. Calc
for C17H19ClN2Pt: C, 42.37; H, 3.97; N, 5.81. FAB-MS, m/z: 481
[M], 446 [M - Cl].
OM030674T
(29) (a) Song, D.; Wang, S. J . Organomet. Chem. 2002, 648, 302. (b)
Rashidi, M.; Fakhroeian, Z.; Puddephatt, R. J . J . Organomet. Chem.
1990, 406, 261.
(30) Sheldrick, G. M. SHELXS97, A computer program for crystal
structure determination; University of Go¨ttingen: Germany, 1997.
[P tP h (Me2NCH2CH2NCHC6H4)(P P h 3)] (7a ) was prepared
from 52 mg (1.2 × 10-4 mol) of 4a and an equimolar amount
of phosphine (32 mg) in acetone. After continuous stirring,