Stereoselective oxidative addition of methyl iodide to chiral cyclometallated platinum(II) compounds derived from (R)-(+)-1-(1-naphthylethylamine). Crystal structure of [PtMe{3-(R)-(C10H7)CHMeNCHC4H 2S}PPh3]

Article abstract of DOI:10.1016/S0022-328X(01)01043-9

The reaction of 3-(R)-(C₁₀H₇)CHMeNCHC₄H₃S (2a) with [Pt₂Me₄(μ-SMe₂)₂] in acetone gave the new chiral cyclometallated platinum(II) compound [PtMe{3-(R)-(C₁₀H₇)CHMeNCHC₄H ₂S}SMe₂] (3a). Addition of PPh₃ produced compound [PtMe{3-(R)-(C₁₀H₇)CHMeNCHC₄H ₂S}PPh₃] (4a) which was characterized by X-ray diffraction methods. While oxidative addition of methyl iodide to 3a gave two pairs of diastereomers, the analogous reaction for 4a produced only one diastereomer of the platinum(IV) compound [PtMe₂I{3-(R)-(C₁₀H₇)CHMeNCHC₄H ₂S}PPh₃] (7a). Subsequent isomerization of the resulting platinum(IV) compound gave a new pair of diastereomers in relative amounts 90 and 10%. Analogous proportions of final diastereomers were obtained for the oxidative addition of methyl iodide to the new chiral compounds [PtMe{3-(R)-(C₁₀H₇)CHMeNCHAr}PPh₃] (Ar=C₆H₄ (4b), 2-FC₆H₃ (4c), 2-CF₃C₆H₃ (4d)). The reaction of [Pt₂Me₄(μ-SMe₂)₂] with imines (R)-(C₁₀H₇)CHMeNCH(2-BrC₆H₄) (2e) and (R)-(C₁₀H₇)CHMeNCH(2,6-Cl₂C₆H ₃) (2f) produced intramolecular oxidative addition to yield platinum(IV) compounds with some degree of stereoselectivity.

Full text of DOI:10.1016/S0022-328X(01)01043-9

Journal of Organometallic Chemistry 631 (2001) 164–174
www.elsevier.com/locate/jorganchem
Stereoselective oxidative addition of methyl iodide to chiral
cyclometallated platinum(II) compounds derived from
(R)-(+)-1-(1-naphthylethylamine). Crystal structure of
[PtMe{3-(R)-(C10H7)CHMeNCHC4H2S}PPh3]
Craig Anderson a,b,c,d, Margarita Crespo a,*, Fernande D. Rochon b
a Departament de Qu´ımica Inorga`nica, Facultat de Qu´ımica, Uni6ersitat de Barcelona, Diagonal 647, E-08028 Barcelona, Spain
b De´partement de Chimie, Uni6ersite´ du Que´bec a` Montre´al, P.O. Box 8888, Succ. Centre Ville, Montreal, Canada H3C 3P8
c Bard College, Annandale-on-Hudson, NY 12504, USA
d Orgometa Laboratories, 6254 St Denis, Montreal, Canada H2S 2R7
Received 18 April 2001; accepted 18 May 2001
Abstract
The reaction of 3-(R)-(C10H7)CHMeNCHC4H3S (2a) with [Pt2Me4(m-SMe2)2] in acetone gave the new chiral cyclometallated
platinum(II) compound [PtMe{3-(R)-(C10H7)CHMeNCHC4H2S}SMe2] (3a). Addition of PPh3 produced compound [PtMe{3-(R)-
(C10H7)CHMeNCHC4H2S}PPh3] (4a) which was characterized by X-ray diffraction methods. While oxidative addition of methyl
iodide to 3a gave two pairs of diastereomers, the analogous reaction for 4a produced only one diastereomer of the platinum(IV)
compound [PtMe2I{3-(R)-(C10H7)CHMeNCHC4H2S}PPh3] (7a). Subsequent isomerization of the resulting platinum(IV) com-
pound gave a new pair of diastereomers in relative amounts 90 and 10%. Analogous proportions of final diastereomers were
obtained for the oxidative addition of methyl iodide to the new chiral compounds [PtMe{3-(R)-(C10H7)CHMeNCHAr}PPh3]
(Ar=C6H4 (4b), 2-FC6H3 (4c), 2-CF3C6H3 (4d)). The reaction of [Pt2Me4(m-SMe2)2] with imines (R)-(C10H7)CHMeNCH(2-
BrC6H4) (2e) and (R)-(C10H7)CHMeNCH(2,6-Cl2C6H3) (2f) produced intramolecular oxidative addition to yield platinum(IV)
compounds with some degree of stereoselectivity. © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Platinum; Cyclometallation; Oxidative addition; Stereoselectivity
1. Introduction
ilar study for analogous compounds with ligands
derived from the more sterically demanding (1-naph-
thyl)ethylamine. Naphthalenyl cyclopalladated com-
plexes are frequently superior to benzyl analogues as
resolving agents of phosphines or arsines [7–9], which
has been related to the increased conformational rigid-
ity of the naphthylethylamine derivatives [10,11]. Re-
cently, optically active palladacycles containing imines
derived from 1-(1-naphthyl)ethylamine have been used
to resolve P-chiral ligands [12]. In view of these results,
a high degree of stereoselectivity for the oxidative addi-
tion reaction to platinum(II) complexes containing chi-
ral imines derived from naphthylethylamine could be
anticipated, even if metallation at the naphthyl ring is
not expected.
Oxidative addition reactions involving transition
metals are fundamental steps in stoichiometric and
catalytic processes. Recently, attention has been fo-
cused on the stereoselectivity of oxidative addition of
alkyl halides to chiral square–planar platinum(II) com-
plexes [1–3]. Following our previous results for the
oxidative addition of methyl iodide to platinum(II)
complexes with chiral imines derived from (S)-
phenylethylamine [4–6] we decided to undertake a sim-
* Corresponding author. Tel.: +34-93-4021273; fax: +34-93-
4907725.
E-mail address: margarita.crespo@qi.ub.es (M. Crespo).
0022-328X/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(01)01043-9

C. Anderson et al. / Journal of Organometallic Chemistry 631 (2001) 164–174
165
2. Results and discussion
(C10H7) bond is inhibited by the presence of the bulky
PPh3 in a cis position to the N–Pt bond. As only one
1
Ligands (R)-(C10H7)CHMeNCHAr (2) were pre-
pared by reaction of (R)-(+)-1-(1-naphthyl)ethylamine
with the equimolar amount of the corresponding alde-
set of signals was obtained in the H- and 31P-NMR
spectra, the compound seems to be locked in one
rotamer. It is most likely that the preferred conforma-
tion in solution is the same as the one which was
determined by X-ray diffraction methods (Fig. 1).
Suitable crystals of 4a were obtained as yellow plates
from a dichloromethane solution, which was layered
with hexane. The crystal structure is shown in Fig. 1,
and confirms the expected geometry. No hydrogen
bonds are expected in this type of structure. The
molecules are held together in the crystal only by van
der Waals forces. The methyl ligand is in trans position
to the nitrogen atom, the CꢁN group is endo to the
cycle and the stereochemistry of the asymmetric carbon
is R. The imine adopts an (E)-configuration, the torsion
angle C(7)ꢀNꢀC(6)ꢀC(3) being −175.1(4)°. The plat-
inum atom displays a slightly tetrahedral distorted pla-
1
hyde in refluxing ethanol and characterized by H- and
13C-NMR spectroscopies.
2.1. Oxidati6e addition of methyl iodide to chiral
cyclometallated platinum(II) compounds [PtMe{3-(R)-
(C10H7)CHMeNCHC4H2S}L] (L=SMe2 (3a), PPh3
(4a))
The reaction of 3-(R)-(C10H7)CHMeNCHC4H3S (2a)
with [Pt2Me4(m-SMe2)2] in acetone gave [PtMe{3-(R)-
(C10H7)CHMeNCHC4H2S}SMe2] (3a), which was char-
acterized by 1H- and 13C-NMR spectroscopies and
elemental analysis. Data are consistent with the pro-
posed formula in which the imine acts as a [C,N] donor
ligand and the coordination sphere of the platinum(II)
is completed with a methyl group and a SMe2 ligand.
As reported for related ligands PhCH2NCHC4H3S [13]
and PhCHMeNCHC4H3S [6], metallation took place,
along with methane formation, at the thiophene ring to
yield an endo-metallacycle (containing the imine func-
tionality) and not at the naphthyl group which would
give an exo-metallacycle containing the chiral carbon.
Addition of PPh3 to 3a in acetone produced the
,
nar coordination and the following displacements (A)
are observed from the least-squares plane of the coordi-
nation sphere: Pt, 0.009(2); P, 0.054(2); N, −0.067(3);
C(1), −0.073(3); C(2), 0.077(3). The metallacycle is
approximately planar (mean deviation 0.011(3) A) and
the largest deviation from the mean plane determined
,
,
by the five atoms is 0.017(3) A for C(3). It is nearly
coplanar with the coordination plane, the dihedral an-
gle being 3.5(3)°. The bond distances and angles are
listed in Table 1. These values are in the usual range for
analogous compounds [6,13,14]. The angles between
adjacent atoms in the coordination sphere of platinum
lie in the range 77.5(2)–106.0(1)°, the smallest angle
corresponding to the metallacycle and the largest to the
NꢀPtꢀP angle. The latter is much larger (106.0(1)°) than
for the analogous compound [PtMe{3-(PhCH2NCH)-
C4H2S}PPh3] (98.0(2)°) [13], which indicates a much
more congested molecule due to the presence of the
bulky naphthyl group. In order to minimize the steric
hindrance in the coordination sphere of platinum, the
naphthyl lies away from the triphenylphosphine ligand.
Oxidative addition of methyl iodide to chiral platinu-
m(II) compound 3a was monitored by 1H-NMR in
acetone. Four isomers of the expected cyclometallated
platinum(IV) compound were detected in the NMR
from the early stages of the reaction and their ratio
remained constant over several days in solution.
The reaction was also carried out in a preparative
scale and gave a light yellow solid for which the ele-
mental analysis was consistent with the formulation
[PtMe2I{3-(R)-(C10H7)CHMeNCHC4H2S}SMe2]. The
1H-NMR spectra showed the presence of the four
isomers in the same relative amounts as in the NMR
experiment.
cyclometallated
compound
[PtMe{3-(R)-(C10H7)-
CHMeNCHC4H2S}PPh3] (4a), in which the phosphine
ligand replaced the dimethylsulfide. This compound
1
was characterized by H- and 31P-NMR spectroscopies,
elemental analysis, mass spectroscopy and crystallogra-
phy. The relatively high value for the coupling constant
J(P–Pt) indicates that the PPh3 ligand is trans to the
thienyl group [13]. Manipulation with molecular models
indicates that free rotation around the NꢀCHMe-
From the 2J(1H–195Pt) coupling constants for the
methyl groups, a fac-PtC3 structure is assigned to all
isomers. In agreement with previous studies, the reso-
Fig. 1. View of compound [PtMe{3-(R)-(C10H7)CHMeNCHC4-
H2S}PPh3] (4a) with the thermal ellipsoids represented at the 30%
probability level.

166
C. Anderson et al. / Journal of Organometallic Chemistry 631 (2001) 164–174
Table 1
stereoselectivity in the initial trans oxidative addition—
although subsequent isomerization yields nearly equal
amounts of diastereomers 6a—and (ii) a higher degree
of the isomerization from 5a to 6a.
,
Selected bond lengths (A) and angles (°)
Bond lengths
PtꢀC(2)
PtꢀN
PꢀC(41)
PꢀC(31)
SꢀC(5)
NꢀC(7)
C(3)ꢀC(4)
C(4)ꢀC(5)
C(7)ꢀC(11)
C(11)ꢀC(20)
C(13)ꢀC(14)
C(15)ꢀC(16)
C(16)ꢀC(17)
C(18)ꢀC(19)
2.008(5)
2.197(4)
1.828(4)
1.838(6)
1.714(6)
1.476(6)
1.418(7)
1.380(9)
1.539(7)
1.431(8)
1.344(10)
1.414(9)
1.339(12)
1.364(9)
PtꢀC(1)
PtꢀP
PꢀC(21)
SꢀC(2)
2.078(6)
2.2949(13)
1.831(6)
1.703(6)
1.293(6)
1.392(8)
1.454(7)
1.531(7)
1.361(8)
1.412(10)
1.417(10)
1.434(8)
1.429(11)
1.419(8)
Oxidative addition of methyl iodide to chiral cy-
1
clometallated compound 4a was monitored by H- and
31P-NMR in acetone and the products are depicted in
Chart 1. In the early stages of the reaction only one
isomer was detected (7a; 100% stereoselectivity). NMR
parameters are consistent with the cyclometallated plat-
inum(IV) compound [PtMe2I{3-(R)-(C10H7)CHMe-
NCHC4H2S}PPh3] (7a) in which the axial methyl group
is trans to iodine and the PPh3 ligand is trans to the
thienyl group (J(PPt)=1577 Hz). This consists of one
single diastereomer but it is not possible to assign the
absolute stereochemistry (C or A) at the octahedral
platinum centre. As the reaction proceeded, new signals
appeared and fully replaced the former ones within 18
h. The 31P-NMR spectra reveals clearly the presence of
a major resonance at l= −12.08 ppm (J(P–Pt)=970
Hz) together with a much lower intensity signal (less
than 15%) at l= −6.05 ppm (J(P–Pt)=985 Hz).
These were assigned according to the J(P–Pt) values to
a pair of diastereomers (APt, RC) and (CPt, RC) with the
stereochemistry depicted in Chart 1 for 8a. In the
1H-NMR spectrum, only the resonances due to the
major diastereomer of 8a (ca. 90%) could be unambigu-
ously assigned and the reduced coupling constant of the
axial methyl to platinum (2J(H–Pt)=60 Hz) confirm a
trans arrangement of the axial methyl with the PPh3.
The reaction was also carried out in a preparative
scale and gave a light yellow solid for which the ele-
mental analysis was consistent with the formulation
NꢀC(6)
C(2)ꢀC(3)
C(3)ꢀC(6)
C(7)ꢀC(8)
C(11)ꢀC(12)
C(12)ꢀC(13)
C(14)ꢀC(15)
C(15)ꢀC(20)
C(17)ꢀC(18)
C(19)ꢀC(20)
Bond angles
C(2)ꢀPtꢀC(1)
C(1)ꢀPtꢀN
90.4(3)
167.0(2)
86.3(2)
103.8(2)
102.4(2)
120.2(2)
95.1(3)
112.5(3)
107.3(4)
134.7(4)
113.8(4)
110.7(6)
118.5(5)
114.3(4)
C(2)ꢀPtꢀN
C(2)ꢀPtꢀP
NꢀPtꢀP
C(41)ꢀPꢀC(31)
C(41)ꢀPꢀPt
C(31)ꢀPꢀPt
C(6)ꢀNꢀC(7)
C(7)ꢀNꢀPt
C(3)ꢀC(2)ꢀPt
C(2)ꢀC(3)ꢀC(4)
C(4)ꢀC(3)ꢀC(6)
C(4)ꢀC(5)ꢀS
NꢀC(7)ꢀC(8)
C(8)ꢀC(7)ꢀC(11)
77.5(2)
175.4(2)
105.99(11)
105.4(3)
112.5(2)
111.1(2)
119.9(4)
127.3(3)
117.6(4)
116.3(5)
129.8(5)
110.6(4)
107.7(4)
112.9(5)
C(1)ꢀPtꢀP
C(41)ꢀPꢀC(21)
C(21)ꢀPꢀC(31)
C(21)ꢀPꢀPt
C(2)ꢀSꢀC(5)
C(6)ꢀNꢀPt
C(3)ꢀC(2)ꢀS
SꢀC(2)ꢀPt
C(2)ꢀC(3)ꢀC(6)
C(5)ꢀC(4)ꢀC(3)
NꢀC(6)ꢀC(3)
NꢀC(7)ꢀC(11)
nances at lower l correspond to axial methyl groups
trans to iodide and were assigned to a pair of
diastereomers (CPt, RC) and (APt, RC) (5a in Chart 1)
arising from trans oxidative addition of methyl iodide
to the platinum(II) centre. Their relative amounts (16.4
and 5.5%) could be deduced from averaged integration
of the identified signals in NMR, although specific
resonances could not be assigned individually to each
diastereomer. The two more abundant isomers (39.9
and 38.2%) consist of a new pair of diastereomers (APt,
RC) and (CPt, RC) (6a in Chart 1) apparently arising
from cis oxidative addition.
[PtMe2I{3-(R)-(C10H7)CHMeNCHC4H2S}PPh3]
and
1
the H- and 31P-NMR spectra showed the presence of
the two diastereoisomers of compound 8a in relative
amounts ca. 90 and 10%.
The reaction of racemic [PtMe{3-((9)-(C10H7)-
CHMeNCHC4H2S}PPh3] (4a%) with methyl iodide was
also studied by NMR and results were identical to
those obtained for chiral compound 4a.
The reaction of racemic [PtMe{3-(9)-(C10H7)-
CHMeNCHC4H2S}SMe2] (3a%) with methyl iodide was
also monitored by H-NMR. Again, four sets of reso-
2.2. Oxidati6e addition of methyl iodide to chiral
cyclometallated platinum(II) compounds
1
nances in the same ratio as for chiral compound 3a
were observed and assigned to the two pairs of
diastereoisomers, each with its enantiomer.
[PtMe{3-(R)-(C10H7)CHMeNCHAr}PPh3] (Ar=C6H4
(4b), 2-FC6H3 (4c), 2-CF3C6H3 (4d))
It is generally accepted that the oxidative addition of
alkyl halides to platinum(II) compounds gives trans
stereochemistry and compounds with cis stereochem-
istry may be formed in a subsequent isomerization
process [15,16]. A comparison with the results obtained
for the analogous compound [PtMe{3-(S)-(PhCH-
MeNCH)C4H2S}SMe2] indicates for the more sterically
demanding naphthyl group: (i) a higher degree of
In order to compare the results obtained for the
thienyl system with those for other aromatic systems as
well as to study the effect of substituents in the aryl
ring, we prepared new chiral cyclometallated platinu-
m(II) derived from the imines (R)-(C10H7)-
CHMeNCHC6H5 (2b), (R)-(C10H7)CHMeNCH(2-
FC6H4) (2c) and (R)-(C10H7)CHMeNCH(2-CF3C6H4)
(2d).

C. Anderson et al. / Journal of Organometallic Chemistry 631 (2001) 164–174
167

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C. Anderson et al. / Journal of Organometallic Chemistry 631 (2001) 164–174
169
The reactions of 2a–2d with [Pt2Me4(m-SMe2)2] were
carried out in acetone. As reported for analogous lig-
ands [17,18], activation of a C(Ar)–H bond at the
phenyl ring followed by methane elimination gave chi-
ral cyclometallated platinum(II) compounds [PtMe{3-
(R)-(C10H7)CHMeNCHAr}SMe2] (Ar=C6H4 (3b),
2-FC6H3 (3c), 2-CF3C6H3 (3d)) containing a dangling
naphthalenyl group. Addition of PPh3 to compounds
3b–3d in acetone produced the corresponding cy-
electron-withdrawing ability of fluoro- or trifl-
uoromethyl groups, the oxidative addition to the platin-
um(II) centre is less favoured, which leads to some
degree of decomposition, which includes formation of
phosphonium salt and metallic platinum. Nevertheless,
the same ratio of the isomers was obtained for all the
groups under study, which can be related to the fact
that the substituents of the aryl ring lie in the plane of
the metallacycle and are not sterically significant.
From their relative integrated intensities, each set of
signals in the NMR spectra could be assigned to an
individual isomer although it is not possible to assign
the absolute configurations. Both 2J(H–Pt) for the
axial methyl and J(P–Pt) values are consistent with a
trans arrangement of the axial methyl with the PPh3
ligand. As shown in Table 2, for all compounds under
study both the axial methyl group (Meb) and the methyl
group bound to the chiral carbon atom (Mec) are
shifted upfield for the major diastereoisomer when com-
pared to the minor diastereoisomer. An increase in
J(PPt) value is also observed for the minor isomer in all
cases. The consistency of NMR data suggest that the
major and minor isomer adopt the same conformation
for all the compounds.
clometallated
compounds
[PtMe{3-(R)-(C10H7)-
CHMeNCHAr}PPh3] (Ar=C6H4 (4b), 2-FC6H3 (4c),
2-CF3C6H3 (4d)). Compounds 3 and 4 were character-
ized by NMR spectroscopies and elemental analysis.
Data are consistent with the proposed formulae shown
in Chart 2 in which the imine acts as a [C,N] donor
ligand and the coordination sphere of the platinum(II)
is completed with a methyl group and either a SMe2
(compounds 3) or a PPh3 (compounds 4) ligand.
Oxidative addition of methyl iodide to chiral com-
pounds 4b–4d was carried out in acetone and the
obtained products 8b–8d are depicted in Chart 2. When
the reactions were monitored by 1H- and 31P-NMR
spectroscopies, the presence of two platinum(IV)
diastereomers, formally arising from cis-oxidative addi-
tion of the methyl iodide was observed from the early
stages of the reaction. Their relative amounts (85 and
15%) remained constant. According to previous studies
[6,13], it might be assumed that the oxidative addition
gives trans stereochemistry and is followed by a very
fast isomerization process. Since the final proportion of
isomers is similar to that obtained for 4a we might
suggest that the initial trans oxidative addition should
also be highly stereoselective for the phenyl systems.
The oxidative addition of methyl iodide to 4c and 4d
took place along with formation of a small (4c) to fair
(4d) amount of [PPh3Me]I, which could be easily de-
tected by NMR [19] and prevents the possibility of
obtaining good elemental analyses for 8d. Due to the
2.3. Intramolecular oxidati6e addition of C(aryl)ꢀX
bonds of chiral imines
In order to compare the stereochemistry of intra-
versus intermolecular oxidative addition reactions we
extended our studies to chiral imines (R)-(C10H7)-
CHMeNCH(2-BrC6H4)
(2e)
and
(R)-(C10H7)-
CHMeNCH(2,6-Cl2C6H3) (2f). There have been several
reports of the intramolecular oxidative addition of
arylꢀhalogen bonds to a platinum substrate, and re-
cently the stereochemistry of such reactions has been
addressed [20].
Table 2
Selected 1H- and 31P-NMR data for compounds 8 a
l(Me a) [2J(HPt)]
l(Me b) [2J(HPt)]
l (Me )
l(CHN) [3J(HPt)]
l(P) [J(PPt)]
8a major
8a minor b
8b major
8b minor
8c major
8c minor
8d major
8d minor
8e major
8e minor
8f major
8f minor
1.65 (69)
1.10 (60)
0.91
8.23 (46)
−12.08 (970)
−6.05 (985)
−9.39 (982)
−3.95 (1011)
−9.85 (984)
−4.11 (1007)
−11.13 (982)
−4.63 (1013)
−6.53 (976)
−2.55 (1006)
−5.25 (926)
−1.36 (975)
1.44 (71)
1.40 (70)
1.46 (70)
1.44 (70)
1.49 (70)
1.48 (70)
1.30 (70)
1.34 (70)
1.25 (69)
1.35 (70)
0.99 (62)
1.42 (60)
1.00 (61)
1.42 (60)
0.97 (61)
1.40 (60)
0.76 (60)
1.21 (60)
0.64 (60)
1.12 (60)
0.99
1.90
1.10
1.97
1.11
1.71
1.00
2.02
1.14
2.22
8.97 (49)
8.86 (49)
9.06 (48)
8.87 (48)
9.01(49)
8.82 (48)
8.95 (49)
8.50 (48)
9.13 (50)
9.08 (50)
a l in parts per million, J in Hertz, in acetone-d6.
b 1H-NMR data not assigned for the minor isomer.

170
C. Anderson et al. / Journal of Organometallic Chemistry 631 (2001) 164–174
Chart 3.
3. Conclusions
In agreement with previous results [17,18], the reac-
tion of ligands 2e and 2f with [Pt2Me4(m-SMe2)2] is
expected to produce intramolecular oxidative addition
of CꢀBr and CꢀCl bonds, respectively, to yield platin-
um(IV) compounds containing a chelate [C,N] ligand.
The reactions were carried out in acetone and subse-
quent addition of PPh3 produced platinum(IV) com-
A high degree of stereoselectivity has previously
been reported in the oxidative addition of alkyl halides
to [PtMe{1-(NꢁCHC6H4)-2-(NꢁCHC6H5)C6H10}] in
which a locked conformation results from the presence
of a [N,N,C] donor tridentate system [2]. For com-
pound 4a, containing a bidentate [C,N] chelate system
and a chiral carbon in a dangling group, 100%
stereoselectivity has been observed in the initial trans
oxidative addition of methyl iodide. This result can be
related to the locked conformation resulting from
steric hindrance between the bulky PPh3 ligand and
the naphthyl group, which hinders the approach of
CH3I to one side of the platinum(II) substrate. Subse-
quent isomerization of the resulting platinum(IV) com-
pound places the triphenylphosphine in an axial
position in order to minimize steric effects, thus some
loss of diastereoselectivity occurs, along with the re-
duction of steric congestion at the metal centre. This
yields a pair of diastereomers in relative amounts 90
and 10%. Since similar proportions (85 and 15%) of
final diastereomers were obtained for the phenyl
derivatives 4b–4d, the oxidative addition of methyl
iodide to these systems probably follows the same
path. The lower trans influence of the thienyl when
compared to the phenyl group [13] slows down the
isomerization step and a clearer picture of the inter-
molecular oxidative addition is obtained for 4a. The
close relationship of the stereoselectivity with the rela-
tive steric hindrance of the studied systems is evi-
denced by the lower stereoselectivity obtained when
smaller ligands such as SMe2 (5a/6a) or chlorine
(8f) are present in the platinum(IV) coordination
sphere.
pounds
[PtMe2Br{3-(R)-(C10H7)CHMeNCHC6H4}-
PPh3] (8e) and [PtMe2Cl{3-(R)-(C10H7)CHMeNCH-
(C6H3Cl}PPh3] (8f), which were characterized by
NMR spectroscopies and elemental analyses.
A pair of diastereomers (APt, RC) and (CPt, RC)
with a fac-PtC3 geometry are possible and as evi-
denced from NMR, the relative amounts of the two
diastereomers are 85 and 15% for 8e and 60 and 40%
for 8f. The NMR data are fully consistent with those
obtained for compounds 8a–8d and upfield shifts of
the axial methyl–platinum (Meb) and the methyl sub-
stituent of the chiral carbon (Mec) are observed for
the major isomer. Therefore, the stereochemistries de-
picted in Chart 3 formally arising from trans oxidative
addition of the C(aryl)ꢀhalogen bond can be assigned
to 8e and 8f. It is not evident however if trans in-
tramolecular oxidative addition takes place or if cis
addition is followed by isomerization of either the
resulting
platinum(IV)
compounds
or
the
triphenylphosphine derivatives.
The bromo derivative proportions of the final
diastereomers are similar to those observed for the
intermolecular oxidative addition. It seems likely that
the smaller size of the chlorine atom when compared
to bromine or iodine atoms is responsible for
the lower stereoselectivity observed in the formation of
8f.

C. Anderson et al. / Journal of Organometallic Chemistry 631 (2001) 164–174
171
4. Experimental
(282.26 MHz, CDCl3): l= −166.72 [m]. 2d: Ar=2-
CF3C6H4. Yield 0.7 g (76%). 1H-NMR (200 MHz,
CDCl3): l=1.75 [d, J(Ha–Hb)=7, Ha]; 5.42 [q, J(Ha–
Hb)=7, Hb]; {7.22 [m, 2H]; 7.44–7.64 [m, 5H]; 7.82 [m,
2H]; 8.25 [d, J(H–H)=7, 1H]; 8.34 [d, J(H–H)=7,
1H], aromatics}; 8.83 [d, J(H–H)=2, Hc]. 2e: Ar=2-
BrC6H4. Yield 0.8 g (81%). 1H-NMR (200 MHz,
CDCl3): l=1.75 [d, J(Ha–Hb)=6.6, Ha]; 5.42 [q,
J(Ha–Hb)=6.6, Hb]; {7.20–7.57 [m, 6H]; 7.75–7.90
[m, 3H]; 8.17 [dd, J(HH)=8;2, 1H]; 8.27 [d, J(HH)=
8, 1H], aromatics}; 8.83 [s, Hc]. 13C-NMR (50.28,
CDCl3): l=24.64 [Cb]; 65.83 [Ca]; {123.45, 123.82,
125.29, 125.60, 125.79, 127.34, 127.51, 128.88, 128.98,
131.67, 132.88, [125.03, 127.60, 130.49, 133.91, 134.72,
Cf,l,m,n], aromatics}; 158.71 [Cc].
4.1. Instrumentation
1H-, 13C-{1H}-, 31P-{1H}- and 19F-NMR spectra were
recorded using Varian Gemini 200 (1H, 200 MHz; 13C,
50.28), Varian Unity 300 (13C, 75.43 MHz; 19F, 282.26),
Varian 500 (1H, 500 MHz) and Bruker 250 (31P, 101.25
MHz) spectrometers, and referenced to SiMe4 (1H, 13C),
H3PO4 (31P) and CF3COOH (19F). l Values are given in
ppm and J values in Hz. Microanalyses and FABMS
were performed by the Serveis Cient´ıfico-Te`cnics de la
Universitat de Barcelona.
4.2. Preparation of compounds
1
2f: Ar=2,6-C6H3Cl2. Yield 0.75 g (78%). H-NMR
Compound [Pt2Me4(m-SMe2)2] (1) was prepared as
(200 MHz, CDCl3): l=1.80 [d, J(HaHb)=7, Ha]; 5.51
[q, J(HaHb)=7, Hb]; {7.19–7.35 [m, 3H]; 7.45–7.57 [m,
3H]; 7.62–7.91 [m, 3H]; 8.22 [d, J(HH)=7, 1H], aro-
matics}; 8.56 [s, Hc]. 13C-NMR (50.28, CDCl3): l=
24.21 [Cb]; 66.19 [Ca]; {123.55, 124.17, 125.31, 125.61,
125.81, 127.49, 128.51[Ch], 128.85, 130.14, [130.58,
133.16, 133.87, 134.60, 139.68, Cf,g,j,k,l], aromatics};
155.85 [Cc].
reported [21].
4.2.1. Synthetic procedure for compounds 2
The compounds (R)-(C10H7)CHMeNCHAr (2) were
prepared by the reaction of 0.5 g (2.92 mmol) of
(R)-(+)-1-(1-naphthyl)ethylamine with the equimolar
amount of the corresponding aldehyde (2a, 0.327 g; 2b,
0.310 g; 2c, 0.362 g; 2d, 0.508 g; 2e, 0.540 g; 2f, 0.511 g)
in refluxing EtOH (20 ml). After 4 h, the solvent was
removed in a rotary evaporator to yield white solids.
Racemic (C10H7)CHMeNCHC4H3S (2a%) was prepared
by an analogous procedure from (9)-1-(1-naph-
thyl)ethylamine. 2a: Ar=C4H3S. Yield 0.65 g (84%).
1H-NMR (200 MHz, CDCl3): l=1.73 [d, J(HaHb)=
6.8, Ha]; 5.30 [q, J(Ha–Hb)=6.8, Hb]; {7.31 [dd, J(H–
H)=5; 3, 2H]; 7.44–7.65 [m, 4H]; 7.74–7.90 [m, 3H];
8.20 [d, J(H–H)=8, 1H], aromatics}; 8.41 [s, Hc].
13C-NMR (50.28, CDCl3): l=24.43 [Cb]; 65.33 [Ca];
{123.55, 123.96, 125.25, 125.60, 125.74, 125.93, 126.19,
127.28, 128.28, 128.85, [130.59, 133.90, 140.73, 140.93,
Cf,l,m,n]; aromatics}; 153.92[Cc].
4.2.2. Synthetic procedure for the compounds 3a–3d
Compounds [PtMe{(R)-(C10H7)CHMeNCHR}SMe2]
(3) were obtained by adding a solution of 3.5×10−4
mol of the corresponding imine (2a, 93 mg; 2b, 91 mg;
2c, 97 mg; 2d, 114 mg) in acetone (10 ml) to a solution
of 100 mg (1.74×10−4 mol) of compound [Pt2Me4(m-
SMe2)2] in acetone (10 ml). The mixture was stirred for
3 h (3a) or 16 h (3b–3d) at room temperature (r.t.) and
the acetone was removed in a rotary evaporator. The
residue was washed with hexane and dried in vacuum
to yield orange (3a) or yellow (3b–3d) solids. Racemic
[PtMe{(C10H7)CHMeNCHC4H2S}SMe2] (3a%) was pre-
pared in an analogous way from racemic 2a%. 3a: R=
C4H2S. Yield 140 mg (75%). 1H-NMR (200 MHz,
2b: Ar=C6H5. Yield 0.6 g (79%). 1H-NMR (200
MHz, CDCl3): l=1.74 [d, J(Ha–Hb)=6.6, Ha]; 5.36
[q, J(Ha–Hb)=6.6, Hb]; {7.15–7.29 [m, 3H]; 7.39–7.54
[m, 4H]; 7.74–7.89[m, 4H]; 8.25 [d, J(H–H)=8, 1H],
aromatics}; 8.42 [s, Hc]. 13C-NMR (50.28, CDCl3):
l=24.55 [Cb]; 65.54 [Ca]; {123.52, 123.94, 125.23,
125.60, 125.72, 127.24, 128.14, [128.19, 128.46, Cg,h],
128.85, 130.52, [128.96, 133.88, 136.37, 141.03, Cf,l,m,n],
aromatics}; 159.55 [Cc]. 2c: Ar=2-FC6H4. Yield 0.7 g
(86%). 1H-NMR (200 MHz, CDCl3): l=1.74 [d,
J(Ha–Hb)=7, Ha]; 5.39 [q, J(Ha–Hb)=7, Hb]; {7.01–
7.23 [m, 2H]; 7.34–7.58 [m, 4H]; 7.74–7.90 [m, 3H];
8.15 [m, 1H]; 8.26[d, J(H–H)=8, 1H], aromatics}; 8.77
[s, Hc]. 13C-NMR (50.28, CDCl3): l=24.62 [Cb]; 66.11
[Ca]; {115.60 [d, J(CF)=21, Ch]; 123.45, 123.86, 124.21
[d, J(HF)=4, Ci], 125.26, 125.59, 125.76, 127.31,
127.85 [d, J(CF)=3, Cj], 128.85, 130.47, 132.06,
133.90, 140.88, aromatics}; 152.91 [Cc]. 19F-NMR
2
acetone-d6): l=1.12 [s, J(Pt–H)=78, Mea]; 1.79 [d,
3
J(Hc–Hd)=7, Hc]; 1.95 [s, J(Hb–Pt)=30, Hb]; 6.02
[q, J(Hc–Hd)=7, Hd]; {7.19 [m, 2H]; 7.49 [m, 4H], 7.85
[m, 2H], 8.06 [d, J(H–H)=8, 1H], aromatics}; 8.39 [s,
3J(Pt–He)=54, He]. 13C-NMR (75.43, CDCl3): l= −
21.25 [J(CPt)=888, Ca]; 18.91 [Cb]; 20.02 [Cc]; 58.53
[Cd]; {129.16, 130.97, 134.06, 138.44, 148.47, Cf,g,l,m,n};
{123.21, 123.83, 124.07, 125.14, 125.39, 125.57, 126.32,
127.96, 128.67, aromatics}; 163.57 [J(CPt)=71, Ce].
Anal. Found: C, 44.6; H, 4.4; N, 2.6. Calc. for
C20H23NPtS2: C, 44.77; H, 4.32; N, 2.61%. 3b: R=
1
C6H4. Yield 140 mg (76%). H-NMR (200 MHz, ace-
tone-d6): l=0.91 [s, 2J(Pt–H)=83, Mea]; 1.80 [d,
3
J(Hc–Hd)=7, Hc]; 2.04 [s, J(Hb–Pt)=26, Hb]; 6.21
[q, J(Hc–Hd)=7, Hd]; {6.92 [td, J(H–H)=6;1, 1H];
7.14 [td, J(H–H)=8;1, 1H], 7.29–7.32 [m, 1H], 7.44–
7.62 [m, 4H], 7.86–7.96 [m, 3H], 8.19 [d, J(H–H)=9,

172
C. Anderson et al. / Journal of Organometallic Chemistry 631 (2001) 164–174
1H], aromatics}; 8.62 [s, 3J(Pt–He)=57, He]. 13C-
NMR (75.43, acetone-d6): l= −14.65 [Ca]; 18.67 [Cb];
19.95 [Cc]; 58.76 [J(CPt)=21, Cd]; 127.82 [J(CPt)=38,
Ci]; 122.51 [Ch]; 130.01 [J(CPt)=72, Cj]; 131.43
[J(CPt)=100, Ck]; {134.11, 138.05, Cf,g}; {123.85,
124.24, 125.14, 125.62, 126.36, 128.12, 128.69,
Co,p,q,r,s,t,u}; {148.86, 156.10, Cl,m,n}; 171.91 [J(CPt)=
83, Ce]. Anal. Found: C, 49.7; H, 4.8; N, 2.6. Calc. for
C22H25NPtS: C, 49.80; H, 4.75; N, 2.64%. 3c: R=2-
FC6H3. Yield 150 mg (78%). 1H-NMR (200 MHz,
7.47 [m, 15H], 7.88–7.92 [m, 9H], aromatics}; 8.32 [s,
3J(Pt–He)=59, He]. 31P-NMR (101.25 MHz, acetone-
d6): l=33.50 [s, 1J(P–Pt)=2149]. Anal. Found: C,
62.5; H, 4.6; N, 1.8. Calc. for C38H34NPPt: C, 62.46; H,
4.69; N, 1.92%. 4c: R=2-FC6H3. Yield 52 mg (76%).
1H-NMR (200 MHz, acetone-d6): l=0.73 [d, 3J(P–
H)=7, 2J(Pt–H)=82, Mea]; 1.34 [d, J(Hc–Hd)=7,
Hc]; 4.89 [q, J(Hc–Hd)=7, Hd]; {6.62 [dd, J(H–F)=
10; J(H–H)=9, 1H]; 7.35–7.49 [m, 15H], 7.83–7.98
3
[m, 9H], aromatics}; 8.56 [s, J(Pt–He)=59, He]. 19F-
2
acetone-d6): l=0.95 [s, J(Pt–H)=83, Mea]; 1.84 [d,
NMR (282.26 MHz, CDCl3): l= −157.55 [dt, J(F–
Pt)=46, J(F–P)=8, J(F–H)=8; 6]. 31P-NMR
(101.25 MHz, acetone-d6): l=32.95 [d, J(P–F)=8,
1J(P–Pt)=2213]. Anal. Found: C, 61.3; H, 4.6; N, 1.9.
Calc. for C38H33FNPPt: C, 60.96; H, 4.44; N, 1.87%.
3
J(Hc–Hd)=7, Hc]; 2.08 [s, J(Hb–Pt)=28, Hb]; 6.29
[q, J(Hc–Hd)=7, Hd]; {6.64 [dd, J(H–F)=10; J(H–
H)=8, 1H]; 7.21–7.42 [m, 3H], 7.51–7.63 [m, 3H], 7.93
[m, 2H], 8.18 [d, J(H–H)=8, 1H], aromatics}; 8.85 [s,
3J(Pt–He)=58, He]. 19F-NMR (282.26 MHz, CDCl3):
l= −157.23 [dd, J(F–Pt)=59.3, J(F–H)=11; 6].
FABMS (NBA): 533 [M−CH3], 470 [M−CH3–
SMe2]. Anal. Found: C, 48.6; H, 4.5; N, 2.5. Calc. for
C22H24FNPtS: C, 48.17; H, 4.41; N, 2.55%. 3d: R=2-
1
4d: R=2-CF3C6H3. Yield 53 mg (80%). H-NMR (200
MHz, acetone-d6): l=0.75 [d, 3J(P–H)=7, 2J(Pt–
H)=82, Mea]; 1.35 [d, J(Hc–Hd)=7, Hc]; 4.95 [q,
J(Hc–Hd)=7, Hd]; {7.26 [d, J=7; 4; 1, 1H]; 7.35–7.50
[m, 15H], 7.83–7.97 [m, 9H], aromatics}; 8.62 [s, 3J(Pt–
He)=59, He]. 31P-NMR (101.25 MHz, acetone-d6): l=
1
CF3C6H3. Yield 160 mg (77%). H-NMR (200 MHz,
CDCl3): l=1.01 [s, 2J(Pt–H)=80, Mea]; 1.83 [d,
32.66 [s, J(P–Pt)=2214]. Anal. Found: C, 58.5; H,
1
3
J(Hc–Hd)=6, Hc]; 1.88 [s, J(Hb–Pt)=24, Hb]; 6.15
4.0; N, 1.5. Calc. for C39H33F3NPPt: C, 58.64; H, 4.16;
N, 1.75%.
[q, J(Hc–Hd)=6, Hd]; {7.35 [m, 3H]; 7.45 [t, J(H–
H)=8, 1H]; 7.55 [td, J(H–H)=8; 2, 3H]; 7.81 [d,
J(H–H)=8, 1H]; 7.89 [d, J(H–H)=10, 1H]; 7.98 [m,
1H]; 8.08 [d, J(H–H)=8, 1H], aromatics}; 8.85 [s,
3J(Pt–He)=58, He]. Anal. Found: C, 46.2; H, 4.1; N,
2.3. Calc. for C23H24F3NPtS: C, 46.15; H, 4.04; N,
2.34%.
4.2.4. Synthetic procedure for the intermolecular
oxidati6e addition reactions
Compounds 5a/6a were obtained from the reaction
of 50 mg (0.93×10−4 mol) of 3a with an excess of
methyl iodide (0.1 ml) in acetone (10 ml). The mixture
was stirred for 4 h at r.t., and the solvent was removed
4.2.3. Synthetic procedure for the compounds 4a–4d
Compounds [PtMe{(C10H7)CHMeNCHR}PPh3] (4)
were obtained by the reaction of 50 mg (3a: 0.93×
10−4 mol; 3b: 0.94×10−4 mol; 3c: 0.91×10−4 mol;
3d: 0.83×10−4 mol) of the corresponding compound 3
with 25 mg (0.95×10−4 mol) of PPh3 in acetone (20
ml). After continuous stirring at r.t. during 3 h, the
solvent was removed in a rotary evaporator and the
resulting yellow solid was filtered, washed with hexane
and Et2O and dried in vacuum. Racemic
[PtMe{(C10H7)CHMeNCHC4H2S}PPh3] (4a%) was pre-
pared in an analogous way from racemic 3a%. 4a: R=
C4H2S. Yield 48 mg (70%). 1H-NMR (200 MHz,
acetone-d6): l=0.93 [d, 3J(P–H)=8, 2J(Pt–H)=80,
Mea]; 1.29 [d, J(Hc–Hd)=7, Hc]; 4.75 [q, J(Hc–Hd)=
7, Hd]; {7.09–7.20 [m, 1H]; 7.35–7.45 [m, 15H], 7.70–
under vacuum to yield
a
light yellow solid.
[PtMe2I{(C10H7)CHMeNCHC4H2S}SMe2]
(5a/6a).
1
Yield 48 mg (76%). H-NMR (500 MHz, acetone-d6):
5a: Major isomer: l=0.71 [s, 2J(Pt–H)=68, Meb];
2
1.41 [s, J(Pt–H)=68, Mea]; 1.88 [d, J(H–H)=7, Hc];
6.59 [q, J(H–H)=7, Hd]; 8.74 [s, J(Pt–H)=40, He].
3
Minor isomer: l=0.87 [s, 2J(Pt–H)=68, Meb]; 1.63 [s,
2J(Pt–H)=68, Mea]. 6a: Major isomer: l=1.44 [s,
2J(Pt–H)=70, Meb]; 1.68 [s, 2J(Pt–H)=68, Mea]; 1.93
[d, J(H–H)=6.5, Hc]; 6.79 [q, J(H–H)=7, Hd]; 8.16
[s, 3J(Pt–H)=45, He]. Minor isomer: l=1.40 [s,
2J(Pt–H)=70, Meb]; 1.68 [s, 2J(Pt–H)=68, Mea]; 1.93
[d, J(H–H)=6.5, Hc]; 6.94 [q, J(H–H)=7, Hd]; 8.05
[s, 3J(Pt–H)=43, He]. Anal. Found: C, 37.3; H, 3.9; N,
1.9. Calc. for C21H26INPtS2: C, 37.17; H, 3.86; N,
2.06%.
3
7.86 [m, 8H], aromatics}; 8.14 [s, J(Pt–He)=55, He].
Compounds
[PtMe2I{(C10H7)CHMeNCHR}PPh3]
31P-NMR (101.25 MHz, acetone-d6): l=30.01 [s,
1J(P–Pt)=2589]. FABMS (NBA): 737 [M], 721 [M−
CH3]. Anal. Found: C, 58.6; H, 4.4; N, 1.9. Calc. for
C36H32NPPtS: C, 58.69; H, 4.38; N, 1.90%. 4b: R=
(8) were obtained in an analogous way from com-
pounds 4. 8c and 8d were washed with tiny amounts of
water prior to be dried under vacuum. 8a: R=C4H2S.
1
Yield 45 mg (75%). H-NMR (500 MHz, acetone-d6):
1
C6H4. Yield 50 mg (73%). H-NMR (200 MHz, ace-
Major isomer: l=0.91 [d, J(H–H)=7, Hc]; 1.10 [d,
3J(H–P)=7.6, 2J(Pt–H)=60, Meb]; 1.65 [d, 3J(H–
P)=7.6, 2J(Pt–H)=69, Mea]; 6.61 [q, J(H–H)=7,
Hd]; 8.33 [s, 3J(Pt–H)=46, He]. 31P-NMR (101.26
tone-d6): l=0.70 [d, 3J(P–H)=8, 2J(Pt–H)=83,
Mea]; 1.31 [d, J(Hc–Hd)=7, Hc]; 4.86 [q, J(Hc–Hd)=
7, Hd]; {6.93 [t, J(H–H)=9, 1H]; 7.19 [m, 1H], 7.39–

C. Anderson et al. / Journal of Organometallic Chemistry 631 (2001) 164–174
173
MHz, acetone-d6): Major isomer: l= −12.08 [s, J(Pt–
P)=970]. Minor isomer: l= −6.05 [s, J(Pt–P)=985].
FABMS (NBA): 847 [M−2Me], 734 [M−I–CH3], 720
[M−I]. Anal. Found: C, 50.4; H, 4.2; N, 1.5. Calc. for
C37H35INPPtS: C, 50.57; H, 4.01; N, 1.59%. 8b: R=
C6H4. Yield 45 mg (75%).1H-NMR (500 MHz, acetone-
d6): Major isomer: l=0.99 [d, 3J(HP)=7.5,
2J(Pt–H)=62, Meb]; 0.99 [d, J(H–H)=7, Hc]; 1.44 [d,
3J(H–P)=7.5, 2J(Pt–H)=71, Mea]; 6.85 [m, Hd];
{6.45 [d, J(H–H)=8, J(H–Pt)=42, 1H], 8.24 [d,
P)=7.6, 2J(Pt–H)=67, Mea]; 1.75 [d, J(H–H)=7,
Hc]; 6.28 [q, J(H–H)=7, Hd]; {6.42 [d, J(H–H)=9,
3
1H], 7.01–7.89 [23H], aromatics}; 8.62 [s, J(Pt–H)=
45, He]. 31P-NMR (101.26 MHz, acetone-d6): l= −
4.18 [s, J(Pt–P)=1577].
4.2.5. Synthetic procedure for the intramolecular
oxidati6e addition reactions
Compounds 8e and 8f were prepared by the reaction
of 100 mg (1.74×10−4 mol) of [Pt2Me4(m-SMe2)2] (1)
with 3.50×10−4 mol of the corresponding imine (2e:
118 mg; 2f: 114 mg) in acetone (10 ml). The mixture
was stirred for 5 h and 90 mg (3.50×10−4 mol) of
PPh3 were added. After 1 h, hexane (10 ml) was added
and the resulting precipitate was collected by filtration,
washed with hexane, and dried in vacuo. 8e: R=2-
BrC6H3. Yield 150 mg (52%). 1H-NMR (500 MHz,
acetone-d6): Major isomer: l=0.76 [d, 3J(HP)=7.5,
2J(Pt–H)=60, Meb]; 1.00 [d, J(H–H)=7.5, Hc]; 1.30
3
J(H–H)=8, 1H], aromatics}; 8.97 [s, J(Pt–H)=49,
He]. Minor isomer: l=1.40 [d, 3J(H–P)=8, 2J(Pt–
H)=70, Mea]; 1.42 [d, 3J(HP)=7.5, 2J(Pt–H)=60,
Meb]; 1.90 [d, J(H–H)=7, Hc]; 6.78 [m, Hd]; 8.36 [d,
3
J(H–H)=7, 1H aromatic]; 8.86 [s, J(Pt–H)=49, He].
31P-NMR (101.26 MHz, acetone-d6): Major isomer:
l= −9.39 [s, J(Pt–P)=982]. Minor isomer: l= −
3.95 [s, J(Pt–P)=1011]. Anal. Found: C, 53.9; H, 4.4;
N, 1.5. Calc. for C39H37INPPt: C, 53.68; H, 4.27; N,
1
3
2
1.60%. 8c: R=2-FC6H3. Yield 47 mg (79%). H-NMR
[d, J(H–P)=8, J(Pt–H)=70, Mea]; 6.84 [qd, J(H–
H)=7.5; 1.5, Hd]; {6.50 [d, J(H–H)=8, J(H–Pt)=
42.5, 1H], 7.76 [d, J(H–H)=8.5, 1H], 7.88 [d,
J(H–H)=8.5, 1H], 8.30 [d, J(H–H)=8.5, 1H], aro-
matics}; 8.95 [s, 3J(Pt–H)=49, He]. Minor isomer:
(500 MHz, acetone-d6): Major isomer: l=1.00 [d,
3J(H–P)=7.5, 2J(Pt–H)=61, Meb]; 1.10 [d, J(H–
H)=7, Hc]; 1.46 [d, 3J(H–P)=8, 2J(Pt–H)=70, Mea];
6.52 [m, Hd]; {6.31 [d, J(H–H)=7.5, J(H–Pt)=41.5,
3
3
2
1H], 8.58 [m, 1H], aromatics}; 9.06 [s, J(Pt–H)=48,
l=1.21 [d, J(H–P)=7.5, J(Pt–H)=60, Meb]; 1.34
He]. Minor isomer: l=1.42 [d, 3J(HP)=7.5, 2J(Pt–
H)=60, Meb]; 1.44 [d, 3J(HP)=8, 2J(Pt–H)=70,
Mea]; 1.97 [d, J(H–H)=7, Hc]; 6.50 [m, Hd]; 8.87 [s,
J(H–Pt)=48, 1H aromatic]; 9.20 [s, He]. 31P-NMR
(101.26 MHz, acetone-d6): Major isomer: l= −9.85 [s,
J(Pt–P)=984]. Minor isomer: l= −4.11 [s, J(Pt–
P)=1007]. 19F-NMR (282.26 MHz, CDCl3): Major
isomer: l= −158.39 [dd, J(F–Pt)=39, J(F–H)=11;
6]. Minor isomer: l= −158.06 [dd, J(F–Pt)=38,
J(F–H)=11; 6]. FABMS (NBA): 748 [M−Me–I].
Anal. Found: C, 52.3; H, 4.2; N, 1.5. Calc. for
C39H36FINPPt: C, 52.59; H, 4.07; N, 1.57%. 8d: R=2-
CF3C6H3. Yield 46 mg (78%). 1H-NMR (500 MHz,
[d, 3J(HP)=8, 2J(Pt–H)=70, Mea]; 2.02 [d, J(H–
H)=7, Hc]; 6.95 [m, Hd]; 8.50 [s, J(Pt–H)=48, He].
3
31P-NMR (101.26 MHz, acetone-d6): Major isomer:
l= −6.53 [s, J(Pt–P)=976]. Minor isomer: l= −
2.55 [s, J(Pt–P)=1006]. FABMS (NBA): 795 [M−
2Me], 730 [M−Me–Br], 715 [M−2Me–Br]. Anal.
Found: C, 56.6; H, 4.5; N, 1.7. Calc. for
C39H37BrNPPt: C, 56.73; H, 4.52; N, 1.70%. 8f: R=
1
2,6-Cl2C6H2. Yield 155 mg (56%). H-NMR (500 MHz,
acetone-d6): Major isomer: l=0.64 [d, 3J(HP)=7.5,
2J(Pt–H)=60, Meb]; 1.14 [d, J(H–H)=7, Hc]; 1.25 [d,
3J(H–P)=8, 2J(Pt–H)=69, Mea]; {6.58 [d, J(H–
H)=8, J(Pt–H)=43, 1H], 6.63 [t, J(H–H)=8, 1H],
6.68 [t, J(H–H)=8, 1H], 7.81 [d, J(H–H)=8.5, 1H],
3
acetone-d6): Major isomer: l=0.97 [d, J(H–P)=7.5,
2J(Pt–H)=61, Meb]; 1.11 [d, J(H–H)=7, Hc]; 1.49 [d,
8.39 [d, J(H–H)=8.5, 1H], aromatics}; 9.13 [s, J(Pt–
3
2
3J(H–P)=8.5, J(Pt–H)=70, Mea]; 6.87 [m, Hd]; 9.01
H)=50, He]. Minor isomer: l=1.12 [d, 3J(H–P)=7.5,
2J(Pt–H)=60, Meb]; 1.35 [d, 3J(HP)=8.5, 2J(Pt–
H)=70, Mea]; 2.22 [d, J(H–H)=7, Hc]; 6.54 [d, J(H–
[s, 3J(Pt–H)=49, He]. Minor isomer: l=1.40 [d,
3J(H–P)=7.5, 2J(Pt–H)=60, Meb]; 1.48 [d, 3J(H–
P)=8, 2J(Pt–H)=70, Mea]; 1.71 [d, J(H–H)=6.5,
Hc]; 8.82 [s, 3J(Pt–H)=48, He]. 31P-NMR (101.26
MHz, acetone-d6): Major isomer: l= −11.13 [s, J(Pt–
P)=982]. Minor isomer: l= −4.63 [s, J(Pt–P)=
1013].
3
H)=8, J(Pt–H)=45, Hd]; 9.08 [s, J(Pt–H)=50, He].
31P-NMR (101.26 MHz, acetone-d6): Major isomer:
l= −5.25 [s, J(Pt–P)=926]. Minor isomer: l= −
1.36 [s, J(Pt–P)=975]. Anal. Found: C, 57.3; H, 4.6;
N, 1.7. Calc. for C39H36Cl2NPPt: C, 57.42; H, 4.45; N,
1.72%.
The reactions of compound 4a with methyl iodide
were monitored by NMR in the following way, 10 ml of
methyl iodide were added to 20 mg of the platinum(II)
compound dissolved in 0.6 ml of acetone-d6 in a 5mm
4.3. X-ray structure analysis
1
NMR tube and H- and 31P-NMR spectra were taken,
A yellow rectangular plate (0.48×0.21×0.10 mm)
was selected. The crystallographic measurements were
done on a Siemens P4 diffractometer using graphite-
which allowed spectral characterization of 7a. 7a: R=
1
C4H2S. H-NMR (500 MHz, acetone-d6): l=0.24 [d,
3J(H–P)=6.6, 2J(Pt–H)=68, Meb]; 1.52 [d, 3J(H–
monochromatized Mo–Ka (u=0.71073 A) radiation.
,

174
C. Anderson et al. / Journal of Organometallic Chemistry 631 (2001) 164–174
Table 3
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).
Crystallographic data and structure refinement parameters
Empirical formula
Formula weight
Temperature (K)
C36H32NPPtS
736.75
293(2)
,
Wavelength (A)
0.71073
Orthorhombic
P212121
10.684(2)
16.412(3)
17.089(3)
2996.2(9)
4
Crystal system
Space group
Acknowledgements
,
a (A)
,
b (A)
,
c (A)
This work was supported by the DGICYT (Ministe-
rio de Educacio´n y Cultura, Spain, BQU2000-0652)
and from the Generalitat de Catalunya (project 1997-
SGR-00174).
3
,
V (A )
Z
Dcalc (Mg m−3
)
1.633
4.832
1456
Absorption coefficient (mm−1
F(000)
)
Reflections collected
Independent reflections
Reflections observed
Data/restraints/parameters
Goodness-of-fit on F2
R1(I\2|(I))
18 284
8734 (0.0607)
6965
8734/0/362
1.037
0.0394
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5. Supplementary material
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Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC no. 161706 for compound 4a.
.