Platinum(II) compounds with enantiomerically pure bis(pinene)-fused bipyridine ligands - Diimine-dichloro complexes and their substitution reactions

Article abstract of DOI:10.1002/1099-0682(200105)2001:5<1207::aid-ejic1207>3.0.co;2-4

The synthesis of chiral square-planar Pt^II complexes using symmetrical and unsymmetrical bis(pinene)-fused 2,2′-bipyridine is described. The neutral diimine dichloro complexes show a strong deviation of the coordination sphere from planarity if the pinene groups are attached at the 5-and 6-positions of the pyridine rings. However, this distortion does not occur in parallel with the chiral configuration at the diimine ligands. The substitution of the two cis-chloro ligands with diamines to form five-membered chelate rings shows little diastereoselectivity when racemic mixtures of chiral diamines are used. Also, ligands that are prochiral at the ligating centers show little selectivity upon coordination.

Full text of DOI:10.1002/1099-0682(200105)2001:5<1207::aid-ejic1207>3.0.co;2-4

FULL PAPER
Platinum(II) Compounds with Enantiomerically Pure Bis(pinene)-Fused
Bipyridine Ligands ؊ Diimine-Dichloro Complexes and Their Substitution
Reactions
Brunhilde Kolp,[a] Dirk Abeln,[b] Helen Stoeckli-Evans,[c] and Alexander von Zelewsky*[a]
Keywords: Chirality / Platinum / Substitution reactions / Diastereoselectivity / N ligands
The synthesis of chiral square-planar PtII complexes using
does not occur in parallel with the chiral configuration at the
symmetrical and unsymmetrical bis(pinene)-fused 2,2Ј-bi- diimine ligands. The substitution of the two cis-chloro li-
pyridine is described. The neutral diimine dichloro com- gands with diamines to form five-membered chelate rings
plexes show a strong deviation of the coordination sphere
from planarity if the pinene groups are attached at the 5-
and 6-positions of the pyridine rings. However, this distortion
shows little diastereoselectivity when racemic mixtures of
chiral diamines are used. Also, ligands that are prochiral at
the ligating centers show little selectivity upon coordination.
Introduction
stereoselective reactions to ligands that occupy the coor-
dination sites around the central metal (Scheme 1).
Square-planar coordination geometry, the most frequent
coordination mode of diamagnetic d8-metals do not gener-
ally exhibit chirality, since genuinely planar structures can-
not be chiral in three-dimensional space. Deviations from
planarity can, however, lead to chiral configurations. An
early example of this type was the platinum(II) complex
containing one molecule of meso-stilbenediamine and one
molecule of isobutylenediamine occuring as a pair of en-
Results and Discussion
Chiral Bipyridine Ligands
For the synthesis of the substituted bipyridine ligands
L1ϪL5, the method described by F. Kröhnke[5] was modi-
fied. The synthesis of the compounds L1, L2, and L5 has
already been described.[6,7] The preparation of ligand L3
was similar to that of L2 except that for one of the two
‘Kröhnke cyclizations’, (ϩ)-α-pinene was used as starting
material and for the second one (Ϫ)-α-pinene was used,
which gave the meso ligand L3.
The preparation of compound L4 is shown in Scheme 2.
Chirality was introduced by using enantiomerically pure
(Ϫ)-β-pinene (1) as starting material. Compound 1 was ox-
idized to the (ϩ)-nopinone (2) following a ‘one-pot’ method
described by Brown.[8] The nopinone was treated with
NaNH2 which resulted in the formation of enolate 3. Treat-
ment of 3 with formaldehyde in a Na2CO3 solution gave
the α,β-methylene ketone 4, which was used for the con-
densation with the ‘Kröhnke salt’ 5 in the same way as al-
ready described by von Zelewsky et al.[7] for L2.
antiomers.[1] Complexes in which
a distortion from
planarity occurs in a way that permits chirality have re-
cently been found in the class of bis-cyclometallated com-
pounds. These compounds have a very strong tendency to
form cis-complexes, leading to helical configurations of li-
gands that interact strongly, thereby avoiding co-
planarity.[2] The advent of nonracemic pyridine and bipyr-
idine ligands derived from naturally occurring terpene com-
pounds[3] has prompted us to investigate the possibility of
a stereoselective synthesis of coordination species that show
chiral elements within the ligand and around the metal
center. It has been shown that metal chirality can be prede-
termined in ‘‘square-planar’’ complexes (SP-4-complexes)
by using this type of ligand in diastereoselective syntheses.[4]
Here we present the preparation and characterization of
a series of enantiomerically pure PtII complexes, in which
the chirality is located in the ‘‘chiralized’’ bipyridine li-
gands. The investigations focus on the question whether the
ligands L1ϪL5 induce chiral distortions from planarity in
the complex and whether chirality can be transferred in
Complex Formation and Characterization in Solution
The complexation of L1, L2, L3, L4, and L5 with PtII
was carried out in aqueous hydrochloric acid solution using
K2PtCl4 as starting material (Scheme 1). The yellow, un-
charged dichloro complexes precipitated out of the aqueous
solution and were isolated and purified. As expected, the
formation of bis-diimine complexes was not observed, since
the ligands are sterically bulky.
[a]
´
Institute of Inorganic Chemistry, Perolles,
University of Fribourg,
1700 Fribourg, Switzerland
[b]
[c]
1H NMR Spectroscopy
Laboratory for Crystallography, University of Bern,
Freiestrasse 3, 3012 Bern, Switzerland
All compounds prepared were fully characterized by
ˆ
Institute of Chemistry, University of Neuchatel,
Avenue de Bellevaux 51, 2000 Neuchatel, Switzerland
1H-, 13C-, and 195Pt NMR spectroscopy. Figure 1 shows the
ˆ
Eur. J. Inorg. Chem. 2001, 1207Ϫ1220
WILEY-VCH Verlag GmbH, 69451 Weinheim, 2001
1434Ϫ1948/01/0505Ϫ1207 $ 17.50ϩ.50/0
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B. Kolp, D. Abeln, H. Stoeckli-Evans, A. v. Zelewsky
FULL PAPER
13C NMR
In all cases, the 13C NMR spectra show the expected fea-
tures. Contrary to the 1H NMR spectra, the 13C NMR
spectra of the diastereomeric ligands L2 and L3 exhibit dif-
ferences in the chemical shift values of C5. However the
complexes L2PtCl2 and L3PtCl2 don’t show any differences
1
in the H NMR or in the 13C NMR spectra.
195Pt NMR
More information about the isomeric purity of the com-
plexes can be obtained by 195Pt NMR spectroscopy, since
chemical shifts are usually very large for this nucleus. All
compounds show a single Pt-signal. The values in Table 1
show a small influence (∆δ ϭ 14 ppm) of the pinene groups
at the 4- and 5-positions when compared to the complex
with unsubstituted 2,2Ј-bipyiridine. The shift values for the
complexes with the 5,6-pinene-bipyridine ligands are much
larger, in the order of ∆δ ഠ 400 ppm. The diastereomeric
complexes L2PtCl2 and L3PtCl2 are not distinguishable.
Electronic and CD Spectra
Neither the UV or the CD spectra are very strongly in-
fluenced by complex formation. All free ligands show two
absorption maxima in the UV region. Complexation with
PtCl4Ϫ leads to a red shift of these ligand transitions as well
as to two additional bands above 300 nm (Table 2). The CD
activity, which is very small in the accessible spectral range
(250 nmϪ700 nm) is hardly enhanced through complex
formation. This is in marked contrast to complexes where
two or three chiral bipyridine ligands coordinate to one
metal center.[9]
X-ray Structure Determination
One of the ligands, L2 gave suitable crystals for structure
determination. Tables 3, 6, and 8 contain the relevant crys-
tallographic data. Figure 2 reveals an approximately C2-
symmetric structure with a transoid conformation of the
two pyridine rings. The values of all the internal coordinates
(bond lengths and bond angles) are as expected. A feature
that is worth noting is the banana-like deformation of the
bpy moiety, which can be expressed in terms of the angle
γ, as defined in Scheme 3 and given in Table 6. Although,
the ligand changes its conformation from transoid to cisoid,
this type of distortion is preserved and even significantly
enhanced (vide infra) upon coordination.
The X-ray structures of the complexes L2PtCl2, L3PtCl2,
and L4PtCl2 (no suitable crystals of L1PtCl2 and L5PTCL2
could be obtained), allow for an investigation of the ques-
tion as to whether the metal itself assumes a chiral config-
uration induced by the chiral ligands. Figures 3, 4, and 5
show representations of these molecules in a projection that
stresses the out-of-plane position of the ligand atoms. Se-
lected bond lengths and angles are listed in Tables 3, 4,
and 5.
Scheme 1
1H NMR spectra of L1 and L2, and of their Pt-complexes.
The pairs of diastereotopic protons H7 (H7endo and H7exo
)
are isochronous in free L1 and L2, as well as in L3, L4, and
L5. However, a strong downfield shift with a concomitant
splitting and a large geminal coupling occurs in the com-
plexes L2PtCl2, as well as in L3PtCl2 and L5PtCl2, whereas
L1PtCl2 and L4PtCl2 still show the same behavior as the
free ligand. In L1PtCl2, the complex formation strongly in-
fluences the aromatic proton H6, whereas in the case of
L4PtCl2, the aliphatic proton H10 is shifted strongly down-
field. The aliphatic protons, except for H7 in L2, L3, and
L5, H10 in L4, and the aromatic protons H3 and H4 are
only very slightly influenced by complexation.
Ligands L1ϪL4 and their Pt complexes all show equiva-
lent halves in the 1H NMR spectra (Figure 1). This equival-
ence is due to a C2 axis in L1, L2, and L4, whereas L3
has a mirror plane. These symmetry elements are no longer
L2PtCl2 and L4PtCl2 crystallize in the triclinic space
present in the solid state, as will be discussed later. In the group P1. In the former case, there are two independent
unsymmetrical ligand L5, all the protons of the two halves complex molecules per asymmetric unit, whereas the latter
are nonequivalent, as expected.
1208
contains four independent molecules. Compound L3PtCl2
Eur. J. Inorg. Chem. 2001, 1207Ϫ1220

PtII Compounds with Bis(pinene)-Fused Bipyridine Ligands
FULL PAPER
Scheme 2. Synthesis overview for L4
Table 1. 195Pt NMR spectroscopic data [referenced to NaPtCl6
(δ ϭ 0.0)]
Compound
δ
[Pt(2,2Ј-bpy)Cl2]
L1PtCl2
Ϫ2315
Ϫ2329
Ϫ1884
Ϫ1887
Ϫ1939
Ϫ2066
L2PtCl2
L3PtCl2
L4PtCl2
L5PtCl2
¯
crystallizes in the triclinic, centrosymmetric space group P1
with one independent molecule per asymmetric unit.
The independent molecules in the lattice of L2PtCl2 and
L4PtCl2 do not show strong variations in their structural
parameters (Tables 3, 4, and 8). In both cases, the molecules
designated as I (Tables 3 and 4), serve as a basis for fur-
ther discussion.
All three complexes L2PtCl2, L3PtCl2, and L4PtCl2
show strong deviation from planarity. Table 6 lists bond
angles and distances that characterize these deviations, as
given in Scheme 3. In the complex with the meso-form li-
gand L3, a strong out-of-plane distortion is observed,
whereby both chlorine ligands are displaced to the same
side of the coordination plane defined by the five-mem-
bered chelate ring. Figure 3 shows how the two chloride
ligands are located on the same side as the methyl groups
of the pinene moieties of the bent pinene-bpy-ligand. Most
surprisingly, exactly the same type of deformation is ad-
Figure 1. 1H NMR spectra of the ligands L1 and L2, and their
platinum complexes: a) free ligand L1, b) L1PtCl2, c) free ligand
L2, d) L2PtCl2
Eur. J. Inorg. Chem. 2001, 1207Ϫ1220
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B. Kolp, D. Abeln, H. Stoeckli-Evans, A. v. Zelewsky
FULL PAPER
Table 2. Absorption data and extinction coefficients from UV/Vis
spectra
Ligands
nm
ε
Complexes
nm
ε
L1
256
295
15200
21200
L1PtCl2
289
324
339
387
29400
11700
16700
3400
L2
L3
261
302
12500
22100
L2PtCl2
L3PtCl2
277
291
341
356
21200
20100
10800
11300
261
303
12500
18900
277
295
341
356
20600
21000
11900
13300
L4
L5
258
304
11500
28200
L4PtCl2
L5PtCl2
291
338
354
18700
15400
17200
Scheme 3. Definition of parameters from planar coordination geo-
metry for the distortion in the crystal structures for the L2PtCL2,
L3PtCl2, and L4PtCl2 complexes. α, β, and γ are defined as in
ref.[10], d* is the distance of a Cl ligand to the best plane defined
by the chelate ring
259
298
14600
20900
274
287
334
348
24600
24100
14900
18800
˚
Table 3. Selected bond lengths [A], angles and dihedral angles [°] of the free ligand L2 and the complex L2PtCl2
L2 L2PtCl2: Molecule I Molecule II
N1ϪC6
N1ϪC2
1.335
1.349
Pt1ϪN1
Pt1ϪN2
2.046
2.027
Pt2ϪN3
Pt2ϪN4
2.002
2.054
N1ЈϪC6Ј
N1ЈϪC2Ј
1.341
1.354
Pt1ϪCl1
Pt1ϪCl2
2.303
2.319
Pt2ϪCl3
Pt2ϪCl4
2.306
2.307
C6ϪN1ϪC2
C6ЈϪN1ЈϪC2Ј
N1ϪC2ϪC3
N1ϪC2ϪC2Ј
118.3
117.0
121.5
115.4
N1ϪPtϪN2
Cl1ϪPt1ϪCl2
N1ϪPt1ϪCl1
N2ϪPt1ϪCl2
80.0
85.2
96.0
97.1
N3ϪPt2ϪN4
Cl4ϪPt2ϪCl4
N3ϪPt2ϪCl3
N4ϪPt2ϪCl4
79.3
86.0
96.2
96.6
N1ϪC2ϪC2ЈϪN1Ј
C3ϪC2ϪC2ЈϪC3Ј
Ϫ166.9
Ϫ172.9
C5ϪN1ϪPt1ϪCl1
C17ϪN2ϪPt1ϪCl2
37.8
Ϫ30.5
C29ϪN3ϪPt2ϪCl3
C41ϪN4ϪPt2ϪCl4
Ϫ25.5
34.2
of the coordination plane. Even the crystal packing is very
similar in all three cases. These three complexes are all
strongly distorted from square-planar geometry, yet it
seems that the stereogenic centers are not decisive for the
type of distortion. In addition, the distortions occur in a
counter-intuitive way. We would have expected that both
chloride ligands lie on the opposite side of the plane to
the methyl groups of the pinene moieties in the meso-form
complex, and that the complex with the enantiomerically
pure ligand would adopt approximately C2 symmetry.
A similar phenomenon (mismatched symmetry) was ob-
served by Newkome et al.[10] for palladium complexes with
bipyridine ligands substituted at the 6- and 6,6Ј-positions.
The parameters d1 and d2 in Table 6 are defined in the same
way as in literature[10] (Scheme 3). In addition, we introduce
the distances d1* and d2*, respectively (Scheme 3), which
Figure 2. ORTEP[16] plot and Cerius2[17] representation of the crys-
tal structure of the free ligand L2
opted by the C2-symmetric (in the uncoordinated form) li- we consider to be a more reliable measure of the distortion
gands in their complexes L2PtCl2 and L4PtCl2. Again, from a square-planar arrangement. It is difficult to know
both chlorine ligands are displaced towards the same side whether these distortions are due to packing effects (e.g.
1210
Eur. J. Inorg. Chem. 2001, 1207Ϫ1220

PtII Compounds with Bis(pinene)-Fused Bipyridine Ligands
˚
FULL PAPER
Table 4. Selected bond lengths [A], angles and dihedral angles [°] can adopt a chiral configuration. Coordinated ethylenedia-
mine adopts a chiral conformation.[11] In the complex
of L3PtCl2
[Pt(bpy)(en)]2ϩ, which was also synthesized for reference
Molecule I
purposes[12], the CH2-protons of ‘en’ appear as a singlet at
δ ϭ 2.82. Two satellites due to 1H-195Pt coupling are clearly
Pt1ϪN1
Pt1ϪN2
2.063
2.015
resolved (Figure 6, a). Here, the λ- and δ- conformers of
the five-membered chelate ring of ethylenediamine are en-
antiomers. The achiral time average between the two con-
formers has a C2v symmetry, which results in one signal for
the four CH2 protons of ‘en’ (Scheme 5). In the case of the
complex 13, with the meso-form of the ligand, two signals
for the methylene protons are expected, since the time-aver-
aged symmetry is reduced to CS, rendering the two protons
‘above’ and ‘below’ the coordination plane nonequivalent.
With complex 12, the two conformers are the (RRδ)- and
(RRλ)-diastereomers. Again, two signals for the CH2 pro-
Pt1ϪCl1
Pt1ϪCl2
2.307
2.305
N1ϪPtϪN2
Cl1ϪPt1ϪCl2
N1ϪPt1ϪCl1
N2ϪPt1ϪCl2
80.3
85.9
96.1
96.1
C5ϪN1ϪPt1ϪCl1
C17ϪN2ϪPt1ϪCl2
34.3
Ϫ30.3
˚
Table 5. Selected bond lengths [A], bond angles and dihedral angles [°] of L4PtCl2
Molecule I Molecule II Molecule III
Molecule IV
Pt1ϪN1
Pt1ϪN2
2.041
2.048
Pt2ϪN3
Pt2ϪN4
2.025
2.022
Pt3ϪN5
Pt3ϪN6
2.045
2.022
Pt4ϪN7
Pt4ϪN8
2.030
2.023
Pt1ϪCl1
Pt1ϪCl2
2.294
2.306
Pt2ϪCl3
Pt2ϪCl4
2.305
2.292
Pt3ϪCl5
Pt3ϪCl6
2.306
2.293
Pt4ϪCl7
Pt4ϪCl8
2.289
2.311
N1ϪPtϪN2
Cl1ϪPt1ϪCl2
N1ϪPt1ϪCl1
N2ϪPt1ϪCl2
97.7
86.0
95.2
97.6
N3ϪPt2ϪN4
Cl4ϪPt2ϪCl4
N3ϪPt2ϪCl3
N4ϪPt2ϪCl4
80.4
85.6
96.9
95.7
N5ϪPt3ϪN6
Cl5ϪPt3ϪCl6
N5ϪPt3ϪCl5
N6ϪPt3ϪCl6
80.2
85.6
96.4
96.4
N7ϪPt4ϪN8
Cl7ϪPt4ϪCl8
N7ϪPt4ϪCl7
N8ϪPt4ϪCl8
80.1
86.6
94.8
97.0
C5ϪN1ϪPt1ϪCl1
C17ϪN2ϪPt1ϪCl2
23.5
Ϫ24.7
C29ϪN3ϪPt2ϪCl3
C41ϪN4ϪPt2ϪCl4
31.3
Ϫ25.3
C53ϪN5ϪPt3ϪCl5
C65ϪN6ϪPt3ϪCl6
26.4
Ϫ25.1
C77ϪN7ϪPt4ϪCl7
C89ϪN8ϪPt4ϪCl8
24.4
Ϫ26.8
Table 6. Distortion measurements for the complexes L2PtCl2,
L3PtCl3, and L4PtCl2
L2
L2PtCl2
L3PtCl2
L4PtCl2
Newkome[10]
˚
d1 [A]
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
Ϫ
3.4
7.0
0.427
0.363
0.814
0.778
12.3
0.380
0.368
0.829
0.831
15.5
0.371
0.345
0.720
0.721
16.4
15.9
6.8
0.277
0.496
0.699
0.908
18.8
16.8
7.5
˚
d2 [A]
˚
d1* [A]
˚
d2* [A]
β1 [°]
β2 [°]
γ1 [°]
γ2 [°]
11.4
13.5
17.1
11.1
14.4
11.6
7.1
8.5
π-stacking) or whether they are properties of the isolated
molecules. In solution, all complexes show the expected
symmetrical behavior of the two ligand halves on the NMR
time scale.
Substitution Reactions
Figure 3. ORTEP[16] plot and Cerius2[17] packing representation of
the crystal structure of L2PtCl2
In order to determine the influence of a chiral ligand on
the substitution reactions of the two cis-chloride ligands, a
series of diamine ligands were treated with the [Pt(pinene- tons are expected. Figure 6, b and c, show the relevant parts
bpy)]Cl2 complexes, as shown in Scheme 4. Table 7 shows of the 1H NMR spectra of these compounds. In both cases,
the diamines that were treated with the complexes of the four protons (assigned as ‘15’ in Figure 6) appear as one
Scheme 1. The products are numbered according to their broad signal. Complexes 11, 14, and 15 behave in a very
position in this ‘matrix’. The main point of interest is the similar way as 12 and 13, except that the lack of C2 sym-
stereoselectivity in these cases, where the incoming ligands metry in 15 is clearly discernible in its NMR spectrum.
Eur. J. Inorg. Chem. 2001, 1207Ϫ1220
1211

B. Kolp, D. Abeln, H. Stoeckli-Evans, A. v. Zelewsky
FULL PAPER
Figure 4. ORTEP[16] plot and Cerius2[17] packing representation of
the crystal structure of L3PtCl2
Scheme 4. Bidentate ligands used for the substitution reactions and
numbering scheme of the resulting complexes
Table 7. Matrix for the numbering scheme of the substitution reac-
tions (en ϭ ethylenediamine; R,R-DACH ϭ (1R,2R)-(Ϫ)-1,2-diam-
inocyclohexane; S,S-DACH ϭ (1S,2S)-(ϩ)-1,2-diaminocyclohex-
ane; dmen ϭ N,NЈ-dimethylethylenediamine; men ϭ N-methyl-
ethylenediamine)
L1PtCl2 L2PtCl2 L3PtCl2 L4PtCl2 L5PtCl2
en
11
21
31
41
51
61
71
81
12
22
32
42
13
-
14
24
-
15
-
R,R-DACH
S,S-DACH
S,S/R,R-DACH
dmen
-
35
45
-
44
men
piperazine
homopiperazine
-
-
-
-
-
-
-
-
Figure 5. ORTEP[16] plot and Cerius2[17] packing representation of
the crystal structure of L4PtCl2
The substitution reactions with ‘dmen’, ‘men’, piperazine,
and homopiperazine were successfully carried out only with
L1PtCl2. Complexation by replacing the two chlorine
atoms with the achiral bidentate ligand ‘dmen’ with this
compound creates stereogenic centers at the nitrogen atoms.
The formation of four different diastereomers is possible, as
represented in Scheme 6. In addition, the two conformers
of the chelate ring, δ and λ, will now probably differ more
Figure 6. Part of the 1H NMR aliphatic region of a) [Pt(bpy)-
in energy relative to ‘en’. In the NMR spectrum of 51 (Fig- (en)](PF6)2, b) compound 13, c) compound 12
1212 Eur. J. Inorg. Chem. 2001, 1207Ϫ1220

PtII Compounds with Bis(pinene)-Fused Bipyridine Ligands
FULL PAPER
In the case of ‘men’, the number of possible diastereo-
mers is reduced to two since only one nitrogen atom be-
comes stereogenic and in addition a complete loss of sym-
metry occurs upon complexation with this unsymmetrical
ligand. The NMR spectrum of compound 61 shows that
both diastereomers, those with (R)- and (S)- configurations
at the methylated N-atom, are formed in an approximate
ratio of 1:1. Most of the signals of the ligands are quad-
rupled. Furthermore, the H2ϪC(15) ethylene protons ap-
pear as two separate doublets, whereas the H2ϪC(15Ј) pro-
tons, which are not influenced by a close stereogenic center,
gave rise to a singlet (the methyl-bearing nitrogen atom was
assigned arbitrarily as N(14)]. The substitution of L1PtCl2
with piperazine yields only one possible isomer. Compound
71 shows the expected NMR pattern. The diastereotopic
protons of the CH2 groups of the piperazine ring are separ-
ated by 0.78 ppm, with a geminal coupling constant of
8.2 Hz.
Scheme 5
In the case of homopiperazine, also only one isomer is
possible, but the substitution results in a complete loss of
symmetry owing to the absence of a C2 axis of symmetry
in the ligand. However, the influence of the unsymmetrical
homopiperazine on the proton signals of the pinene group
is small. The loss of symmetry could only be observed in
the 500 MHz NMR spectra of compound 81. All the pro-
ton signals of the pinene group show the same pattern as
in the case of the symmetrical complexes, except that a
doubling of the exo-oriented CH3 groups and the endo-ori-
ented HϪC(9) protons is also evident. Furthermore, two
separate signals for the aromatic protons at the 6- and 6Ј-
positions were observed. The signals for the protons of the
CH2 groups 15 and 15Ј, as well as 16 and 16Ј are separated
by 0.25 ppm and 0.51 ppm, respectively, in the latter case
because of their diastereotopicity. The two protons at the
C(17)-position do not show this phenomenon.
1
Figure 7. H NMR spectrum (500 MHz) of compound 51; a) ali-
phatic region, b) aromatic region
ure 7, a and b) most of the signals appear twice, with a ratio
of 1:1. Small additional signals are observed in the region
of the aromatic protons, as well as for the NH signal and
the C(13)-methyl protons in an approximate ratio of 1:0.15.
This indicates the formation of two main diastereomers,
which are probably the two less constraining (R,R)- and
(S,S)- forms. Furthermore, in this case we observed the ex-
The ligand trans-1,2-diaminocyclohexane (DACH) is of
pected nonequivalence (as discussed above) of the ‘en’- special interest because of its configurations that are fixed
methylene protons, which appear separated by 0.82 ppm as by the six-membered ring. Substitution reactions were car-
doublets with a coupling constant of 8.8 Hz. The diastereo- ried out with the pure (S,S) and (R,R)-forms, as well as
topicity is much more pronounced owing to the new ste- with the racemic mixture (S,S)/(R,R) ϭ 1:1. In the case of
reogenic centers located at the neighboring N-atoms.
ligand L1, all the spectra of the substitution products 21,
Scheme 6. The four possible diastereoisomers after the substitution reaction of L1PtCl2 with ‘dmen’
Eur. J. Inorg. Chem. 2001, 1207Ϫ1220
1213

B. Kolp, D. Abeln, H. Stoeckli-Evans, A. v. Zelewsky
FULL PAPER
(0.81 g, 5.40 mmol) prepared from (ϩ)-α-pinene[7], and dry ammo-
nium acetate (3.6 g) were dissolved in glacial acetic acid (7 mL)
and stirred at 100 °C for 15 h. After cooling the dark brown reac-
tion mixture to room temperature, water (100 mL) was added, fol-
lowed by extraction of the water phase with hexane (at least 7 ϫ
50 mL). The collected organic phases were washed with water (100
mL), dried with MgSO4 and filtered. Evaporation of the solvent
yielded L3 (780 mg, 42%). The product was recrystallized from
acetone. Ϫ 1H NMR (300 MHz, CDCl3): δ ϭ 8.02 [d, 3J ϭ 7.9 Hz,
31, and 41 are indistinguishable. Although this does not
exclude a diastereoselective reaction, it is highly improbable
that such selectivity occurs. In the case of the much bulkier
ligand L2, complexes 22 and 32 can be distinguished by a
difference in chemical shifts of one of the methyl groups
and of one of the protons of the CH2-group in the pinene
part. From this, a diastereomeric ratio of (RR)/(SS) ϭ 1:1.3
is calculated. The corresponding analysis for ligand L4
yields a slightly higher diastereoselectivity for the (R,R)-
form [(R,R)/(S,S) ϭ 1.5:1].
3
2 H, HϪC(3,3Ј)], 7.30 [d, J ϭ 7.9 Hz, 2 H, HϪC(4,4Ј)], 3.19 [d,
3J ϭ 2.6 Hz,4 H, H2ϪC(7)], 2.78 [dd, 3J ϭ 5.6, 5.6 Hz, 2 H, H-
(10,10Ј)], 2.68 [ddd, 2J ϭ 9.6 Hz, 3J ϭ 5.6, 5.6 Hz, 2 H,
HbϪC(9,9Ј)], 2.37 [m,
2 H, HϪC(8,8Ј)], 1.40 [s, 6 H,
2
H3ϪC(12,12Ј)], 1.28 [d, J ϭ 9.6 Hz, 2 H, HaϪC(9,9Ј)], 0.65 [s, 6
H, H3ϪC(13,13Ј)]. Ϫ 13C NMR (75 MHz, CDCl3): δ ϭ 156.2
[C(2,2Ј)], 141.8 [C(4,4Ј)], 133.9 [C(3,3Ј)], 117.9 [C(2,2Ј)], 112.8
[C(5,5Ј)], 46.5 [C(10,10Ј)], 40.3 [C(8,8Ј)], 39.5 [C(11,11Ј)], 36.6
[C(7,7Ј)], 31.9 [C(9,9Ј)], 26.1 [C(12,12Ј)], 21.3 (13,13Ј)]. Ϫ EI-MS:
m/z (%) ϭ 344 (100) [Mϩ], 329 (58) [Mϩ Ϫ CH3], 303 (59), 271
(22), 257 (42), 154 (10). Ϫ C24H28N2 (344.5): calcd. C 83.68, H
8.19, N 8.13, found C 82.92, H 8.40, N 7.94.
Conclusions
Chiral bipyridine ligands induce significant distortions in
square-planar platinum complexes if the ‘substituents’ of
the pyridine are at the 6- and 6Ј-positions. However, C2-
symmetric, homochiral ligands yield molecules of low sym-
metry if the two other ligand positions are occupied by ClϪ.
The distortions are not determined by the chiral nature of
these ligands, since an overall achiral meso-form behaves
in a very similar way. Consequently, substitution of these
chlorides by amines proceeds in a nonstereoselective man-
ner.
(6R,8R)-2-(1Ј-Ethyloxime)-5,6,7,8-tetrahydro-9,9-dimethyl-6,8-
metaquinoline (6): The Kröhnke salt 5 (6.90 g, 26.6 mmol), NH4
acetate (17.7 g), glacial acetic acid (28 mL), and
4 (4.0 g,
26.6 mmol) were heated at reflux for 15 h. The reaction mixture
was cooled to room temperature, diluted with water (100 mL) and
extracted with hexane [7 ϫ 50 mL). The combined organic phases
were washed with water (100 mL), dried with MgSO4 with active
charcoal, and filtered. After evaporating the solvent a brown vis-
cous liquid (3.84 g, 63%) was obtained. Ϫ 1H NMR (300 MHz,
CDCl3): δ ϭ 7.51 [d, 3J ϭ 7.7 Hz, 1 H, HϪC(3)], 7.40 [d, 3J ϭ
Experimental Section
Products: Solvents and reagents were purchased from Fluka and
Aldrich. Iodine was sublimed before use. Pyridine was dried with
KOH and freshly distilled prior to use. Ammonium acetate was
dried for 5Ϫ6 h before use in a vacuum oven at 40 °C. Diethyl
ether was distilled from sodium/benzophenone prior to use. The
precursor platinum complex K2[PtCl4] was prepared following pro-
cedures described by Livingstone.[13]
3
7.7 Hz, 1 H, HϪC(4)], 3.09 [dd, J ϭ 5.8, 5.8 Hz, 1 H, HϪC(8)],
2
2.93 [d, 3J ϭ 2.9 Hz, 2 H, H-(5)], 2.72 [ddd, J ϭ 9.8 Hz, 3J ϭ 5.8,
5.8 Hz, 1 H, HaϪC(7)], 2.35 [s, 3 H, H3ϪC(11)], 1.28 [d, 2J ϭ
9.8 Hz, 1 H, HbϪC(7)], 0.65 [s, 3 H, H3ϪC(10)].
1-{2-(Pineno[2,3-e]pyridin-2-yl)acetyl}pyridinium Iodide (7): Product
6 (3.80 g, 15 mmol) was reacted with HCl (70 mL, 25%) and heated
at reflux for 8 h. After cooling the reaction mixture to room tem-
perature, the black solution was brought to pH ϭ 3 by the addition
of NaOH (30%), and then carefully adjusted to pH ϭ 7Ϫ8 with
Na2CO3. This mixture was then extracted with hexane (7 ϫ 50
mL). The organic phases were washed with water (100 mL), dried
with MgSO4 and filtered. Evaporation of the solvent gave a
brownϪyellow, viscous liquid (2.96 g). A portion of this product
(2.70 g) was dissolved in pyridine (4 mL) in a 250-mL flask. Iodine
(3.20 g, 12.5 mmol) dissolved in pyridine (10 mL) was added, and
the mixture was heated at reflux for 3 h. After removing excess
pyridine by vacuum distillation, dry diethyl ether (180 mL) was
added to the black residue and kept at 4 °C overnight. The brown
powder was filtered off, washed twice with diethyl ether and dried
under high vacuum for 2 d. In order to obtain a good precipitate,
it was essential to carry out this reaction with the exclusion of
water, resulting in an hygroscopic product (7.05 g, 90%). The prod-
uct was a mixture of the desired product 7 and pyridinium iodide.
The ratio was determined to be 1:1. Ϫ 1H NMR (300 MHz,
Measurements: NMR spectra were recorded on a ‘Varian Gemini
300’ (300.075 MHz) or on
a
‘Bruker Avance DRX500’
(500.13 MHz) spectrometer. Chemical shifts are given in ppm using
TMS or the solvent itself as internal standard, and coupling con-
stants J are given in Hz. Assignment of the 1H and 13C NMR
signals was performed by COSY, DEPT and HETCOR techniques.
Diastereotopic protons are labeled as Ha for the endo-oriented pro-
tons and Hb for the exo-oriented protons. The exo methyl groups
of the pinene moieties are assigned as 12 and 12Ј, the exo-oriented
ones as 13 and 13Ј. The 195Pt NMR spectra were recorded on the
Varian Gemini 300 at 64.376 MHz. The signals were referenced
[14]
to Na2PtCl6
(δ ϭ 0.0). Ϫ UV/Vis spectra were measured on a
PerkinϪElmer Lambda 40 spectrometer. Ϫ Mass spectral data
were acquired on ‘VG Instrument 7070E’ equipped with a FAB
inlet system. Ϫ Elemental analysis were obtained from CIBA Spe-
´
cialties, Marly (Switzerland) and ‘Ecole d’ingeneurs de Fribourg’
(Switzerland).
General: Compounds 3 and 4 (Scheme 2) were synthesized follow-
ing a method described by M.Gianini.[7] The preparation of the
appropriate Kröhnke salt 5 (Scheme 2) for condensation with 4 was
3
[D6]DMSO): (numbering see Scheme 2) δ ϭ 9.00 [d, J ϭ 6.8 Hz,
2 H, HϪC(15)], 8.70 [t, 3J ϭ 7.8 Hz, 1 H, HϪC(13)], 8.25 [dd, 3J ϭ
3
7.8, 6.7 Hz, 2 H, HϪC(14)], 7.89 [d, J ϭ 7.7 Hz, 1 H, HϪC(3)],
described by Rupprecht.[7] The preparation of ligand L5 was first
3
7.86 [d, J ϭ 7.7 Hz, 1 H, HϪC(4)], 6.48 [s, 2 H, HϪC(16)], 3.05
[6]
´
described by Philippe Laine in a private communication.
2
3
[m, 3 H, HϪC(8), HϪC(5)], 2.80 [dd, J ϭ 9.8 Hz, J ϭ 5.8 Hz, 1
H, HaϪC(7)], 2.38 [m, 1 H, HϪC(6)], 1.44 [s, 3 H, H3ϪC(11)],
L3: [2-{(Ϫ)-α-Pineno[2,3-e]pyridin-2-yl}acetyl]pyridinium iodide
2
(2.27 g, 5.4 mmol, prepared as described in ref.[7]), pinocarvone
1.21 [d, J ϭ 9.8 Hz, 1 H, HbϪC(7)], 0.65 [s, 3 H, H3ϪC(10)]. Ϫ
1214
Eur. J. Inorg. Chem. 2001, 1207Ϫ1220

PtII Compounds with Bis(pinene)-Fused Bipyridine Ligands
FULL PAPER
3
Pyridinium iodide: δ ϭ 8.91 [d, J ϭ 6.5 Hz, 2 H, HϪC(15)], 8.55
146.4 [C(5,5Ј)], 145.2 [C(6,6Ј)], 121.2 [C(3,3Ј)], 44.8 [C(10,10Ј)], 39.5
[C(8,8Ј)], 33.5 [C(11,11Ј)], 31.3 [C(7,7Ј)], 29.7 [C(9,9Ј)], 25.6
[C(12,12Ј)], 21.5 [C(13,13Ј)]. Ϫ 195Pt NMR (64.376 MHz, CDCl3):
see Table 1. Ϫ FAB-MS: m/z (%) ϭ 610 (25) [Mϩ]; 575 (86) [Mϩ
Ϫ Cl]; 537 (18) [Mϩ Ϫ 2 Cl]; 460 (20), 391 (43), 345 (98) [L1], Ϫ
C24H28Cl2N2Pt (610.5): calcd. C 47.20, H 4.62, N 4.59, found C
47.40, H 4.69, N 5.07.
[t, 3J ϭ 7.8 Hz, 1 H, HϪC(13)], 8.03 [dd, 3J ϭ 7.7, 6.6 Hz, 2 H,
HϪC(14)].
L4: Compound 7 (3.0 g, 4.78 mmol), ammonium acetate (3.1 g)
and 4 (0.72 g, 4.78 mmol) were dissolved in glacial acetic acid (6
mL) and stirred at reflux for 15 h. The reaction temperature was
gradually raised over a period of 4 h starting at 50 °C. After cooling
the reaction mixture to ambient temperature, water (80 mL) was [{Bis[(؊)-pineno]؊2,2Ј-bipyridine}(ethylenediamine)PtII](PF6)3 (11):
added. The mixture was extracted with hexane [7 ϫ 50 mL). Wash-
ing, drying and evaporation of the solvent yielded a yellow powder
(0.94 g, 57%). Recrystallization from hexane gave white crystals of
To a suspension of L1PtCl2 (100 mg, 0.16 mmol) in water/acetone
(1:1, 25 mL), ethylenediamine (10 µL) was added. After heating the
reaction mixture at reflux for 8 h, the solution was cooled to room
L4. Ϫ 1H NMR (300 MHz, CDCl3): δ ϭ 8.08 [d, 3J ϭ 7.7 Hz, 2 temperature and unreacted starting material was filtered off. The
H, HϪC(3,3Ј)], 7.49 [d, 3J ϭ 7.7 Hz, 2 H, HϪC(4,4Ј)], 3.09 [dd, acetone was evaporated from the filtrate and solid NH4PF6 was
3J ϭ 5.8, 5.8 Hz, 2 H, HϪC(10,10Ј)], 2.94 [d, 3J ϭ 2.9 Hz, 4 H, added to the aqueous solution. The mixture was kept for 1 h at 4
H2ϪC(7,7Ј)], 2.71 [ddd, 2J ϭ 9.8 Hz, 3J ϭ 5.8, 5.8 Hz, 2 H,
HbϪC(9,9Ј)], 2.31 [m, H, HϪC(8,8Ј)], 1.40 [s,
H3ϪC(12,12Ј)], 1.32 [d, J ϭ 9.8 Hz, 2 H, HaϪC(9,9Ј)], 0.65 [s, 6
°C. The white precipitate was filtered off, washed with water, and
H, dried in vacuum. Purification by recrystallization from ethanol/di-
ethyl ether gave 11 (90 mg, 62%). Ϫ 1H NMR (300 MHz,
2
6
2
H, H3ϪC(13,13Ј)]. Ϫ 13C NMR (75 MHz, CDCl3): δ ϭ 165.8 [D3]ACN): δ ϭ 8.07 [s, 2 H, HϪC(3,3Ј)], 7.97 [s, JPt-H ϭ 29.8 Hz,
[C(2,2Ј)], 152.6 [C(6,6Ј)], 136.0 [C(4,4Ј)], 130.0 [C(5,5Ј)], 118.9 2 H, HϪC(6,6Ј)], 5.11 [b, 4 H, H2ϪN(14,14Ј)], 3.17 [d, 3J ϭ 2.3 Hz,
3
[C(3,3Ј)], 50.5 [C(10,10Ј)], 40.3 [C(8,8Ј)], 39.9 [C(11,11Ј)], 31.2 4 H, H2ϪC(7,7Ј)], 2.96 [dd, J ϭ 5.4, 5.4 Hz, 2 H, HϪC(10,10Ј)],
(C7,7Ј)], 30.9 [C(9,9Ј)], 26.0 [C(12,12Ј)], 21.5 [C(13,13ЈЈ)]. Ϫ EI-
MS: m/z (%) ϭ 344 (25) [Mϩ], 329 (10) [Mϩ Ϫ CH3], 315 (7) [Mϩ
Ϫ 2 CH3], 301 (100) [Mϩ Ϫ 3 CH3]. Ϫ C24H28N2 (344.5): calcd. C
83.7, H 8.2, N 8.1; found C 83.6, H 8.2, N 7.9.
2.80 [m, 6 H, HbϪC(9,9Ј), H2ϪC(15,15Ј)], 2.40 [m, 2 H,
HϪC(8,8Ј)], 1.45 [s, 6 H, H3ϪC(12,12Ј)], 1.23 [d, 2J ϭ 9.9 Hz, 2
H, HaϪC(9,9Ј)], 0.66 [s, 6 H, H3ϪC(13,13Ј)]. Ϫ 13C NMR (MHz,
[D3]ACN): δ ϭ 147.0 [C(6,6Ј)], 124.3 [C(3,3Ј)], 47.9 (C15,15Ј)], 45.4
[C(10,10Ј)], 40.2 [C(8,8Ј)], 33.9 [C(7,7Ј)], 31.3 [C(9,9Ј)],
25.2 [C(12,12Ј)], 21.3[C(13,13Ј)], (the quaternary carbon atoms
L5: [2-{(Ϫ)-α-Pineno[2,3-e]pyridin-2-yl}acetyl]pyridinium iodide
(5.46 g, 13.0 mmol, prepared as described in ref.[7]) was suspended
in formamide (50 mL). (1R)-(Ϫ)-Myrtenal (1.96 g, 13.0 mmol) and
dry ammonium acetate (2.51 g) were added to this suspension and
the reaction mixture was stirred at reflux for 15 h. After cooling
the mixture to 0 °C, water (80 mL) was added and the mixture was
stirred for 30 min. The black solution was extracted with diethyl
could not be detected). Ϫ FAB-MS: m/z (%) ϭ 744 (12) [Mϩ
Ϫ
PF6], 598 (69) [Mϩ Ϫ 2 PF6], 537 (13) [Mϩ Ϫ en], 307 (29), 171
(57), 154 (100).
[{Bis[(؊)-pineno]؊2,2Ј-bipyridine}(R,R-DACH)PtII](PF6)2
Compound L1PtCl2 (100 mg, 16 mmol) was suspended in water/
(21):
ether (at least 8 ϫ 70 mL). The collected organic phases were acetone (1:1, 25 mL). (R,R)-diaminocyclohexane (30 mg, 26 mmol)
washed twice with water (80 mL), dried with MgSO4 and filtered.
Evaporation of the solvent yielded a brown powder (3.2 g). Recrys-
was added. After the reaction mixture was heated at reflux for 10 h,
unreacted starting materials were filtered off and the acetone was
tallization from acetone gave pure L5 (2.50 g, 56%). Ϫ 1H NMR evaporated from the filtrate. To this solution, solid NH4PF6 was
(300 MHz, CDCl3): δ ϭ 8.17 [s, 1 H, HϪC(6Ј)], 8.14 [s, 1 H, added and the solution was allowed to stand for 4 h at 4 °C. The
HϪC(3Ј)], 7.99 [d, 3J ϭ 7.8 Hz, 1 H, HϪC(3)], 7.30 [d, 3J ϭ 7.8 Hz,
white product was filtered off and washed with water. The product
3
3
1
1 H, HϪC(4)], 3.18 [d, J ϭ 2.6 Hz, 2 H, H2ϪC(7)], 3.03 [d, J ϭ (95 mg, 61%), was recrystallized from ethanol/diethyl ether. Ϫ H
2.7 Hz, 2 H, H2ϪC(7Ј)], 2.84 [dd, 3J ϭ 5.5 Hz, 1 H, HϪC(10Ј)], NMR (300 MHz, [D3]acetonitrile): δ ϭ 8.07 [s, 2 H, HϪC(3,3Ј)],
3
2.78 [dd, J ϭ 5.7 Hz, 1 H, HϪC(10)], 2.68 [m, 2 H, HbϪC(9,9Ј)],
8.00 [s, 2 H, HϪC(6,6Ј)], 5.38 [b, 2 H, HbϪN(14,14Ј)], 4.77 [b, 2
2.38 [m, 1 H, HϪC(8)], 2.28 [m, 1 H, HϪC(8Ј)], 1.40 [s, 6 H, H, HaϪN(14,14Ј)], 3.17 [d, 3J ϭ 3.4 Hz, 4 H, H2ϪC(7,7Ј)], 2.96
2
2
2
H3ϪC(12,12Ј)], 1.30 [d, J ϭ 9.6 Hz, 1 H, HaϪC(9)], 1.22 [d, J ϭ
[dd, 3J ϭ 5.3, 5.3 Hz, 2 H, HϪC(10,10Ј)], 2.83 [ddd, J ϭ 10.0 Hz,
9.6 Hz, 1 H, HaϪC(9Ј)], 0.66 [s, 3 H, H3ϪC(13)], 0.62 [s, 3 H, 3J ϭ 5.8, 5.8 Hz, 2 H, HbϪC(9,9Ј)], 2.63 [m, 2 H, HϪC(15,15Ј)],
H3ϪC(13Ј)]. Ϫ 13C NMR (75 MHz, CDCl3): δ ϭ 156.3 [C(2)], 2.40 [m,
2
H, HϪC(8,8Ј)], 2.15 [d, 2J
ϭ
12.0 Hz,
2
H,
2
154.8 [C(4Ј)], 154.2 [C(6)], 145.5 [C(2Ј)], 145.2 [C(6Ј)], 142.6 [C(5Ј)],
HaϪC(16,16Ј)], 1.65 [d, J ϭ 8.9 Hz, 2 H, HaϪC(17,17Ј)], 1.45 [s,
141.4 [C(5)], 133.8 [C(4)], 120.3 [C(3Ј)], 117.6 [C(3)], 46.4 [C(10)], 8 H, H3ϪC(12,12Ј), HbϪC(16,16Ј)], 1.25 [d, 2J ϭ 8.9 Hz, 2 H,
2
44.4 [C(10Ј)], 40.2 [C(8)], 40.1 [C(8Ј)], 39.5 [C(11)], 39.3 [C(11Ј)], HbϪC(17,17Ј)], 1.24 [d, J ϭ 10.0 Hz, 2 H, HaϪC(9,9Ј)], 0.67 [s, 6
36.7 [C(7)], 32.9 [C(7Ј)], 31.9 [C(9)], 31.8 [C(9Ј)], 26.0 [C(12,12Ј)],
21.3 [C(13,13Ј)]. Ϫ EI-MS: m/z (%) ϭ 345 (100) [Mϩ], 330 (44)
[Mϩ Ϫ CH3], 301 (78), 271 (26), 257 (44), 154 (9).
H, H3ϪC(13,13Ј)]. Ϫ 13C NMR (75 MHz, [D3]acetonitrile): δ ϭ
155.8; 154.5; 153.3; 148.9 [C(4,4Ј)], 146.9 [C(6,6Ј)], 124.2 [C(3,3Ј)],
62.5 [C(15,15Ј)], 45.3 [C(10,10Ј)], 40.4 [C(8,8Ј)], 36.7 [C(11,11Ј)],
34.2 [C(7,7Ј)], 33.2 (16,16Ј)], 31.6 [C(9,9Ј)], 25.8 [C(12,12Ј)], 24.8
[C(17,17Ј)], 21.5 [C(13,13Ј)]. Ϫ FAB-MS: m/z (%) ϭ 799 (18) [Mϩ
Ϫ PF6], 653 (11) [Mϩ Ϫ 2 PF6], 327 (100).
L1PtCl2: Compound L1 (600 mg, 1.7 mmol) was added to a solu-
tion of K2PtCl4 (723 mg, 1.7 mmol) dissolved in HCl (0.2 , 80
mL). After stirring for 3 h at reflux, the yellow precipitate was fil-
tered off and washed with water. The crude product was dried at [{Bis[(؊)-pineno]؊2,2Ј-bipyridine}(S,S-DACH)PtII](PF6)2 (31): The
50 °C in a vacuum oven. Recrystallization from chloroform/hept-
synthesis, and purification of compound 31 was carried out as de-
scribed for compound 21 with L1PtCl2 (53 mg, 0.086 mmol) in
ane gave bright yellow L1PtCl2 (1.02 g, 1.6 mmol, 96%). Ϫ 1H
NMR (300 MHz, CDCl3): δ ϭ 9.20 [s, 2 H, HϪC(6,6Ј)], 7.66 [s, 2 water/acetone (15 mL) and (S,S)-diaminocyclohexane (22 mg,
3
1
H, HϪC(3,3Ј)]; 3.02 [d, J ϭ 2.5 Hz, 4 H, H2ϪC(7,7Ј)], 2.95 [dd, (0.19 mmol). Yield: 54 mg (66%). Ϫ H NMR (300 MHz, [D3]ace-
3J ϭ 5.4, 5.4 Hz, 2 H, HϪC(10,10Ј)], 2.77 [m, 2 H, HbϪC(9,9Ј)],
tonitrile): δ ϭ 8.07 [s, 2 H, HϪC(3,3Ј)], 8.00 [s, 2 H, HϪC(6,6Ј)],
2.36 [m, 2 H, HϪC(8,8Ј)], 1.42 [s, 6 H, H3ϪC(12,12Ј)], 1.19 [d, 5.38 [b, 2 H, HbϪN(14,14Ј)], 4.77 [b, 2 H, HaϪN(14,14Ј)], 3.17 [d,
2J ϭ 10.2 Hz, 2 H, HaϪC(9,9Ј)], 0.66 [s, 6 H, H3ϪC(13,13Ј)]. Ϫ 3J ϭ 3.4 Hz, 4 H, H2ϪC(7,7Ј)], 2.96 [dd, 3J ϭ 5.3, 5.3 Hz, 2 H,
13C NMR (75 MHz, CDCl3): δ ϭ 181.7 [C(2,2Ј)], 148.8 [C(4,4Ј)], HϪC(10,10Ј)], 2.83 [ddd, 2J ϭ 10.0 Hz, 3J ϭ 5.8, 5.8 Hz, 2 H,
Eur. J. Inorg. Chem. 2001, 1207Ϫ1220
1215

B. Kolp, D. Abeln, H. Stoeckli-Evans, A. v. Zelewsky
FULL PAPER
HbϪC(9,9Ј)], 2.63 [m,
2
H, HϪC(15,15Ј)], 2.40 [m,
2
H, [{Bis[(؊)-pineno]؊2,2Ј-bipyridine}(N-methylethylenediamine)-
PtII](PF6)2 (61): The synthesis, and purification of compound 61
HϪC(8,8Ј)], 2.15 [d, 2J ϭ 12.0 Hz, 2 H, HaϪC(16,16Ј)], 1.65 [d,
2J ϭ 8.9 Hz, 2 H, HaϪC(17,17Ј)], 1.45 [s, 8 H, H3ϪC(12,12Ј), was carried out as described for compound 11 with L1PtCl2
2
HbϪC(16,16Ј)]; 1.25 [d, J ϭ 8.9 Hz, 2 H, HbϪC(17,17Ј)]; 1.24 [d, (57 mg, 0.093 mmol) and methylethylenediamine (17 µL,
2J ϭ 10.0 Hz, 2 H, HaϪC(9,9Ј)]; 0.67 [s, 6 H, H3ϪC(13,13Ј)]. Ϫ 13C 0.19 mmol) in water/acetone (15 mL). Yield: 50 mg (60%) of 61. Ϫ
NMR (75 MHz, [D3]acetonitrile): δ ϭ 155.2; 154.3; 153.1; 149.0
1H NMR (500 MHz, [D3]acetonitrile): δ ϭ 8.08 [s, 2 H, HϪC(3 or
[C(4,4Ј)], 146.8 [C(6,6Ј)], 124.6 [C(3,3Ј)], 62.5 [C(15,15Ј)], 45.4 3Ј), HϪC(3 or 3Ј)*], 8.07 [s, 2 H, HϪC(3 or 3Ј), HϪC(3 or 3Ј)*],
[C(10,10Ј)], 40.8 [C(8,8Ј)], 36.6 [C(11,11Ј)], 34.3 [C(7,7Ј)], 33.4 8.00 [s, 1 H, HϪC(6 or 6Ј)], 7.99 [s, 1 H, HϪC(6 or 6Ј)*], 7.91 [s,
[C(16,16Ј)], 31.7 [C(9,9Ј)], 25.9 [C(12,12Ј)], 24.6 [C(17,17Ј)], 21.5 2 H, HϪC(6 or 6Ј), HϪC(6 or 6Ј)*], 5.64 [b, 2 H, HϪN(14),
[C(13,13Ј)], (the aromatic quaternary carbon atoms could not be
HϪN(14)*], 5.22 [b, 2 H, HbϪN(14Ј), HbϪN(14Ј)*], 5.13 [b, 2 H,
assigned). Ϫ FAB-MS: m/z (%) ϭ 799 (9) [Mϩ Ϫ PF6], 652 (13) HaϪN(14Ј), HaϪN(14Ј)*], 3.17 [d, 3J ϭ 2.5 Hz, 10 H, H2ϪC(7,7Ј),
[Mϩ Ϫ 2 PF6], 631 (14), 327 (100).
H2ϪC(7,7Ј)*, HbϪC(15), HbϪC(15)*], 3.06 [m, 6 H, H2ϪC(15Ј),
H2ϪC(15Ј)*, HϪC(10 or 10Ј), HϪC(10 or 10Ј)*], 2.96 [dd, 3J ϭ
5.5, 5.5 Hz, 2 H, HϪC(10 or 10Ј), HϪC(10 or 10Ј)*], 2.86 [d, 3J ϭ
6.7 Hz, 3 H, H3CϪN(14)], 2.85 [d, 3J ϭ 6.7 Hz, 3 H, H3CϪN(14)*
], 2.82 [m, 4 H, HbϪC(9), HbϪC(9Ј), HbϪC(9)*, HbϪC(9Ј)*], 2.68
[d, 2J ϭ 9.6 Hz, 2 H, HaϪC(15), HaϪC(15)*], 2.40 [m, 4 H,
HϪC(8), HϪC(8Ј), HϪC(8*), HϪC(8Ј)*], 1.46 [s, 6 H, H3ϪC(12
or12Ј), H3ϪC(12 or12Ј)*], 1.44 [s, 3 H, H3ϪC(12 or 12Ј)*], 1.43 [s,
3 H, H3ϪC(12 or 12Ј)*], 1.24 [m, 4 H, HaϪC(9), HaϪC(9Ј),
HaϪC(9)*, HaϪC(9Ј)*], 0.69 [s, 3 H, H3ϪC(13 or 13Ј), 0.67 [s, 3
H, H3ϪC(13 or 13Ј)*], 0.66 [s, 3 H, H3ϪC(13 or 13Ј)*], 0.65 [s, 3
H, H3ϪC(13 or 13Ј)*]. Ϫ 13C NMR (125 MHz, [D3]acetonitrile):
δ ϭ 155.6, 153.5, 149.4, 149.3, 148.8, 146.7, 146.3 [C(6 or 6Ј), 146.0
[C(6 or 6Ј)], 124.3 [C(3 or 3Ј)], 124.2 [C(3 or 3Ј)], 57.8 [C(15)], 45.5
[C(10 or 10Ј)], 45.3 [C(10 or 10Ј)], 43.9 [C-(15Ј)], 41.7 [CϪN(14)],
41.6 [(CϪN(14)*], 40.3 [C(8 or 8Ј)], 40.2 [C(8 or 8Ј)], 39.7 [C(11 or
11Ј)*], 39.6 [C(11 or 11Ј)*], 34.1 [C(7), C(7Ј)], 31.5 [C(9 or 9Ј)], 31.4
[C(9 or 9Ј)], 25.8 [C(12 or 12Ј)], 25.7 [C(12 or 12Ј)], 21.5 [C(13 or
[{Bis[(؊)-pineno]؊2,2Ј-bipyridine}(S,S/R,R-DACH)PtII](PF6)2 (41):
The synthesis, and purification of compound 41 was carried out as
described for compound 21 with L1PtCl2 (105 mg, 0.17 mmol),
(S,S)-diaminocyclohexane (23 mg, 0.20 mmol), and (R,R)-diamino-
cyclohexane (23 mg, 0.20 mmol) in water/acetone (25 mL). Yield:
1
115 mg (71%). Ϫ H NMR (300 MHz, [D3]acetonitrile): δ ϭ 8.07
[s, 2 H, HϪC(3,3Ј)], 8.00 [s, 2 H, HϪC(6,6Ј)], 5.38 [b, 2 H,
3
HbϪN(14,14Ј)], 4.77 [b, 2 H, HaϪN(14,14Ј)], 3.17 [d, J ϭ 3.4 Hz,
4 H, H2ϪC(7,7Ј)], 2.96 [m, 2 H, HϪC(10,10Ј)], 2.83 [ddd, 2J ϭ
11.2 Hz, 3J ϭ 5.2, 5.2 Hz, 2 H, HbϪC(9,9Ј)], 2.63 [m, 2 H,
2
HϪC(15,15Ј)], 2.40 [m, 2 H, HϪC(8,8Ј)], 2.15 [d, J ϭ 12.0 Hz, 2
2
H, HaϪC(16,16Ј)], 1.65 [d, J ϭ 8.9 Hz, 2 H, HaϪC(17,17Ј)], 1.45
2
[s, 8 H, H3ϪC(12,12Ј), HbϪC(16,16Ј)], 1.25 [d, J ϭ 8.9 Hz, 2 H,
2
HbϪC(17,17Ј)], 1.24 [d, J ϭ 11.2 Hz, 2 H, HaϪC(9,9Ј)], 0.67 [s, 6
H, H3ϪC(13,13Ј)]. Ϫ 13C NMR (75 MHz, [D3]acetonitrile): δ ϭ
155.1, 154.4, 153.3, 148.9 [C(4,4Ј)], 146.7 [C(6,6Ј)], 124.1 [C(3,3Ј)],
62.5 [C(15,15Ј)], 45.2 [C(10,10Ј)], 40.3 [C(8,8Ј)], 36.7 [C(11,11Ј)],
34.2 [C(7,7Ј)], 33.2 [C(16,16Ј)], 31.6 [C(9,9Ј)], 25.8 [C(12,12Ј)], 24.8
[C(17,17Ј)], 21.5 [C(13,13Ј)]. Ϫ FAB-MS: m/z (%) ϭ 798 (25) [Mϩ
Ϫ PF6], 654 (75) [Mϩ Ϫ 2 PF6], 541 (19) [Mϩ Ϫ DACH], 326 (21),
307 (83), 248 (30), 154 (100).
13Ј)], 21.4 [C(13 or 13Ј)]. Ϫ FAB-MS: m/z (%) ϭ 758 (12) [Mϩ
Ϫ
PF6], 612 (51) [Mϩ Ϫ 2 PF6], 598 (11) [Mϩ Ϫ CH3], 538 (21) [Mϩ
Ϫ en], 307 (100). Ϫ The asterisk * denotes NMR signals of the
other possible diastereomers.
[{Bis[(؊)-pineno]؊2,2Ј-bipyridine}(piperazine)PtII](PF6)2 (71): The
synthesis, and purification of compound 71 was carried out as de-
scribed for compound 11 with L1PtCl2 (56 mg, 0.092 mmol) and
piperazine (14 mg, 0.16 mmol) in water/acetone (20 mL). Yield:
30 mg (36%). Ϫ 1H NMR (360 MHz, [D3]acetonitrile): δ ϭ 8.37 [s,
PtϪHJ ϭ 33.5 Hz, 2 H, HϪC(6,6Ј)], 8.04 [s, 2 H, HϪC(3,3Ј)], 5.73
[{Bis[(؊)-pineno]؊2,2Ј-bipyridine}(N,NЈ-dimethylethylenediamine)-
PtII](PF6)2 (51): The synthesis, and purification of compound 51
was carried out as described for compound 11 with L1PtCl2
(60 mg, 0.098 mmol) and dimethylethylenediamine (20 µL,
0.18 mmol) in water/acetone (20 mL). Yield: 55 mg (61%). Ϫ 1H
NMR (500 MHz, [D3]acetonitrile): δ ϭ 8.09 [s, 4 H, HϪC(3,3Ј),
HϪC(3,3Ј)*], 8.06 [s, 0.30 H, HϪC(3,3Ј)*], 8.03 [s, 0.30 H,
HϪC(3,3Ј)*], 7.97 [s, 2 H, HϪC(6,6Ј)], 7.96 [s, 2 H, HϪC(6,6Ј)*],
7.95 [s, 0.30 H, HϪC(6,6Ј)*], 7.94 [s, 0.30 H, HϪC(6,6Ј*), 5.78 [b,
2
[b, 2 H, HϪN(14,14Ј)], 3.78 [d, J ϭ 7.0 Hz, 4 H, HbϪC(15,15Ј),
HbϪC(16,16Ј)], 3.19 [d, 3J ϭ 2.3 Hz, 4 H, H2ϪC(7,7Ј)], 3.00 [d,
2J ϭ 7.0 Hz, 4 H, HaϪC(15,15Ј), HaϪC(16,16Ј)], 2.95 [dd, 3J ϭ 5.1,
2
2
3
0.30 H, HϪN(14,14Ј)*], 5.60 [b, 4 H, HϪN(14,14Ј)], 3.47 [d, J ϭ
5.1 Hz, 2 H, HϪC(10,10Ј)], 2.84 [dd, J ϭ 10.0 Hz, J ϭ 5.1 Hz, 2
H, HbϪC(9,9Ј)], 2.41 [m, H, HϪC(8,8Ј)], 1.47 [s, H,
3
8.8 Hz, 4 H, HaϪC(15,15Ј), HaϪC(15,15Ј)*], 3.19 [d, J ϭ 2.3 Hz,
2
6
8 H, H2ϪC(7,7Ј), H2ϪC(7,7Ј)*], 3.04 [dd, 3J ϭ 5.4, 5.4 Hz, 4 H,
2
H3ϪC(12,12Ј)], 1.25 [d, J ϭ 10.0 Hz, 2 H, HaϪC(9,9Ј)], 0.69 [s, 6
H, H3ϪC(13,13Ј)].
HϪC(10,10Ј), HϪC(10,10Ј)*], 2.89 [d, 3J
ϭ
6.5 Hz,
6 H,
H3ϪC(N14,14Ј)], 2.88 [d, 3J ϭ 6.5 Hz, 6 H, H3ϪC(N14,14Ј)*], 2.83
[dd, 2J ϭ 9.9 Hz, 3J ϭ 5.4 Hz, 4 H, HbϪC(9,9Ј), HbϪC(9,9Ј)*], [{Bis[(؊)-pineno؊2,2Ј-bipyridine}(homopiperazine)PtII](PF6)2 (81):
2.65 [d, 2J ϭ 8.8 Hz, 4 H, HbϪC(15,15Ј), HbϪC(15,15Ј)*], 2.40 [m, The synthesis, and purification of compound 81 was carried out as
4 H, HϪC(8,8Ј), HϪC(8,8Ј)*], 1.46 [s, 6 H, H3ϪC(12,12Ј)], 1.45 [s, described for compound 11 with L1PtCl2 (100 mg, 0.16 mmol) and
6 H, H3ϪC(12,12Ј)*], [1.25 [d, 2J ϭ 9.9 Hz, 2 H, HaϪC(9,9Ј)], 1.23
homopiperazine (50 mg, 0.5 mmol) in water/acetone (30 mL).
[d, 2J ϭ 9.9 Hz, 2 H, HaϪC(9,9Ј)*], 0.68 [s, 6 H, H3ϪC(13,13Ј), Yield: 110 mg (72%). Ϫ 1H NMR (500 MHz, [D3]acetonitrile): δ ϭ
0.66 [s, 6 H, H3ϪC(13,13Ј)*]. Ϫ 13C NMR (125 MHz, [D3]aceton-
8.28 [s, 1 H, HϪC(6 or 6Ј)], 8.27 [s, 1 H, HϪC(6 or 6Ј)], 8.06 [s, 2
itrile): δ ϭ 155.7 [C(2, 4 or 5)], 155.6 [C(2, 4 or 5)*], 153.6 [C(2, 4 H, HϪC(3,3Ј)], 6.06 (b, 1 H, HϪN(14 or 14Ј)],)], 6.03 [b, 1 H,
or 5)], 153.5 [C(2, 4 or 5)*], 149.4 [C(2, 4 or 5)], 149.3 [C(2, 4 or HϪN(14 or 14Ј)], 3.61 [m, 2 H, HbϪC(16,16Ј)], 3.49 [m, 2 H,
3
5)*], 146.1 [C(6,6Ј), 145.9 [C(6,6Ј)*], 124.8 [C(3,3Ј)], 54.1 HbϪC(15,15Ј)], 3.36 [m, 2 H, HaϪC(16,16Ј)], 3.18 [d, J ϭ 2.4 Hz,
[C(15,15Ј)], 45.5 [C(10,10Ј)], 45.3 [C(10,10Ј)*], 43.6 [CϪN(14,14Ј)],
43.5 (CϪN(14,14Ј)*], 40.2 [C(8,8Ј)], 40.1 [C(11,11Ј)*], 34.1
4 H, H2ϪC(7,7Ј)], 2.98 [m, 4 H, HaϪC(15, 15Ј), HϪC(10,10Ј)],
2.82 [dd, J ϭ 9.9 Hz, J ϭ 5.8 Hz, 2 H, HbϪC(9,9Ј)], 2.40 [m, 2
2
3
[C(7,7Ј)], 34.0 [C(7,7Ј)*], 31.5 [C(9,9Ј)], 31.4 [C(9,9Ј)*], 25.8 H, HϪC(8,8Ј)], 2.14 [m, 2 H, H2ϪC-(17)], 1.46 [s, 3 H, H3ϪC(12
2
[C(12,12Ј)], 25.7 [C(12,12Ј)*], 21.5 [C(13,13Ј)], 21.4 [C(13,13Ј)*]. Ϫ or 12Ј)], 1.45 [s, 3 H, H3ϪC(12 or 12Ј)], 1.24 [d, J ϭ 9.9 Hz, 2 H,
FAB-MS: m/z (%) ϭ 772 (10) [Mϩ Ϫ PF6], 627 (44) [Mϩ Ϫ 2 PF6],
598 (13) [Mϩ Ϫ 2 CH3], 537 (17), 460 (26), 307 (100). Ϫ The aster-
isk * denotes NMR signals of the other possible diastereomers.
HaϪC(9,9Ј)], 0.68 [s, 6 H, H3ϪC(13,13Ј)]. Ϫ 13C NMR (125 MHz,
[D3]acetonitrile): δ ϭ 153.9 [C(2,2Ј)], 151.9 [C(5 or 5Ј)], 151.8 [C(5Ј
or 5)], 147.4 [C(4 or 4Ј)], 147.3 [C(4Ј or 4)], 146.2 [C(6 or 6Ј)], 146.1
1216
Eur. J. Inorg. Chem. 2001, 1207Ϫ1220

PtII Compounds with Bis(pinene)-Fused Bipyridine Ligands
FULL PAPER
[C(6Ј or 6)], 122.6 [C(3,3Ј)], 50.9 [C(16, 16Ј)], 50.0 [C(15,15Ј)], 43.9
[{Bis[(؊)-pineno]؊2,2Ј-bipyridine}(S,S-DACH)PtII](PF6)2 (32): The
[C(10,10Ј)], 38.9 [C(8,8Ј)], 38.3 [C(11,11Ј)], 32.7 [C(7,7Ј)], 30.1 synthesis, and purification of compound 32 was carried out as de-
[C(9,9Ј)], 24.5 [C(12 or 12Ј)], 24.4 [C(12Ј or 12)], 20.2 [C(13,13Ј)],
18.6[C(17)].
scribed for compound 21 with L2PtCl2 (106 mg, 0.17 mmol) and
(S,S)-diaminocyclohexane (34 mg, 0.30 mmol) in water/acetone (25
mL). Yield: 112 mg (68%) white powder of 32. Ϫ 1H NMR
(300 MHz, [D3]acetonitrile): δ ϭ 7.95 [d, 3J ϭ 8.1 Hz, 2 H,
HϪC(3,3Ј)], 7.79 [d,3J ϭ 8.1 Hz, 2 H, HϪC(4,4Ј)], 5.48 [b, 2 H,
HaϪN(14,14Ј)], 4.83 [b, 2 H, HbϪN(14,14Ј)], 3.01 [dd, 2J ϭ
17.1 Hz, 3J ϭ 2.7 Hz, 4 H, Ha-HbϪC(7,7Ј)], 2.97 [dd, 3J ϭ 5.8,
L2PtCl2: K2PtCl4 (1.20 g, 2.90 mmol) was dissolved in HCl (0.2 ,
100 mL) and L2 (1.0 g, 2.90 mmol) was added. The synthesis and
purification was carried out in the same way as described for
L1PtCl2 above, except that the reaction time was increased to 10 h.
Yellow crystals (1.32 g, 75%) of L2PtCl2 were obtained. Ϫ 1H
NMR (300 MHz, CDCl3): δ ϭ 7.97 [d, 3J ϭ 7.7 Hz, 2 H,
2
3
5.8 Hz, 2 H, HϪC(10,10Ј)], 2.74 [dd, J ϭ 10.1 Hz, J ϭ 5.1 Hz, 2
H, HbϪC(9,9Ј)]; 2.46 [m, 6 H, HϪC(8,8Ј), H2ϪC(15,15Ј)], 2.19 [d,
2J ϭ 12.4 Hz, 2 H, HaϪC(16,16Ј)], 1.63 [d, 2J ϭ 8.8 Hz, 2 H,
HbϪC(16,16Ј)], 1.42 [s, 6 H, H3ϪC(12,12Ј)], 1.38 (b, 2 H,
HaϪC17,17Ј)], 1.30 [d, 2J ϭ 10.1 Hz, 2 H, HaϪC(9,9Ј)], 1.22 [d,
2J ϭ 10.1 Hz, 2 H, HbϪC(17,17Ј)], 0.64 [s, 6 H, H3ϪC(13,13Ј)]. Ϫ
13C NMR (75 MHz, [D3]acetonitrile): δ ϭ 139.1, 122.2, 62.7, 47.7,
40.9, 37.4, 32.7, 31.5, 30.5, 25.6, 24.9, 21.7. Ϫ FAB-MS: m/z (%) ϭ
3
2
HϪC(3,3Ј)], 7.39 [d, J ϭ 7.7 Hz, 2 H, HϪC(4,4Ј)], 4.03 [dd, J ϭ
3
2
18.1 Hz, J ϭ 2.6 Hz, 2 H, HbϪC(7,7 Ј)], 3.91 [dd, J ϭ 18.1 Hz,
3J ϭ 3.1 Hz, 2 H, HaϪC(7,7 Ј)], 2.71 [dd, 3J ϭ 5.8, 5.8 Hz, 2 H,
HϪC(10,10,Ј)], 2.61 [ddd, 2J ϭ 9.8 Hz, 3J ϭ 5.8, 5.8 Hz, 2 H,
HbϪC(9,9Ј)], 2.36 [m, 2 H, HϪC(8,8Ј)], 1.35 [s, H3ϪC(12,12Ј)],
1.16 [d, J ϭ 9.8 Hz, HaϪC(9,9Ј)], 0.62 [s, H3ϪC(13,13Ј)]. Ϫ 13C
2
NMR (75 MHz, CDCl3): δ ϭ 163.6 [C(2,2Ј)], 156.8 [C(6,6Ј)], 145.9
[C(5,5Ј)], 135.9 [C(4,4Ј)], 119.8 [C(3,3Ј)], 46.8 [C(10,10Ј)], 40.0
[C(8,8Ј)], 39.1 [C(7,7Ј)], 36.4 [C(11,11Ј)], 30.9 [C(9,9Ј)], 25.6
[C(12,12Ј)], 21.9 [C(13,13Ј)]. Ϫ 195Pt NMR (64.376 MHz, CDCl3):
798 (11) [Mϩ Ϫ PF6], 652 (54) [Mϩ Ϫ 2 PF6], 538 (41) [Mϩ
Ϫ
DACH], 439 (12), 345 (18), 307 (20), 154 (100).
[{Bis[(؊)-pineno]؊2,2Ј-bipyridine}(S,S/R,R-DACH)PtII](PF6)2 (42):
The synthesis, and purification of compound 32 was carried out as
described for compound 21 with L2PtCl2 (92 mg, 0.15 mmol),
(S,S)-diaminocyclohexane (32 mg, 0.28 mmol) and (R,R)-diamino-
cyclohexane (32 mg, 0.28 mmol) in water/acetone (25 mL). Yield:
108 mg (76%) white powder of 42. Ϫ 1H NMR (300 MHz, [D3]ace-
ϩ
see Table 1. Ϫ FAB-MS: m/z (%) ϭ 1185 (80) [M2 Ϫ Cl], 1112*
(9), 1075* (4), 1015* (4), 919* (45), 882* (23), 841* (21), 575 (80)
[Mϩ
Ϫ Cl], 537 (100) (* further dimer fragments). Ϫ
C24H28Cl2N2Pt (610.5): calcd. C 47.22, H 4.62, N 4.59, found C
49.0, H 4.71, N 4.49. Ϫ Crystal structure analysis see Tables 3 and
8, Figure 2.
3
tonitrile): δ ϭ 7.95 [d, 3J ϭ 8.1 Hz, 2 H, HϪC(3,3Ј)], 7.79 [d, J ϭ
[{Bis[(؊)-pineno]؊2,2Ј-bipyridine}(ethylenediamine)PtII](PF6)2 (12):
The synthesis, and purification of compound 12 was carried out as
described for compound 11 with L2PtCl2 (100 mg, 0.16 mmol) and
ethylenediamine (13 µL, 0.19 mmol) in water/acetone (20 mL).
Yield: 105 mg (72%). Ϫ 1H NMR (300 MHz, [D3]acetonitrile): δ ϭ
8.1 Hz, 2 H, HϪC(4,4Ј)], 5.48 [b, 2 H, HaϪN(14,14Ј)], 4.82 [b, 2
2
3
H, HbϪN(14,14Ј)], 3.01 [dd, J ϭ 17.1 Hz, J ϭ 2.7 Hz, 4 H, Ha-
3
HbϪC(7,7Ј)], 2.97 [dd, J ϭ 5.8 Hz, 2 H, HϪC(10,10Ј)], 2.74 [dd,
2J ϭ 10.1 Hz, 3J ϭ 5.1 Hz, 2 H, HbϪC(9,9Ј)], 2.46 [m, 4 H,
HϪC(8,8Ј), HϪC(15,15Ј)], 2.19 [d, 2J
ϭ 12.4 Hz, 2 H,
3
3
2
7.96 [d, J ϭ 8.1 Hz, 2 H, HϪC(3,3Ј)], 7.80 [d, J ϭ 8.1 Hz, 2 H,
HaϪC(16,16Ј)], 1.63 [d, J ϭ 8.8 Hz, 2 H, HbϪC(16,16Ј)], 1.42 [s,
6 H, H3ϪC(12,12Ј)], 1.38 (b, 2 H, HaϪC17,17Ј)], 1.30 [d, 2J ϭ
10.1 Hz, 2 H, HaϪC(9,9Ј)-(S,S-DACH), 1.24 [d, 2J ϭ 10.1 Hz, 2
3
HϪC(4,4Ј)], 5.24 [b, 4 H, H2ϪN(14,14,Ј)], 2.98 [d, J ϭ 3.0 Hz, 4
H, H2ϪC(7,7Ј)], 2.97 [dd, 3J ϭ 5.6, 5.6 Hz, 2 H, HϪC(10,10Ј)],
2
3
H, HaϪC(9,9Ј)-(R,R-DACH)], 1.22 [d, 2J
ϭ 10.1 Hz, 2 H,
2.75 [dd, J ϭ 10.1 Hz, J ϭ 5.6 Hz, 2 H, HbϪC(9,9Ј)], 2.60 [b, 4
H, H2ϪC(15,15Ј)], 2.45 [m, 2 H, HϪC(8,8Ј)], 1.43 [s, 6 H,
H3ϪC(12,12Ј)], 1.26 [d, J ϭ 10.1 Hz, 2 H, HaϪC(9,9Ј)], 0.66 [s, 6
HbϪC(17,17Ј)], 0.68 [s, 6 H, H3ϪC(13,13Ј)-(R,R-DACH)], 0.64 [s,
6 H, H3ϪC(13,13Ј)-(S,S-DACH)]. Ϫ 13C NMR (75 MHz, [D3]ace-
tonitrile): δ ϭ 139.1, 122.2, 62.7, 47.7, 40.9, 37.4, 32.7, 31.5, 30.5,
25.6, 24.9, 21.7. Ϫ FAB-MS: m/z (%) ϭ 798 (12) [Mϩ Ϫ PF6], 652
(38) [Mϩ Ϫ 2 PF6], 538 (20) [Mϩ Ϫ DACH], 345 (11), 307 (73),
154 (100).
2
H, H3ϪC(13,13Ј)]. Ϫ 13C NMR (75 MHz, [D3]acetonitrile): δ ϭ
161.1 [C(2,2Ј)], 157.3 [C(6,6Ј)], 148.0 [C(5,5Ј)]; 138.9 [C(4,4Ј)], 121.9
[C(3,3Ј)], 47.8 [C(15,15Ј)]; 47.4 [C(10,10Ј)], 40.6 [C(8,8Ј)], 39.7
[C(11,11Ј)], 37.1 [C(7,7Ј)], 31.0 [C(9,9Ј)], 25.4 [C(12,12Ј)], 21.3
[C(13,13Ј)]. Ϫ FAB-MS: m/z (%) ϭ 744 (12) [Mϩ Ϫ PF6], 598 (70)
[Mϩ Ϫ 2 PF6], 538 (33) [Mϩ Ϫ en], 154 (100).
L3PtCl2: K2PtCl4 (240.7 mg, 0.58 mmol) was dissolved in HCl (0.2
[{Bis[(؊)-pineno]؊2,2Ј-bipyridine}(R,R-DACH)PtII](PF6)2
(22): , 33 mL) and L3 (200 mg, 0.58 mmol) was added. The synthesis
The synthesis, and purification of compound 22 was carried out as
described for compound 21 with L2PtCl2 (112 mg, 0.18 mmol) and
(R,R)-diaminocyclohexane (35 mg, 0.30 mmol) in water/acetone
(25 mL). Yield: 120 mg (70%) white powder of 22. Ϫ 1H NMR
(300 MHz, [D3]acetonitrile): δ ϭ 7.95 [d, 3J ϭ 8.1 Hz, 2 H,
and purification was carried the same way as described for L2PtCl2
above. Yellow crystals (260 mg, 73%) of L3PtCl2 were obtained.
Ϫ1H NMR (300 MHz, CDCl3): δ ϭ 7.97 [d, 3J ϭ 8.1 Hz, 2 H,
3
2
HϪC(3,3Ј)], 7.37 [d, J ϭ 8.1 Hz, 2 H, HϪC(4,4Ј)], 4.03 [dd, J ϭ
3
2
18.7 Hz, J ϭ 2.6 Hz, 2 H, HbϪC(7,7 Ј)], 3.91 [dd, J ϭ 18.7 Hz,
HϪC(3,3Ј)], 7.79 [d,3J ϭ 8.1 Hz, 2 H, HϪC(4,4Ј)], 5.46 [b, 2 H, 3J ϭ 3.1 Hz, 2 H, HaϪC(7,7 Ј)], 2.72 [dd, 3J ϭ 5.4, 5.4 Hz, 2 H,
HaϪN(14,14Ј)], 4.80 [b, 2 H, HbϪN(14,14Ј)], 3.01 [dd, 2J ϭ HϪC(10,10,Ј)], 2.61 [ddd, 2J ϭ 9.6 Hz, 3J ϭ 5.6 Hz, 2 H,
17.1 Hz, 3J ϭ 2.7 Hz, 4 H, Ha-HbϪC(7,7Ј)], 2.97 [dd, 3J ϭ 5.1, HbϪC(9,9Ј)], 2.38 [m, 2 H, HϪC(8,8Ј)], 1.37 [s, H3ϪC(12,12Ј)],
2
3
2
5.1 Hz, 2 H, HϪC(10,10Ј)], 2.74 [dd, J ϭ 10.1 Hz, J ϭ 5.1 Hz, 2
1.13 [d, J ϭ 9.6 Hz, HaϪC(9,9Ј)], 0.66 [s, H3ϪC(13,13Ј)]. Ϫ 13C
H, HbϪC(9,9Ј)], 2.46 [m, 4 H, HϪC(8,8Ј), HϪC(15,15Ј)], 2.19 [d, NMR (75 MHz, CDCl3): δ ϭ 163.6 [C(2,2Ј)], 156.8 [C(6,6Ј)], 145.9
2J ϭ 12.4 Hz, 2 H, HaϪC(16,16Ј)], 1.63 [d, 2J ϭ 8.8 Hz, 2 H, (5,5Ј)], 135.9 [C(4,4Ј)], 119.8 [C(3,3Ј)], 46.8 [C(10,10Ј)], 40.0
HbϪC(16,16Ј)], 1.42 [s, 6 H, H3ϪC(12,12Ј)], 1.38 (b, 2 H,
[C(8,8Ј)], 39.1 [C(11,11Ј)], 36.4 [C(9,9Ј)], 25.6 [C(12,12Ј)], 21.9
HaϪC17,17Ј)], 1.24 [d, 2J H, HbϪC(17,17Ј), [C(13,13Ј)]. Ϫ 195Pt NMR (64.376 MHz, CDCl3): see Table 1. Ϫ
ϭ
10.1 Hz,
4
HaϪC(9,9Ј)], 0.68 [s, 6 H, H3ϪC(13,13Ј)]. Ϫ 13C NMR (75 MHz, FAB-MS: m/z (%) ϭ 609 (13) [Mϩ], 578 (80) [Mϩ Ϫ Cl], 539 (48)
[D3]acetonitrile): δ ϭ 139.1, 122.2, 62.7, 47.7, 40.9, 37.4, 32.7, 31.5,
[Mϩ Ϫ 2 Cl], 506 (18), 462 (12), 345 (40), 307 (78), 289 (68), 154
(100). Ϫ C24H28Cl2N2Pt (610.5): calcd. C 47.22, H 4.62, N 4.59,
30.5, 25.6, 24.9, 21.7. Ϫ FAB-MS: m/z (%) ϭ 798 (16) [Mϩ Ϫ PF6],
653 (73) [Mϩ Ϫ 2 PF6], 539 (51) [Mϩ Ϫ DACH], 345 (26), 307 (31), found C 45.77, H 4.74, N 4.70. Ϫ Crystal structure analysis see
176 (32), 154 (100).
Tables 4 and 8, Figure 3.
Eur. J. Inorg. Chem. 2001, 1207Ϫ1220
1217

B. Kolp, D. Abeln, H. Stoeckli-Evans, A. v. Zelewsky
[{Bis[(؊)-(؉)-pineno]؊2,2Ј-bipyridine}(ethylenediamine)PtII](PF6)2 H, HbϪC(9,9Ј)], 2.44 (b, 2 H, DACH), 2.42 [m, 2 H, HϪC(8,8Ј)],
FULL PAPER
(13): The synthesis, and purification of compound 13 was carried
out as described for compound 11 with L3PtCl2 (50 mg,
2.04 (b, 2 H, DACH), 1.61 (b, 2 H, DACH), 1.50 [s, 6 H,
H3ϪC(12,12Ј)], 1.39 [d, 2J ϭ 10.4 Hz, 2 H, HaϪC(9,9Ј)], 1.19 (b, 2
0.081 mmol) and ethylenediamine (10 µL, 0.15 mmol) in water/ H, DACH), 0.68 [s, 6 H, H3ϪC(13,13Ј)]. Ϫ FAB-MS: m/z (%) ϭ
acetone (15 mL). Yield: 51 mg (70%). Ϫ 1H NMR (300 MHz,
799 (12) [Mϩ Ϫ PF6], 652 (70) [Mϩ Ϫ 2 PF6], 537 (34) [Mϩ
Ϫ
DACH], 345 (11), 307 (14), 154 (100).
3
[D3]acetonitrile): δ ϭ 7.96 [d, J ϭ 8.1 Hz, 2 H, HϪC(3,3Ј)], 7.80
[d, 3J ϭ 8.1 Hz, 2 H, HϪC(4,4Ј)], 5.26 [b, 4 H, H2ϪN(14,14Ј)],
2.98 [d, 3J ϭ 2.4 Hz, 6 H, H2ϪC(7,7Ј), HϪC(10,10Ј)], 2.76 [dd,
2J ϭ 10.1 Hz, 3J ϭ 5.2 Hz, 2 H, HbϪC(9,9Ј)]; 2.60 [b, 4 H,
[{Bis[(؊)-β-pineno]؊2,2Ј-bipyridine}(R,R/S,S-DACH)PtII](PF6)2
(44): The synthesis, and purification of compound 44 was carried
out as described for compound 21 with L4PtCl2 (87 mg,
0.14 mmol), (R,R)-diaminocyclohexane (20 mg, 0.18 mmol), and
(S,S)-diaminocyclohexane (20 mg, 0.18 mmol) in water/acetone (15
mL). Yield: 70 mg (52%) white powder of 44. Ϫ 1H NMR
H2ϪC(15,15Ј)], 2.45 [m,
2 H, HϪC(8,8Ј)], 1.42 [s, 6 H,
H3ϪC(12,12Ј)], 1.32 [d, 2J ϭ 10.1 Hz, HaϪC(9,9Ј)], 0.63 [s, 6 H,
H3ϪC(13,13Ј)]. Ϫ 13C NMR (75 MHz, [D3]acetonitrile): δ ϭ 161.3
[C(2,2Ј)], 157.4 [C(6,6Ј)], 148.2 [C(5,5Ј)]; 139.0 [C(4,4Ј)], 121.9
[C(3,3Ј)], 47.7 [C(15,15Ј)]; 47.5 [C(10,10Ј)], 40.6 [C(8,8Ј)], 39.7
[C(11,11Ј)], 37.1 [C(7,7Ј)]; 31.2 [C(9,9Ј)], 25.4 [C(12,12Ј)]; 21.2
[C(13,13Ј)]. Ϫ FAB-MS: m/z (%) ϭ 744 (14) [Mϩ Ϫ PF6], 600 (66)
[Mϩ Ϫ 2 PF6], 541 (42) [Mϩ Ϫ en], 345 (16), 165 (28), 154 (100).
(300 MHz, [D3]acetonitrile):
δ
ϭ
8.02 [s,
4
H, HϪC(3,3Ј),
H,
HϪC(4,4Ј)], 4.58 [b, H, H2ϪN(14,14Ј)], 3.11 [m,
4
6
2
3
H2ϪC(7,7Ј), HϪC(10,10Ј)], 2.87 [dd, J ϭ 10.7 Hz, J ϭ 5.7 Hz 2
H, HbϪC(9,9Ј)], 2.44 (b, 2 H, DACH), 2.42 [m, 2 H, HϪC(8,8Ј)],
2.03 (b, 2 H, DACH), 1.60 (b, 2 H, DACH), 1.50 [s, 6 H,
H3ϪC(12,12Ј)-R,R-DACH], 1.49 [s, H3ϪC(12,12Ј)-S,S-DACH, ra-
L4PtCl2: Compound L4 (700 mg, 2.03 mmol) was added to a solu-
tion of K2PtCl4 (843.5 mg, 2.03 mmol) dissolved in HCl (0.2 ,
80 mL). After stirring for 10 h at reflux, the yellow precipitate was
2
tio see discussion], 1.39 [d, J ϭ 10.7 Hz, 2 H, HaϪC(9,9Ј)], 1.37
(b, 2 H, DACH), 1.19 (b, 2 H, DACH), 0.72 [s, 6 H, H3ϪC(13,13 Ј)-
filtered off and washed with water. The crude product was dried at S,S-DACH, ratio see discussion], 0.68 [s, 6 H, H3ϪC(13,13 Ј)-R,R-
50 °C in the vacuum oven. Recrystallization from chloroform/hept-
ane gave yellow crystals (786 mg, 63%) of L4PtCl2. Ϫ 1H NMR
(300 MHz, [D3]acetonitrile): δ ϭ 8.15 [d, 3J ϭ 7.7 Hz, 2 H,
DACH]. Ϫ FAB-MS: m/z (%) ϭ 798 (16) [Mϩ Ϫ PF6], 653 (63)
[Mϩ Ϫ 2 PF6], 539 (34) [Mϩ Ϫ DACH], 307 (28), 154 (100).
L5PtCl2: Compound L5 (437 mg, 1.26 mmol) was added to a solu-
tion of K2PtCl4 (524 mg, 1.26 mmol) dissolved in HCl (0.2 , 50
mL). After stirring for 10 h at reflux, the yellow precipitate was
filtered off and washed with water. The crude product was dried at
50 °C in a vacuum oven. Recrystallization from chloroform/hept-
3
3
HϪC(3,3Ј)], 7.50 [d, J ϭ 7.7 Hz, 2 H, HϪC(4,4Ј)], 4.23 [dd, J ϭ
5.8, 5.8 Hz, 2 H, HϪC(10,10Ј)], 2.86 [d, 3J ϭ 2.6 Hz, 4 H,
H2ϪC(7,7Ј)], 2.79 [dd, 3J ϭ 5.8 Hz, 2J ϭ 9.8 Hz, 2 H, HbϪC(9,9Ј)],
2.25 [m, 2 H, HϪC(8,8Ј)], 1.42 [s, 6 H, H3ϪC(12,12Ј)], 1.27 [d,
2J ϭ 9.8 Hz, 2 H, HaϪC(9,9Ј)], 0.64 [s, 6 H, H3ϪC(13,13Ј)]. Ϫ 13C
NMR (75 MHz, CDCl3): δ ϭ 171.3 [C(2,2Ј)], 154.2 [C(6,6Ј)], 137.0
[C(4,4Ј)], 134.0 [C(5,5Ј)], 120.5 [C(3,3Ј)], 51.4 [C(10,10Ј)], 39.3
[C(11,11Ј)], 39.1 [C(8,8Ј)], 31.7 [C(7,7Ј)], 31.2 [C(9,9Ј)],
24.8[C(13,13Ј)], 21.6 [C(12,12Ј)]. Ϫ 195Pt NMR (64.376 MHz,
1
ane gave a yellow powder (560 mg, 72%) of L4PtCl2. Ϫ H NMR
(300 MHz, CDCl3): δ ϭ 9.15 [s, 1 H, HϪC(6Ј)], 7.85 [d, 3J ϭ
7.9 Hz, 1 H, HϪC(3)], 7.75 [s, 1 H, HϪC(3Ј)], 7.50 [d, 3J ϭ 7.9 Hz,
1 H, HϪC(4)], 4.39 [dd, 2J ϭ 18.8 Hz, 3J ϭ 3.2 Hz, 1 H, HbϪC(7)],
3.60 [dd, 2J ϭ 18.8 Hz, 3J ϭ 2.8 Hz, 1 H, HaϪC(7)], 3.15 [dd, 2J ϭ
17.7 Hz, 3J ϭ 3.3 Hz, 1 H, HbϪC(7Ј)], 2.94 [dd, 2J ϭ 17.7 Hz, 3J ϭ
2.6 Hz, 1 H, HaϪC(7Ј)], 2.87 [dd, 3J ϭ 5.8, 5.8 Hz, 1 H, HϪC(10Ј)],
ϩ
CDCl3): see Table 1. Ϫ FAB-MS: m/z (%) ϭ 1186 (6) [M2 Ϫ Cl],
920 (20) and 883 (8) further dimer fragments, 610 (7) [Mϩ], 575
(54) [Mϩ Ϫ Cl], 536 (87) [Mϩ Ϫ 2 Cl], 522 (26), 345 (100). Ϫ
C24H28Cl2N2Pt (610.5): calcd. C 47.22, H 4.62, N 4.59; found C
47.00, H 4.62, N 4.44. Ϫ Crystal structure analysis see Tables 5 and
8, Figure 4.
3
2
2.79 [dd, J ϭ 5.8, 5.8 Hz, 1 H, HϪC(10)], 2.71 [dd, J ϭ 9.9 Hz,
3J ϭ 5.8 Hz, 1 H, HbϪC(9Ј)], 2.62 [dd, J ϭ 9.9 Hz, J ϭ 5.8 Hz,
1 H, HbϪC(9)], 2.42 [m, 1 H, HϪC(8)], 2.34 [m, 1 H, HϪC(8Ј)],
1.39 [s, 3 H, H3ϪC(12Ј)], 1.36 [s, 3 H, H3ϪC(12)], 1.15 [d, 2J ϭ 9.9
Hz, 2 H, HaϪC(9,9Ј)], 0.59 [s, 3 H, H3ϪC(13 or 13Ј)], 0.55 [s, 3 H,
H3ϪC(13Ј or 13)]. Ϫ 13C NMR (75 MHz, CDCl3): δ ϭ 164.7
[C(2Ј)], 156.1 [C(2)], 155.9 [C(6)], 149.3 [C(4Ј)], 147.5 [C(5)], 145.3
[C(5Ј)], 144.2 (6Ј)], 135.2 [C(4)], 122.4 (3Ј)], 120.3 (3)], 47.2 (10)],
2
3
[{Bis[(؊)-β-pineno]؊2,2Ј-bipyridine}(ethylenediamine)PtII](PF6)2
(14): The synthesis, and purification of compound 14 was carried
out as described for compound 11 with L4PtCl2 (100 mg,
0.16 mmol) and ethylenediamine (12 µL, 0.18 mmol) in water/acet-
1
one (20 mL). Yield: 85 mg (58%) white powder of 14. Ϫ H NMR 44.7 [C(10Ј)], 39.9 [C(8)], 39.4 [C(8Ј)], 39.1 [C(11)], 38.9 [C(7)], 38.6
(300 MHz, [D3]acetonitrile):
δ ϭ 8.02 [s, 4 H, HϪC(3,3Ј), [C(9)], 33.4 [C(11Ј)], 31.1 [C(7Ј)], 30.3 [C(9Ј)], 25.6 [C(12)], 25.2
HϪC(4,4Ј)], 4.61 [b, H, H2ϪN(14,14Ј)], 3.10 [m,
4
6
H,
[C(12Ј)], 21.3 [C(13)], 21.2 [C(13Ј)]. Ϫ FAB-MS: m/z (%) ϭ 1186
2
3
H2ϪC(7,7Ј), HϪC(10,10Ј)], 2.87 [dd, J ϭ 10.0 Hz, J ϭ 5.7 Hz, 2 (8) [M2ϩ Ϫ Cl], 920 (9) and 842 (10) [further dimer fragments], 574
H, HbϪC(9,9Ј)], 2.65 [b, 4 H, H2ϪC(15,15Ј)], 2.40 [m, 2 H, (80) [Mϩ Ϫ Cl], 537 (54) [Mϩ Ϫ 2 Cl], 493 (20), 345 (66), 154 (100).
2
HϪC(8,8Ј)], 1.50 [s, 6 H, H3ϪC(12,12Ј)], 1.36 [d, J ϭ 10.0 Hz, 2 Ϫ C24H28Cl2N2Pt (610.5): calcd. C 47.22, H 4.62, N 4.59, found C
H, HaϪC(9,9Ј)], 0.70 [s, 6 H, H3ϪC(13,13Ј)]. Ϫ 13C NMR 47.37, H 4.70, N 4.59.
(75 MHz, [D3]acetonitrile): δ ϭ 141.1, 136.2, 121.6, 51.3, 48.3, 40.6,
[{Bis[(؊)-pineno]؊2,2Ј-bipyridine}(ethylenediamine)PtII](PF6)2 (15):
The synthesis and purification of compound 15 was carried out as
40.3, 31.8, 30.8, 25.6, 21.8, (two carbon atoms could not be ob-
served). Ϫ FAB-MS: m/z (%) ϭ 744 (36) [Mϩ Ϫ PF6], 599 (80)
described for compound 11 with L5PtCl2 (70 mg, 0.11 mmol) and
[Mϩ Ϫ 2 PF6], 536 (25) [Mϩ Ϫ en], 345 (100), 307 (81), 154 (100).
ethylenediamine (10 µL, 0.15 mmol) in water/acetone (20 mL).
[{Bis[(؊)-β-pineno]؊2,2Ј-bipyridine}(R,R-DACH)PtII](PF6)2 (24):
The synthesis, and purification of compound 24 was carried out as
described for compound 21 with L4PtCl2 (50 mg, 0.082 mmol) and
Yield: 65 mg (63%) white powder of 14. Ϫ 1H NMR (300 MHz,
CDCl3): δ ϭ 8.08 [s, 1 H, HϪC(6Ј)], 8.01 [d, 3J ϭ 7.8 Hz, 1 H,
HϪC(3)], 7.86 [s, 1 H, HϪC(3Ј)], 7.84 [d, 3J ϭ 7.9 Hz, 1 H,
(R,R)-diaminocyclohexane (15 mg, 0.13 mmol) in water/acetone HϪC(4)], 5.30 [b,
(15 mL). Yield: 43 mg (55%) white powder of 24. Ϫ 1H NMR HaϪN(14,14Ј)], 3.16 [d, 3J ϭ 2.7 Hz, 2 H, H2ϪC(7Ј)], 3.03 [dd,
(300 MHz, [D3]acetonitrile): 8.03 [s,
H, HϪC(3,3Ј), 3J ϭ 5.6, 5.6 Hz, 1 H, HϪC(10Ј)], 2.95 [m, 3 H, HϪC(10),
HϪC(4,4Ј)], 4.58 [b, H, H2ϪN(14,14Ј)], 3.11 [m, H, H2ϪC(7)], 2.84Ϫ2.61 [m, 6 H, H2ϪC(15), H2ϪC(15Ј), HbϪC(9),
H2ϪC(7,7Ј), HϪC(10,10Ј)], 2.86 [dd, J ϭ 10.4 Hz, J ϭ 5.6 Hz, 2 HaϪC(9Ј)], 2.47 [m, 1 H, HϪC(8)], 2.40 [m, 1 H, HϪC(8Ј)], 1.46
2 H, HbϪN(14,14Ј)], 5.18 [b, 2 H,
δ
ϭ
4
4
6
2
3
1218
Eur. J. Inorg. Chem. 2001, 1207Ϫ1220

PtII Compounds with Bis(pinene)-Fused Bipyridine Ligands
FULL PAPER
[s, 3 H, H3ϪC(12Ј)], 1.44 [s, 3 H, H3ϪC(12)], 1.27 [d, 2J ϭ 9.9 Hz, 2.8 Hz, 2 H, H2ϪC(7Ј)], 3.07Ϫ2.72 [m, 6 H, HϪC(10Ј), HϪC(10Ј),
2
1 H, HaϪC(9 or 9Ј)], 1.22 [d, J ϭ 9.9 Hz, 1 H, HaϪC(9 or 9Ј)],
H2ϪC(7), HbϪC(9), HbϪC(9Ј)], 2.54 (b, 2 H, DACH), 2.49 (b, 2
0.69 [s, 3 H, H3ϪC(13)], 0.67 [s, 3 H, H3ϪC(13Ј)]. Ϫ FAB-MS: H, DACH), 2.40 (m, 1 H, HϪC(8 or 8Ј)], 2.22 (m, 1 H, HϪC(8 or
m/z (%) ϭ 744 (21) [Mϩ Ϫ PF6], 600 (95) [Mϩ Ϫ 2 PF6], 543 (58) 8Ј)], 1.66 (b, 2 H, DACH), 1.46 [s, 3 H, H3ϪC(12Ј)], 1.44 [s, 3 H,
[Mϩ -en], 345 (40), 289 (82), 165 (42), 154 (100).
H3ϪC(12)], 1.43 (b, 2 H, DACH), 1.27Ϫ1.23 [m, 4 H, HaϪC(9),
HaϪC(9Ј), DACH], 0.67 [s, 3 H, H3ϪC(13)], 0.65 [s, 3 H,
H3ϪC(13)].
[{Bis[(؊)-pineno]؊2,2Ј-bipyridine}(S,S-DACH)PtII](PF6)2 (35): The
synthesis and purification of compound 35 was carried out as de-
scribed for compound 31 with L5PtCl2 (50 mg, 0.082 mmol) and
(S,S)-diaminocyclohexane (15 mg, 0.13 mmol) in water/acetone (20
mL). Yield: 55 mg (71%) white powder of 35. Ϫ 1H NMR
(300 MHz, CDCl3): δ ϭ 8.06 [s, 1 H, HϪC(6Ј)], 8.01 [d, 3J ϭ
7.9 Hz, 1 H, HϪC(3)], 7.86 [s, 1 H, HϪC(3Ј)], 7.85 [d, 3J ϭ 7.9 Hz,
1 H, HϪC(4)], 5.44 [b, 2 H, HbϪN(14,14Ј)], 4.86 [b, 2 H,
HaϪN(14,14Ј)], 3.16 [d, 3J ϭ 2.6 Hz, 2 H, H2ϪC(7Ј)], 3.07Ϫ2.73
[m, 6 H, HϪC(10Ј), HϪC(10Ј), H2ϪC(7), HbϪC(9), HbϪC(9Ј)],
2.54 (b, 2 H, DACH), 2.48 (b, 2 H, DACH), 2.40 [m, 1 H, HϪC(8
or 8Ј)], 2.21 [m, 1 H, HϪC(8 or 8Ј)], 1.66 (b, 2 H, DACH), 1.46 [s,
3 H, H3ϪC(12Ј)], 1.44 [s, 3 H, H3ϪC(12)], 1.43 (b, 2 H, DACH),
1.27Ϫ1.23 [m, 4 H, HaϪC(9), HaϪC(9Ј), DACH], 0.67 [s, 3 H,
H3ϪC(13)], 0.65 [s, 3 H, H3ϪC(13)].
Crystallographic Measurements and Structure Solution:[13] Suitable
crystals of L2 were grown from acetone as pale yellow rods. Intens-
ity data were collected at room temperature on a Stoe AED2 4-
circle diffractometer using Mo-Kα graphite-monochromated radi-
˚
ation (λ ϭ 0.71073 A) with ω/2Θ scans in the 2Θ range 5Ϫ51°.
The structure was solved by direct methods using the program
SHELXS-97[14]. The refinement and all further calculations were
carried out using SHELXL-97[15]. H-atoms were located from dif-
ference Fourier maps and refined isotropically. The non-H atoms
were refined anisotropically, using weighted full-matrix least-
squares method on F2. The absolute structure was assigned with
reference to the absolute structure of the ligand.
Crystallographic details are given in Table 8 and significant bond
lengths and bond angles are listed in Table 3.
[{Bis[(؊)-pineno]؊2,2Ј-bipyridine}(S,S/R,R-DACH)PtII](PF6)2 (45):
The synthesis and purification of compound 45 was carried out
as described for compound 41 with L5PtCl2 (50 mg, 0.082 mmol),
(R,R)-diaminocyclohexane (15 mg, 0.13 mmol) and (S,S)-diamino-
Suitable crystals for the platinum complexes were grown by dif-
fusion of heptane into a chloroform solution. The data for L2PtCl2
and L4PtCl2 were collected on a ‘Siemens SMART CCDЈ System,
cyclohexane (15 mg, 0.13 mmol) in water/acetone (20 mL). Yield:
1
55 mg (70%) white powder of 44. Ϫ H NMR (300 MHz, CDCl3): whereas a ‘STOE Image Plate Diffraction SystemЈ was used to col-
3
δ ϭ 8.07 [s, 1 H, HϪC(6Ј)], 8.02 [d, J ϭ 8.0 Hz, 1 H, HϪC(3)],
lect data for L3PtCl2. Determinations of the crystal class, orienta-
tion matrix, and unit-cell dimensions were performed in a standard
3
7.88 (s, 1 H, HϪC(3Ј)], 7.85 [d, J ϭ 8.0 Hz, 1 H, HϪC(4)], 5.45
3
[b, 2 H, HbϪN(14,14Ј)], 4.86 [b, 2 H, HaϪN(14,14Ј)], 3.16 [d, J ϭ fashion. The data were collected using monochromated Mo-Kα
Table 8. Crystallographic data
Compound
L2
L2PtCl2
L3PtCl2
L4PtCl2
Empirical formula
Mol. wt.
C24H28N2
344.48
C24H28Cl2N2Pt·2CHCl3
849.21
C24H28Cl2N2Pt·2CHCl3
849.21
C24H28Cl2N2Pt·1.25CHCl3
759.68
Temperature [K]
293 (2)
133 (2)
223 (2)
133 (2)
˚
Radiation, λ [A]
Mo-Kα, 0.71073
Monoclinic
P21 (No.4)
6.1105 (7)
10.9121 (18)
14.5203 (12)
90.0
Mo-Kα, 0.71073
Triclinic
Mo-Kα, 0.71073
Triclinic
Mo-Kα, 0.71073
Triclinic
Crystal system
Space group
¯
P1 (No.1)
11.1430 (3)
12.2591 (3)
12.9160 (3)
95.9000 (10)
114.4540 (10)
97.8210 (10)
1566.19 (7)
2
P1 (No.2)
P1 (No.1)
11.1789 (2)
13.4606 (2)
19.4045 (3)
74.6130 (10)
87.3960 (10)
83.63
˚
a [A]
11.2775 (11)
12.2377 (12)
12.8743 (13)
95.475 (12)
114.540 (11)
98.311 (12)
1575.3 (3)
2
˚
b [A]
˚
c [A]
α [°]
β [°]
γ [°]
94.383 (9)
90.0
965.4 (2)
2
1.185
3
˚
Z
V [A ]
2797.47 (8)
4
Density (calculated)
1.801
1.790
1.804
[g cmϪ3
]
Absorption coefficient
0.069
5.182
5.152
5.583
[mmϪ1
]
F [000]
372
828
828
1482
Crystal size [mm]
θ min. and max. [°]
Reflections
0.46 ϫ 0.23 ϫ 0.11
2.34 to 25.47
3802/1901
0.45 ϫ 0.29 ϫ 0.22
2.05 to 27.28
13528/10833
0.60 ϫ 0.30 ϫ 0.10
2.23 to 25.80
12237/5604
0.34 ϫ 0.28 ϫ 0.11
1.58 to 26.70
23429/18354
collected/unique
Absorpt. correct.
T min/T max
none
ψ-scan
0.196/0.308
Emp.-DIFABS
0.230/0.693
ψ-scan
0.197/0.514
Refinement method
Full-matrix least-squares
on F2
Full-matrix least-squares
Full-matrix least-squares
Full-matrix least-squares
on F2
10833/3/679
on F2
5604/4/339
on F2
18354/172/1259
Data/restraints/parameters
1901/1/348
Final R indices [I Ͼ 2σ(I)] R1 ϭ 0.0551 wR2 ϭ 0.0925 R1 ϭ 0.0280 wR2 ϭ 0.0703 R1 ϭ 0.0670 wR2 ϭ 0.1733 R1 ϭ 0.0384 wR2 ϭ 0.0880
R indices all data
Absolute structure
parameter
R1 ϭ 0.0979 wR2 ϭ 0.1067 R1 ϭ 0.0303 wR2 ϭ 0.0718 R1 ϭ 0.0732 wR2 ϭ 0.1787 R1 ϭ 0.0430 wR2 ϭ 0.0909
Ϫ1.00 (6)
0.034 (5)
Ϫ
0.000 (5)
Largest diff. peak
0.143 and Ϫ0.125
0.945 and Ϫ0.738
3.056 (near Pt-atom)
1.352 and Ϫ2.309
Ϫ3
˚
and hole [e.A
]
and Ϫ4.470
Eur. J. Inorg. Chem. 2001, 1207Ϫ1220
1219

B. Kolp, D. Abeln, H. Stoeckli-Evans, A. v. Zelewsky
FULL PAPER
[5]
[6]
˚
F. Kröhnke, Synthesis 1976, 1.
graphite-monochromated radiation (λ ϭ 0.71073 A). Absorption
correction for all three compounds were applied. The structures
were solved by direct methods using SHELXS-97[14] and refined
on F2 against all reflections with anisotropic thermal parameters
by full-matrix least-squares method using SHELXL-97.[15] Crystal
data and further details of structure refinement are summarized in
Table 8 and significant bond lengths and bond angles are listed in
Tables 3, 4, 5, and 6.
[6a]N. C. Fletcher, F. R. Keene, M. Ziegler, H. Stoeckli-Evans,
H. Viebrock, A. v. Zelewsky, Helvet. Chim. Acta. 1996, 79,
[6b]
´
Philippe Laine, private communication.
1192Ϫ1202. Ϫ
[7a]P. Collomb, S. Rupprecht, A. v. Zelewsky, to be published.
[7]
[8]
Ϫ
[7b]M. Gianini, A. v. Zelewsky, Synthesis 1996, 702Ϫ706
H. C. Brown, S. A. Weissman, P. T. Perumal, U. P. Dhokte, J.
Org. Chem. 1990, 55, 1217.
M. Ziegler, A. v. Zelewsky, Coordination Chemistry Reviews
1998, 177, 257Ϫ300.
G. R. Newkome, F. R. Fronczek, V. K. Gupta, W. E. Puckett,
D. C. Pantaleo, G. E. Kiefer, J. Am. Chem. Soc. 1982, 104,
1782Ϫ1783.
[9]
[10]
The molecular structures and crystallographic numbering
schemes for these compounds are illustrated in the PLATON[16]
and Cerius2[17] drawings in Figures 2, 3, 4, and 5.
[11]
E. J. Corey, J. C. Bailar, J. Am. Chem. Soc. 1959, 81,
2620Ϫ2629.
[12]
[13]
Acknowledgments
The authors wish to thank the Swiss National Science Foundation
for financial support. We also thank Felix Fehr for performing the
500 MHz Spectra.
T. G. Morgan, H. F. Burstall, J. Chem. Soc. 1934, 965.
Crystallographic data (excluding structure factors) for the
structures reported in this paper have been deposited with the
Cambridge Crystallographic Data Centre as supplementary
publication no. CCDC-117441 (L2), CCDC-115332 (L2PtCl2),
CCDC-115333 (L4PtCl2), and CCDC-115334 (L3PtCl2).
Copies of the data can be obtained free of charge on
application to CCDC, 12 Union Road, Cambridge CB2
1EZ, UK [Fax: (internat.) ϩ44Ϫ1223/336-033; E-mail:
deposit@ccdc.cam.ac.uk].
[1]
W. H. Mills, T. H. H. Quibell, J. Chem. Soc. 1935, 839.
C. Deuschel-Cornioley, H. Stoeckli-Evans, A. v. Zelewsky, J.
[2]
Chem. Soc., Chem. Commun. 1990, 121Ϫ212. Ϫ P. Jolliet, M.
Gianini, A. v. Zelewsky, G. Bernardinelli, H. Stoeckli-Evans,
Inorg. Chem. 1996, 35, 4883.
P. Hayoz, A. v. Zelewsky, Tetrahedron Lett. 1992, 33,
5165Ϫ5168. Ϫ P. Hayoz, A. v. Zelewsky, H. Stoeckli-Evans, J.
Am. Chem. Soc. 1993, 115, 5111Ϫ5114.
M. Gianini, A. v. Zelewsky, H. Stoeckli-Evans, Inorg. Chem.
1997, 36, 6094. M. Gianini, A. Forster, P. Haag, A. v. Zelewsky,
H. Stoeckli-Evans, Inorg. Chem. 1996, 35, 4889.
[14]
[15]
G. M. Sheldrick, Acta Crystallograph. 1990, A46, 467Ϫ273.
G. M. Sheldrick, SHELXL-97, Ϫ Program for Crystal Struc-
ture Refinement, University of Göttingen, Germany, 1997.
A. L. Spek, Acta Crystallogr. 1990, A46, C34.
Reprinted with permission from Cerius2, Version 3.8, 1998,
Molecular Simulations Inc., San Diego.
[3]
[16]
[17]
[4]
Received April 28, 2000
[I00169]
1220
Eur. J. Inorg. Chem. 2001, 1207Ϫ1220