The first transition metal complexes of 15-membered triolefinic macrocycles: (E,E,E)-1,6,11-Tris(arenesulfonyl)-1,6,11-triazacyclopentadeca-3,8,13-triene complexes of palladium(0), platinum(0), and silver(I)

Article abstract of DOI:10.1002/1099-0682(200108)2001:8<1999::AID-EJIC1999>3.0.CO;2-V

(E,E,E)-1,6,11-Tris(arenesulfonyl)-1,6,11-triazacyclopentadeca-3,8,13-trienes (1) form very stable complexes with Pd⁰ and Pt⁰, and moderately stable complexes with Ag¹. The three olefins in the macrocycle are responsible f

Full text of DOI:10.1002/1099-0682(200108)2001:8<1999::AID-EJIC1999>3.0.CO;2-V

FULL PAPER
The First Transition Metal Complexes of 15-Membered Triolefinic
Macrocycles: (E,E,E)-1,6,11-Tris(arenesulfonyl)-1,6,11-triazacyclopentadeca-
3,8,13-triene Complexes of Palladium(0), Platinum(0), and Silver(I)
[a]
[a]
[b]
[b]
[a]
`
˜
Silvia Cerezo, Jordi Cortes, Elena Lago, Elies Molins, Marcial Moreno-Manas,*
[c]
[a]
[a]
[a]
´
Teodor Parella, Roser Pleixats, Javier Torrejon, and Adelina Vallribera
Keywords: Palladium / Platinum / Silver / Macrocyclic ligands / Heterocycles
(E,E,E)-1,6,11-Tris(arenesulfonyl)-1,6,11-triazacyclopenta-
deca-3,8,13-trienes (1) form very stable complexes with Pd0
and Pt0, and moderately stable complexes with AgI. The
three olefins in the macrocycle are responsible for the com-
plexation. The X-ray structures of two complexes of Pd0 and
Pt0 are presented; both complexes are planar trigonal.
Introduction
Nitrogen-containing 15-membered macrocycles are com-
monplace.[1,2] However, nitrogen-containing 15-membered
macrocycles featuring internal olefinic double bonds are ex-
ceptional. The few known examples contain only one
double bond, and metathesis is the key step for their pre-
paration.[3] In 1998 we described the serendipitous forma-
tion of (E,E,E)-1,6,11-tris(arenesulfonyl)-1,6,11-triazacyclo-
pentadeca-3,8,13-trienes (1) and the complex 2b-Pd0
(Scheme 1)
by
nonselective
palladium(0)-catalyzed
TsujiϪTrost allylation of arenesulfonamides with cis-2-but-
ene-1,4-diol dicarbonate.[4] The macrocycle 1b affords the
complex 2b-Pd0 by treatment with sources of Pd0. This
complex is very stable, catalyses certain Suzuki-type cross-
coupling reactions, and is easily recovered after catalysis.[5]
Later we published the optimized preparations of macro-
cycles 1 featuring a vast array of substituents at the arenes-
ulfonyl moieties.[6]
The complexes Pd2(dba)3-solvent and Pd2(dba)4
Scheme 1. Preparation of complexes 2: a) Pd(PPh3)4 in THF for
2a-Pd0 and 2b-Pd0; b) Pd(dba)2 in THF for 2c-Pd0 and 2d-Pd0; c)
Pt(PPh3)4 in THF for 2a-Pt0 and in DMF for 2b-Pt0; d) AgBF4 in
acetone for 2a-AgIBF4 and 2b-AgIBF4
[7]
are
very well-known and their catalytic effect has been recog-
nized. Many other complexes of olefins with palladium(0)
and platinum(0) have been described.[8Ϫ10] However, only a
few complexes of transition metals with triolefinic macro-
cycles are known. Thus, the diverse configurational isomers
of the 12-membered carbocycle cyclododeca-1,5,9-triene
have a rich coordination chemistry, and their Ni0 complexes
have played a fundamental role in catalysis and in or-
ganonickel chemistry.[11] X-ray diffraction data of the
(E,E,E) isomer show that the complex is planar tri-
gonal.[11b] Other metals form complexes with cyclododeca-
trienes: CuI,[12] PdII,[13] AgI,[14] RhIII [15] and RuII.[16] Re-
,
lated 12-membered carbocycles also form nickel(0) com-
plexes.[17] At the upper limit of ring size, 13-membered
(Z,E,Z)-cyclotrideca-1,5,9-triene forms a complex with
AgI.[18] A special case is the complexation of AgI by
[2.2.2]paracyclophanes, which occurs in an η2 manner at
each of the three benzene rings.[19] The related
[26](1,2,4,5)cyclophane (deltaphane) presents the same be-
havior.[19b] In contrast, (Z,Z,Z)-tribenz[12]annulene, the
triunsaturated analogue of [2.2.2]orthocyclophane coordin-
ates AgI through the three olefins.[20] Metal complexes of
macrocyclic triolefins higher than 13-membered are un-
known.
[a]
`
Department of Chemistry, Universitat Autonoma de
Barcelona, Cerdanyola,
08193 Barcelona, Spain
Fax: (internat.) ϩ34-93/581-1265
E-mail: marcial.moreno@uab.es
[b]
[c]
`
Institut de Ciencia de Materials de Barcelona (CSIC), Campus
de la UAB,
08193 Cerdanyola, Spain
Servei de RMN, Universitat Autonoma de Barcelona,
`
Cerdanyola,
08193 Barcelona, Spain
Eur. J. Inorg. Chem. 2001, 1999Ϫ2006
WILEY-VCH Verlag GmbH, 69451 Weinheim, 2001
1434Ϫ1948/01/0808Ϫ1999 $ 17.50ϩ.50/0
1999

˜
M. Moreno-Manas et al.
FULL PAPER
Spurred on by these findings we decided to study the metals. Both tetrakis(triphenylphosphane)palladium(0) and
complexing ability of macrocycles 1 towards transition Pd(dba)2 gave excellent results as Pd sources, whereas only
metals.
tetrakis(triphenylphosphane)platinum(0) was tested for
platinum (Scheme 1). Silver tetrafluoroborate was used for
the formation of the silver complexes. These complexes are
much less stable than those of Pd0 and Pt0. Strong evidence
for the structures was secured by X-ray diffraction for 2a-
Pd0 (Figure 1 and 2) and 2a-Pt0 (Figure 3 and 4) and in all
cases by MALDI-TOF mass spectrometry.
Results and Discussion
Complexes 2 were very easily prepared by the reaction of
macrocycles 1 with familiar sources of the corresponding
Complexes 2a-Pd0 and 2a-Pt0 are planar trigonal, with
the distances from the metal atoms to the plane defined by
the central points of the three olefin bonds being 0.018 and
˚
0.015 A, respectively. The complexes crystallize with one
molecule of dichloromethane. They are not symmetrical,
and in particular they lack a C3 axis of symmetry. Two Cϭ
C bonds are longer than in the corresponding free ligand
1a[6] (see Table 1). However, the third CϭC bond is shorter
than the other two in both complexes, and is close to the
distance in the free ligand. These facts suggest that com-
plexation by one olefin is weaker than complexation by the
other two, a feature that is also evident in solution from
NMR spectroscopic data.
The 13C NMR spectrum of 2a-Pd0 shows three signals of
about the same intensity for three different types of CH2
groups at δ ϭ 45.1, 48.2, and 49.5 (Table 2). Also, three
different signals appear, again of similar intensities, for
three different types of olefinic CH groups, at δ ϭ 78.5,
78.7, and 82.8. Moreover, the signals of the aromatic pro-
Figure 1. Perspective view of the 2a-Pd0 molecule with the crystal-
lographic atom numbering; atoms are represented as their thermal
vibration ellipsoids (50% probability)
Figure 2. Perspective view of the unit cell of 2a-Pd0
2000
Eur. J. Inorg. Chem. 2001, 1999Ϫ2006

The First Transition Metal Complexes of 15-Membered Triolefinic Macrocycles
FULL PAPER
for complexes 2-Pd0 and 2-Pt0, and can only be compatible
with an averaged plane of symmetry rather than with a C3
symmetry axis. The 1H NMR spectra were further complic-
ated by the fact that the protons pertaining to the same
methylene group are not averaged, due to conformational
rigidity. These methylenic protons are in different environ-
ments and therefore they give signals at very different chem-
ical shifts. Selective 1D TOCSY experiments performed on
complexes 2a-Pd0, 2a-Pt0, and 2b-Pd0 permitted the deter-
mination of the chemical shifts and coupling constants in-
dicated in Table 2. Thus, the pairs of positions C2ϪC15,
C3ϪC14, C4ϪC13, and C5ϪC12 are connected by an aver-
aged plane of symmetry, as are the pairs C7ϪC10 and
C8ϪC9 (see Scheme 2 for numbering). A simplified repres-
entation of the equilibrium causing this averaged response
is shown in Scheme 2. As a consequence, the olefinic carbon
atoms (and their corresponding hydrogen atoms) in posi-
tions C3 and C14 give the same signals, which are different
from the signals due to the other bound carbons (positions
C4 and C13). Moreover, the third double bond at positions
C8 and C9 is different from the others, and positions C8
and C9 give the same signal. In other words the NMR spec-
troscopic data show that, in solution, two olefins complex
the metal with the same strength, and the third one com-
plexes differently, as already shown in the solid phase by X-
ray diffraction studies.
Figure 3. Perspective view of the 2a-Pt0 molecule with the crystallo-
graphic atom numbering; atoms are represented as their thermal
vibration ellipsoids (50% probability)
tons appear in two sets, one set of signals being about twice
the intensity of the other, confirming that two olefins be-
1
have the same both in the H NMR and 13C NMR spectra
and the third behaves differently. This is a general behavior
Figure 4. Perspective view of the unit cell of 2a-Pt0
Eur. J. Inorg. Chem. 2001, 1999Ϫ2006
2001

˜
M. Moreno-Manas et al.
FULL PAPER
Table 1. Selected bond lengths and angles found in 2a-Pd0 and 2a-Pt0
PdϪolefin distances
Bond lengths
Torsion angles
˚
˚
(A)
(A)
(°)
2a-Pd0
2a-Pd0
2a-Pd0
2a-Pt0
2a-Pt0
2a-Pt0
1a[6]
PdϪC10
2.142(6)
2.244(6)
2.186(6)
2.261(6)
2.167(5)
2.234(6)
2.128(15)
2.146(12)
2.145(11)
2.154(15)
2.135(11)
2.152(11)
C10ϪC11
C22ϪC23
C34ϪC35
C10ϪC11
C22ϪC23
C34ϪC35
1.301(7)
1.368(7)
1.368(7)
1.365(14)
1.389(14)
1.274(15)
H10ϪC10ϪC11ϪH11
148.1(9)
146.7(9)
147.9(9)
146.4(12)
145.6(12)
162.6(12)
PdϪC11
PdϪC22
PdϪC23
PdϪC34
PdϪC35
PtϪC10
PtϪC11
PtϪC22
PtϪC23
PtϪC34
PtϪC35
H22ϪC22ϪC23ϪH23
H34ϪC34ϪC35ϪH35
H10ϪC10ϪC11ϪH11
H22ϪC22ϪC23ϪH23
H34ϪC34ϪC35ϪH35
C10ϪC11
C22ϪC23
C34ϪC35
1.292(7)
1.291(7)
1.277(7)
Table 2. NMR spectroscopic data for Complexes 2a-Pd0, 2b-Pd0, and 2a-Pt0
Positions
2a-Pd0 [a]
2a-Pd0
2b-Pd0[b]
2b-Pd0
2a-Pt0[a]
2a-Pt0
1H NMR
13C NMR 1H NMR
13C NMR 1H NMR
13C NMR
2 and 15 (ϪCH2Ϫ) 3.07 (dd, J ϭ 14.2, 11.3) 45.1
4.78 (d, J ϭ 14.3)
3.05 (dd, J ϭ 12.6, 12.4) 43.8
2.98 (dd, J ϭ 13.6, 11.5) 44.3
4.55 (d, J ϭ 12.6)
2.80 (t, J ϭ 12.4)
5.02 (d, J ϭ 12.7)
2.07 (td, J ϭ 13.3, 2.3)
3.41 (td, J ϭ 11.6, 3.8)
3 and 14 (ϭCHϪ) 2.79 (t, J ϭ 11.7)
4 and 13 (ϭCHϪ) 3.93Ϫ4.03 (m)
82.8
78.7
83.7
69.0
63.2
4.10 (dd, J ϭ 12.4, 11.1) 79.3
1.52 (dd, J ϭ 15.6, 11.1) 47.9
4.22 (dd, J ϭ 15.6, 3.2)
5 and 12 (ϪCH2Ϫ) 1.63 (dd, J ϭ 14.3, 10.7) 49.5
4.62 (d, J ϭ 14.3)
1.34 (dd, J ϭ 14.0, 10.9) 48.5
4.58 (dd, J ϭ 14.0, 3.8)
7 and 10 (ϪCH2Ϫ) 1.50Ϫ1.80 (m)
4.64 (d, J ϭ 14.3)
48.2
1.58 (dd, J ϭ 15.3, 9.5) 46.5
4.30 (d, J ϭ 15.3)
1.35Ϫ1.46 (m),
4.62 (d, J ϭ 12)
3.22Ϫ3.25 (m)
47.2
8 and 9 (ϭCHϪ)
3.75 (m)
78.5
3.85 (d, J ϭ 9.5)
79.2
62.7
[a] 1H and 13C NMR spectra for 2a-Pd0 and 2a-Pt0 were recorded in CDCl3. Ϫ [b] 1H and 13C NMR spectra for 2b-Pd0 were recorded
in [D8]toluene.
In the case of different N-substituents, as for 2c-Pd0, two
different isomers are expected depending on which substitu-
ent occupies the position opposite to the singular olefin.
Although no attempts have been performed to separate
these possible isomers, the 13C NMR spectrum for 2c-Pd0
confirms this situation in solution. Thus, the 2α isomer
(Scheme 2) has the unique (2,4,6-triisopropyl)phenylsul-
fonyl group opposite the singular olefin, and therefore it
has an averaged plane of symmetry and three different sig-
nals are predicted for the olefinic protons and for the ring
methylene protons, whereas the 2β isomer has no symmetry
whatsoever, and therefore six different signals are predicted
for the olefinic protons and for the methylenic protons. The
experimental result is that 2c-Pd0 has nine signals in the
olefinic region between δ ϭ 77.6 and 88.4 and eight signals
in the CH2 region between δ ϭ 43.7 and 49.5. Efforts are
presently being made to prepare crystals of different N-sub-
stituted macrocycles.
The silver complexes were not stable and could not be
Scheme 2. Averaged plane of symmetry and equilibrium between
studied in depth.
isomers in complexes 2
2002
Eur. J. Inorg. Chem. 2001, 1999Ϫ2006

The First Transition Metal Complexes of 15-Membered Triolefinic Macrocycles
FULL PAPER
(E,E,E)-1,6,11-Tris[(4-methylphenyl)sulfonyl]-1,6,11-triazacyclo-
pentadeca-3,8,13-trieneplatinum(0) (2a-Pt0): A solution of macrocy-
cle 1a (0.186 g, 0.149 mmol) and tetrakis(triphenylphosphane)plati-
num(0) (0.186 g, 0.149 mmol) in tetrahydrofuran (6 mL) was re-
fluxed for 144 h. The solvent was then evaporated and the residue
was passed through a silica gel column with hexane/ethyl acetate/
dichloromethane (2:1:1) as eluent to afford 2a-Pt0 (0.078 g, 60%)
Conclusion
Preparations of the first Pd0, Pt0, and AgI complexes of
15-membered macrocyclic triolefins are described. X-ray
analysis and NMR spectroscopic data indicate that the
complexes have an averaged plane of symmetry rather than
a C3 axis.
as a solid, m.p. 260Ϫ263 °C (dec., change of crystalline structure
Ϫ1
˜
at 168Ϫ172 °C). Ϫ IR (KBr): ν ϭ 1340, 1162, 1092, 909, 661 cm
.
Ϫ 1H NMR (250 MHz, CDCl3): δ ϭ 1.34Ϫ1.46 (m, 4 H), 2.07 (td,
J ϭ 13.3 and 2.3 Hz, 2 H), 2.40 (s, 9 H), 2.98 (dd, J ϭ 13.6 and
11.5 Hz, 2 H), 3.22Ϫ3.25 (m, 2 H), 3.41 (td, J ϭ 11.6 and 3.8 Hz,
2 H), 4.58 (dd, J ϭ 13.6 and 3.8 Hz, 2 H), 4.62 (d, J ϭ 12.0 Hz, 2
H), 5.02 (d, J ϭ 12.7 Hz, 2 H), 7.26 (d, J ϭ 8.2 Hz, 6 H), 7.62 (d,
J ϭ 8.2 Hz, 4 H), 7.65 (d, J ϭ 8.2 Hz, 2 H). Ϫ 13C NMR
(62.5 MHz, CDCl3): δ ϭ 21.5, 44.3, 47.2, 48.5, 62.7, 63.2, 69.0,
127.0, 127.2, 129.8, 135.0, 136.0, 143.4, 143.6. Ϫ MALDI-TOF
MS: m/z (%) ϭ 864.9 [M]ϩ, 887.9 [M ϩ Na]ϩ, 903.9 [M ϩ K]ϩ. Ϫ
C33H39N3O6PtS3·CH2Cl2 (949.9): calcd. C 43.00, H 4.35, N 4.42,
S 10.11; found C 43.57, H 4.07, N 4.15, S 9.73.
Experimental Section
General: Macrocycles 1 were prepared as described previously.[5,6]
Melting points were determined with a Kofler apparatus and are
uncorrected. Ϫ IR spectra were recorded with a Nicolet FT-IR
510 ZDX. Ϫ NMR spectra were recorded with a Bruker-Analytik
1
AC250. H NMR (250 MHz) chemical shifts are reported relative
to CHCl3 at δ ϭ 7.26 or tetramethylsilane at δ ϭ 0.00. Coupling
constants are reported in Hz. 13C NMR (62.5 MHz) chemical shifts
are expressed relative to CDCl3 at δ ϭ 77.00 or tetramethylsilane
at
δ ϭ 0.00. Mass spectra (EIMS) were obtained with a
HewlettϪPackard 5989A spectrometer and determined at an ioniz-
ing voltage of 70 eV. MALDI-TOF spectra were recorded on a BI-
FLEX spectrometer (BrukerϪFranzen Analytik) equipped with a
pulsed nitrogen laser (337 nm), operating in positive-ion reflector
mode, and using 19 kV acceleration voltage. Matrices (α-cyanocin-
namic acid) were prepared at 5 mg/mL in THF. Analytes were dis-
solved at concentrations between 0.1 and 5 mg/mL in THF or chlo-
roform. Ϫ Elemental analyses were determined at the Servei dЈAn-
`
´
`
alisi Quımica de la Universitat Autonoma de Barcelona.
(E,E,E)-1,6,11-Tris[(4-methylphenyl)sulfonyl]-1,6,11-triazacyclo-
pentadeca-3,8,13-trienepalladium(0) (2a-Pd0): A solution of macro-
cycle 1a (0.150 g, 0.125 mmol) and tetrakis(triphenylphosphane)-
palladium(0) (0.100 g, 0.150 mmol) in tetrahydrofuran (4 mL) was
refluxed for 24 h. More tetrakis(triphenylphosphane)palladium(0)
(0.50 g, 0.75 mol) was then added and the reflux continued for a
further 24 h. The solvent was then evaporated and the residue was
passed through a silica gel column with hexane/ethyl acetate/
dichloromethane (2:1:1) as eluent to afford 2a-Pd0 (0.164 g, 95%)
(E,E,E)-1,6,11-Tris[(4-methylphenyl)sulfonyl]-1,6,11-triazacyclo-
pentadeca-3,8,13-trienesilver(I) Tetrafluoroborate (2a-AgIBF4): A
solution of macrocycle 1a (0.300 g, 0.45 mmol) and silver tetra-
fluoroborate (0.216 g, 0.90 mmol) in acetone (12 mL) was stirred
for 5 min. at room temperature and the mixture was then left for
20 h. The formed precipitate was filtered off to afford 2a-AgIBF4
as a white solid (0.200 g, 54%), m.p. 206Ϫ208 °C (dec). Ϫ IR
˜
(KBr): ν ϭ 1700, 1392, 1349, 1165, 1092, 1058, 1009, 939, 904, 815,
1
754, 659 cmϪ1. Ϫ H NMR (250 MHz, CDCl3): δ ϭ 2.44 (s, 9 H),
˜
as a solid, m.p. 237Ϫ240 °C (dec). Ϫ IR (KBr): ν ϭ 1340, 1162,
1094, 904, 657 cmϪ1. Ϫ 1H NMR (250 MHz, CDCl3): δ ϭ 1.60
(m, 2 H), 1.63 (dd, J ϭ 14.3 and 10.7 Hz, 2 H), 2.39 (s, 9 H), 2.79
(t, J ϭ 11.7 Hz, 2 H), 3.07 (dd, J ϭ 14.2 and 11.3 Hz, 2 H), 3.75
(d, J ϭ 8.9 Hz, 2 H), 3.93Ϫ4.03 (m, 2 H), 4.62 (d, J ϭ 14.0 Hz, 2
H), 4.64 (d, J ϭ 14.3 Hz, 2 H), 4.78 (d, J ϭ 14.3 Hz, 2 H), 7.28 (d,
J ϭ 8.2, 6 H), 7.64 (d, J ϭ 8.2 Hz, 4 H), 7.71 (d, J ϭ 8.2 Hz, 2 H).
3.75 (s, 12 H), 5.74 (s, 6 H), 7.33 (d, J ϭ 7.9 Hz, 6 H), 7.66 (d, J ϭ
7.9 Hz, 6 H). Ϫ MALDI-TOF MS: m/z (%) ϭ 776.1 [M of
cation]ϩ, 692.2 [M
Ϫ
Ag
ϩ
Na]ϩ.
Ϫ
C33H39-
AgBF4N3O6S3·CH3COCH3 (922.6): calcd. C 46.87, H 4.92, N 4.55,
S 10.42; found C 46.91 and 46.90, H 4.98 and 4.89, N 4.71 and
4.60, S 10.52 and 10.48.
Ϫ
13C NMR (62.5 MHz, CDCl3): δ ϭ 21.5, 45.1, 48.2, 49.5, 78.5,
78.7, 82.8, 127.0, 127.2, 129.8, 135.2, 136.1, 143.4, 143.6. Ϫ
MALDI-TOF MS: m/z (%) ϭ 774.9 [M]ϩ, 798.1 [M ϩ Na]ϩ, 813.9
[M ϩ K]ϩ. Ϫ C33H39N3O6PdS3·CH2Cl2 (861.2): calcd. C 47.42, H
4.80, N 4.88, S 11.15; found C 47.47 and 47.46, H 4.82 and 4.80,
N 4.71 and 4.67, S 10.76 and 10.89.
(E,E,E)-1,6,11-Tris[(2,4,6-triisopropylphenyl)sulfonyl]-1,6,11-triaza-
cyclopentadeca-3,8,13-trienepalladium(0) (2b-Pd0): This compound
was prepared as for 2a-Pd0 according to ref.[5]
Eur. J. Inorg. Chem. 2001, 1999Ϫ2006
2003

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M. Moreno-Manas et al.
FULL PAPER
(E,E,E)-1,6-Bis[(3-perfluorooctylphenyl)sulfonyl]-11-[(2,4,6-triiso-
propylphenyl)sulfonyl]-1,6,11-triazacyclopentadeca-3,8,13-triene-
palladium(0) (2c-Pd0): A solution of macrocycle 1c (1.920 g,
1.21 mmol) and bis(dibenzylideneacetone)palladium(0) (0.760 g,
1.33 mmol) in tetrahydrofuran (60 mL) was maintained at room
temperature for 24 h. The mixture was filtered, the solvent was re-
moved from the filtrate in vacuo and the residue was washed with
hexane and passed through a silica gel column with hexane/ethyl
acetate (10:1) as eluent to afford 2c-Pd0 (1.95 g, 95%) as a solid,
m.p. 141Ϫ142 °C (dec). Ϫ IR (KBr): ν˜ ϭ 1351, 1240, 1212, 1162,
(E,E,E)-1,6,11-Tris[(2,4,6-triisopropylphenyl)sulfonyl]-1,6,11-triaza-
cyclopentadeca-3,8,13-trieneplatinum(0) (2b-Pt0):
A solution of
macrocycle 1b (0.083 g, 0.08 mmol) and tetrakis(triphenylphos-
phane)platinum(0) (0.200 g, 0.17 mmol) in DMF (2.5 mL) was
heated at 130 °C for four days. The solvent was then distilled off
at reduced pressure and the residue was passed through a column
of silica gel with hexane/ethyl acetate (5:1) as eluent to afford 2b-
Pt0 (0.07 g, 70%) as a white solid, m.p. 286Ϫ287 °C (dec). Ϫ IR
1
˜
1117, 908, 658 cmϪ1. Ϫ H NMR (250 MHz, CDCl3, αϩβ forms):
(KBr): ν ϭ 2960, 1601, 1461, 1427, 1363, 1315, 1262, 1151, 1103,
1047 cmϪ1. Ϫ 1H NMR (250 MHz, CDCl3): δ ϭ 1.20Ϫ1.26 (m, 54
H), 1.84 (m, 4 H), 2.49 (t, J ϭ 11.1 Hz, 2 H), 2.89 (septet, J ϭ
6.9 Hz, 3 H), 3.14 (t, J ϭ 11.1 Hz, 2 H), 3.38 (d, J ϭ 8.6 Hz, 2 H),
3.58 (dt, J ϭ 12.5 and 3.8 Hz, 2 H), 4.17 (septet, J ϭ 6.8 Hz, 6 H),
4.36Ϫ4.40 (m, 2 H), 4.45 (d, J ϭ 14.7 Hz, 2 H), 4.82 (d, J ϭ
12.4 Hz, 2 H), 7.16 (s, 6 H). Ϫ 13C NMR (62.5 MHz, CDCl3): δ ϭ
23.5, 24.8, 29.3, 34.2, 43.1, 45.6, 47.0, 62.9, 63.4, 69.7, 123.9, 131.3,
151.4, 153.2. Ϫ MALDI-TOF MS: m/z (%) ϭ 1201.3 [M]ϩ, 935.1
[M Ϫ SO2Ar]ϩ, 667.6 [M Ϫ 2SO2Ar]ϩ. Ϫ C57H87N3O6PtS3
(1201.6): calcd. C 56.98, H 7.30, N 3.50, S 8.00; found C 56.97 and
56.91, H 7.18 and 7.27, N 3.52 and 3.48, S 7.85 and 7.83.
δ ϭ 1.21 (m, 18 H), 1.5Ϫ1.9 (m, 2 H), 1.95Ϫ2.2 (m, 2 H), 2.72 (bt,
J ഠ 12.4 Hz), 2.85Ϫ3.00 (m) and 3.0Ϫ3.3 (m) (the three groups of
signals, 6 H), 3.7Ϫ4.0 (m, 2 H), 4.0Ϫ4.3 (m, 3 H), 4.47 (bt, J ഠ
15 Hz, 2 H), 4.68 (bt, J ഠ 14 Hz, 2 H), 4.83 (bd, J ഠ 15 Hz, 2 H),
7.07, 7.12, and 7.19 (three s, 2 H), 7.40Ϫ7.45 (m, 2 H), 7.6Ϫ7.85
(m, 4 H), 7.95Ϫ8.1 (m, 2 H). Ϫ 13C NMR (62.5 MHz, CDCl3, αϩβ
forms): δ ϭ 23.5, 24.7, 24.8, 29.3, 34.1, 43.7, 45.2, 45.4, 46.3, 47.6,
48.2, 49.3, 49.5, 77.6, 77.9, 78.6, 78.8, 79.7, 79.9, 81.9, 82.8, 84.4,
123.9Ϫ153.4 (m). Ϫ MALDI-TOF MS: m/z (%) ϭ 1695.1 [M]ϩ,
1718.1 [M ϩ Na]ϩ, 1734.1 [M ϩ K]ϩ. Ϫ C55H49F34N3O6PdS3
(1696.6): calcd. C 38.94, H 2.91, N 2.48, S 5.67; found C 39.03 and
39.02, H 3.18 and 3.30, N 2.45 and 2.44, S 5.47 and 5.42.
(E,E,E)-1,6,11-Tris[(5-dimethylaminonaphthyl)sulfonyl]-1,6,11-tri-
(E,E,E)-1,6,11-Tris[(2,4,6-triisopropylphenyl)sulfonyl]-1,6,11-triaza- azacyclopentadeca-3,8,13-trienepalladium(0) (2d-Pd0): A solution of
cyclopentadeca-3,8,13-trienesilver(I) Tetrafluoroborate (2b-AgIBF4):
macrocycle 1d (0.180 g, 0.20 mmol) and bis(dibenzylideneacetone)-
A solution of macrocycle 1b (0.100 g, 0.1 mmol) and silver tetra-
palladium(0) (0.127 g, 0.22 mmol) in tetrahydrofuran (10 mL) was
fluoroborate (0.020 g, 0.1 mmol) in acetone (0.5 mL) was refluxed refluxed for 5 h. The mixture was filtered, the solvent was removed
for 5 h in a round-bottomed flask kept in the dark. The solvent
was eliminated by passing a stream of nitrogen though the flask to
from the filtrate in vacuo and the solid residue (0.270 g) was passed
through a silica gel column with hexane/ethyl acetate (8:2) as eluent
afford complex 2b-AgIBF4 quantitatively: This compound was not to afford dibenzylideneacetone (0.054 g) and 2d-Pd0 (0.180 g, 89%)
stable to further purification procedures. M.p. 213Ϫ216 °C (dec).
as a solid, m.p. 167Ϫ169 °C (hexane/ethyl acetate). Ϫ IR (KBr):
˜
˜
Ϫ IR (KBr): ν ϭ 2960, 1602, 1464, 1428, 1364, 1322, 1154, 1108, ν ϭ 2940, 2832, 1574, 1457, 1401, 1322, 1144, 1068, 938, 903, 833,
1041, 997 cmϪ1. Ϫ 1H NMR (250 MHz, CDCl3, at 328 K): δ ϭ 789, 750 cmϪ1. Ϫ UV/Vis (THF): λ (log ε) ϭ 340 (4.11), 254 (4.61).
1.22 (m, 54 H), 2.87 (septet, J ϭ 7.0, 3 H), 3.75Ϫ4.10 (m, 18 H),
Ϫ
1H NMR (250 MHz, CDCl3): δ ϭ 1.86Ϫ2.02 (m, 4 H),
6.06 (br. s, 6 H), 7.15 (s, 6 H). Ϫ 13C NMR (62.5 MHz, CDCl3): 2.85Ϫ2.86 (two s, 18 H), 2.93Ϫ2.98 (m, 2 H), 3.18 (dd, J ϭ 14.0
δ ϭ 23.5, 24.7, 29.4, 34.2, 47.3, 123.7, 123.9, 124.2, 130.1, 151.6, and 10.7 Hz, 2 H), 3.79Ϫ3.82 (m, 2 H), 4.01Ϫ4.12 (m, 2 H), 4.63
153.8. Ϫ MALDI-TOF MS: m/z (%) ϭ 1112.5 [M of cation]ϩ.
(t, J ഠ 13.5 Hz, 4 H), 4.89 (d, J ഠ 13.5 Hz, 2 H), 7.15 (dd, J ϭ 7.5
2004
Eur. J. Inorg. Chem. 2001, 1999Ϫ2006

The First Transition Metal Complexes of 15-Membered Triolefinic Macrocycles
FULL PAPER
Table 3. The crystal data and structure refinement for 2a-Pd0 and 2a-Pt0
2a-Pd0
2a-Pt0
Formula
C34H41Cl2N3O6PdS3
861.18
0.53 ϫ 0.23 ϫ 0.21
Orthorhombic
P212121
11.1844 (13)
17.1818(12)
19.713(3)
C34H41Cl2N3O6PtS3
949.87
0.39 ϫ 0.16 ϫ 0.07
Monoclinic
P21/c
17.15 (9)
11.199 (10)
19.74 (4)
Molecular weight
Crystal size [mm]
Crystal system
Space group
˚
a [A]
˚
b [A]
˚
c [A]
β [°]
V [A ]
Ϫ
90.03 (2)
3793 (2)
3
˚
3788 (2)
Z
4
4
ρcalc [Mg mϪ3
]
1.510
1.663
Temperature [K]
293 (2)
1768
Mo-Kα, 0.710739
0.843
Ϫ13/13, 0/20, 0/23
6633
293 (2)
1896
Mo-Kα, 0.710739
4.052
Ϫ20/20, 0/13, 0/23
6658
F(000)
˚
Wavelength [A]
Absorption coefficient [mmϪ1
hkl range
]
Reflections collected
Data/restraints/parameters
Goodness of fit on F2
Final R indices [I Ͼ 2σ (I)]
6633 / 69/442
1.087
R1 ϭ 0.0667
wR2 ϭ 0.1831
R1 ϭ 0.0956
wR2 ϭ 0.2018
1.378/Ϫ0.861
6658/5/460
0.976
R1 ϭ 0.0622
wR2 ϭ 0.1091
R1 ϭ 0.1370
wR2 ϭ 0.1228
0.838/Ϫ1.220
R indices (all data)
Largest diff. peak and hole
and 5.7 Hz, 3 H), 7.48Ϫ7.56 (m, 6 H), 8.19 (dd, J ϭ 7.5 and 1.4 Hz, meters were refined for the non-hydrogen atoms and the hydrogen
3 H), 8.24Ϫ8.31 (m, 3 H), 8.53 (br. d, J ϭ 8.2 Hz, 3 H). Ϫ 13C atoms were introduced in calculated positions.
NMR (62.5 MHz, CDCl3): δ ϭ 14.5, 22.7, 34.5, 45.1, 45.8, 48.0,
Crystallographic data (excluding structure factors) for the struc-
tures reported in this paper have been deposited with the Cam-
bridge Crystallographic data center as supplementary publications
49.2, 79.6, 79.8, 83.9, 115.7, 119.6, 123.6, 128.6, 130.3, 130.4, 130.8,
131.0, 134.9, 152.3. Ϫ MALDI-TOF MS: m/z (%) ϭ 1012.5 [M]ϩ,
929.7 [M Ϫ Pd ϩ Na]ϩ. Ϫ C48H54N6O6PdS3 (1013.6): calcd. C
nos. CCDC-150655 and -150656 for 2a-Pd0 and 2a-Pt0, respect-
56.88, H 5.37, N 8.29; found C 57.34 and 57.31, H 5.38 and 5.49,
ively. Copies of the data can be obtained free of charge on applica-
N 7.96 and 8.19.
tion to CCDC, 12 Union road, Cambridge CB2 1EZ, UK [Fax:
(internat.) ϩ44-1223/336-033; E-mail: deposit@ccdc.cam.ac.uk].
Acknowledgments
Financial support from MEC of Spain (projects PB93Ϫ0896 and
PB98Ϫ0902), and from CIRIT-Generalitat de Catalunya (projects
98SGR0056 and 2000SGR0062, and predoctoral scholarships to
J. C., S. C., and J. T.) is gratefully acknowledged.
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X-ray Analysis of 2a-Pd0 and 2a-Pt0. Data Collection and Pro-
cessing: Crystal data and experimental conditions for the two com-
plexes are listed in Table 3. The collected reflections were corrected
for Lorentz, polarization and absorption effects [empirical Difabs,
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2a-Pd0 and 50.02 for 2a-Pt0.
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Eur. J. Inorg. Chem. 2001, 1999Ϫ2006
2005

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M. Moreno-Manas et al.
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