Multiple functionalization of bis(2-pyridylimino)isoindole (BPI) ligands: Their modular synthesis and coordination to palladium(II)

Article abstract of DOI:10.1002/zaac.200500067

Polyether dendritic wedges have been attached to bis(2-pyridylimino) isoindole (BPI) ligands, and the corresponding Pd^II complexes have been synthesized and studied as hydrogenation catalysts. The fixation of dendrons at the ligand framework wa

Full text of DOI:10.1002/zaac.200500067

Multiple Functionalization of Bis(2-pyridylimino)isoindole (BPI) Ligands: Their
Modular Synthesis and Coordination to Palladium(II)
Bettina A. Siggelkow and Lutz H. Gade*
Heidelberg/Germany, Anorganisch-Chemisches Institut der Universität
Received January 24th, 2005.
Dedicated to Professor Herbert W. Roesky on the Occasion of his 70th Birthday
Abstract. Polyether dendritic wedges have been attached to bis(2-
pyridylimino)isoindole (BPI) ligands, and the corresponding PdII
complexes have been synthesized and studied as hydrogenation ca-
talysts. The fixation of dendrons at the ligand framework was carr-
ied out at the stage of the phthalodinitrile precursor of the BPI
ligands by nucleophilic substitution of 4-nitrophthalodinitrile with
the in situ generated alcoholates. Reaction of 1,3-dibenzyloxy-2-
the reaction of compound 5a with Me3SiCCH, Ph3SiCCH and
PhCCH, using Sonogashira’s [Pd(PPh3)4]/CuI catalyst, gave the cor-
responding bis(alkynyl)-derivatives. All the protioligands were
cleanly metallated to give the corresponding palladium(II) complexes.
In contrast to the unsubstituted complex, its dendrimer functio-
nalized derivatives [(11-Br)-BPI-[R-(3,5)-G-1]-PdCl] (R ϭ H: 9a,
tBu : 9b) and [(11-Br)-BPI-[(3,5)-G-2]-PdCl] (11) hydrogenated sty-
rene and 1-octene without decomposition (TOF ϭ 5 hϪ1 at T ϭ
295 K, p(H2) ϭ 1 bar, 2 mol% cat.) and among these, catalyst 11,
carrying the 2nd generation dendron displayed sufficient stability to
be isolated and reused several times.
´
propanol [G-1] and the coupling of Frechet’s first and second gene-
ration arylether dendrons [(3,5)-G-1]-OH, [t-Bu-(3,5)-G-1]-OH and
[(3,5)-G-2]-OH with 4-nitrophthalodinitrile gave the corresponding
O-coupled phthalodinitrile derivatives. The synthesis of the BPI li-
gands was achieved by reaction with two molar equivalents of 2-
amino-5-bromopyridine to give the protioligands (11-Br)-BPI-[G-
1] (4) and (11-Br)-BPI-[R-(3,5)-G-1] (R ϭ H: 5a, tBu: 5b) whereas
Keywords: Palladium; N-Donor Ligands; Dendrimer; Sonogashira
Coupling
Introduction
densation reaction of a phthalodinitrile derivative with two
molar equivalents of 2-aminopyridine [4]. This simplicity of
their assembly makes them promising candidates as core
molecules within complex structural architectures. In par-
ticular, it was of interest to assess whether the introduction
of larger peripheral structural units was possible after the
initial assembly of the BPI core. Such novel ligand systems
might confer significantly different chemical properties
upon their complexes, affecting for instance their kinetic
stability and solubility.
We have recently begun to study the catalytic activity of
palladium complexes containing derivatives of the well es-
tablished bis(2-pyridylimino)isoindolate (BPI) ligands (A)
[1]. These BPI-palladium compounds have proved to be a
promising new non-phosphine based class of molecular
hydrogenation catalysts for alkenes. Prior to this work, the
tridentate BPI ligands have been extensively studied in oxi-
dation catalysis induced by the middle and late transition
metals [2Ϫ10].
The protonated neutral precursors of the formally
anionic BPI ligands are readily accessible in a one-step con-
In this work we report the synthesis of BPI derivatives
(B) containing polyether dendritic wedges [11, 12] attached
to the ligand backbone, as well as alkynyl units of variable
steric bulk coupled to the pyridyl groups. By way of the
chosen synthetic strategy a modular assembly of a wide var-
iety of such derivatives is feasible. As examples for their
* Prof. Dr. L. H. Gade
Anorganisch-Chemisches Institut, Universität Heidelberg
Im Neuenheimer Feld 270
D-69120 Heidelberg/Germany
Fax: ϩ49-(0)6221-545609
E-mail: lutz.gade@uni-hd.de
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B. A. Siggelkow, L. H. Gade
complexation to transition metals, the synthesis of several
new dendritic BPI-Pd complexes will be described.
Results and Discussion
Synthesis of Bis(2-pyridylimino)isoindole Containing
Polyether Dendritic Wedges Attached to the Ligand
Framework
The fixation of polyether dendritic wedges at the ligand
framework of bis(2-pyridylimino)isoindole was carried out
at the stage of the phthalodinitrile precursor. As Brewis et
al. have shown in their synthesis of phthalocyanines at the
core of polyarylether dendrimers [13], the coupling of the
dendrons with the ligand or dendrimer core is readily
achieved by the nucleophilic substitution of 4-nitrophthalo-
dinitrile with the in situ generated alcoholates. This strategy
was chosen since Siegl et al. had previously found that the
substitution of a nitro function in the backbone of BPI de-
rivatives is not feasible [4d].
Scheme 2 Synthesis of 1,4-bis{2-(4-bromopyridyl)imino}isoindole
derivatives containing dendritic polyether wedges.
The synthesis of the BPI ligands derived from 1 and 2a,b
was achieved by stirring the dendron-functionalized phthalo-
dinitriles with two molar equivalents of 2-amino-5-bromo-
pyridine in the presence of CaCl2 in hexanol under reflux
for 20 Ϫ 25 h. This gave the protioligands (11-Br)-BPI-[G-
t
1] (4) and (11-Br)-BPI-[R-(3,5)-G-1] (R ϭ H: 5a, Bu: 5b)
as yellow microcrystalline solids (Scheme 2). The prep-
aration of the BPI derivative containing the second genera-
tion arylether dendron required more forcing reaction con-
ditions. Refluxing compound 3 with two equivalents of 2-
amino-5-bromopyridine in the presence of CaCl2 in a 2:3
mixture of mesitylene/hexanol for 10 days gave the corre-
sponding BPI ligand (11-Br)-BPI-[(3,5)-G-2] (6) which was
purified by column chromatography.
Scheme 1 Fixation of polyether dendrons to phthalodinitrile. (i)
K2CO3, DMF, ∆T.
Reaction of 1,3-dibenzyloxy-2-propanol [G-1] [14] with 4-
nitrophthalodinitrile in dimethylformamide (DMF) using
K2CO3 as auxiliary base, cleanly gave the O-coupled phthalo-
dinitrile derivative 4-[G-1]-phthalodinitrile (1) (Scheme 1). In
´
a similar way, the reaction of Frechet’s first and second genera-
tion arylether dendrons [(3,5)-G-1]-OH, [t-Bu-(3,5)-G-1]-OH
and [(3,5)-G-2]-OH [11] with 4-nitrophthalodinitrile gave the
ligand precursors 2a, 2b and 3. Whereas 1, 2a and 2b were ob-
tained in good yield after stirring at 60 °C for two days, the fix-
ation of the second generation dendron in 3 required an ex-
tended reaction time of eight days.
Sonogashira Coupling of a Dendritic Bis(2-
pyridylimino)isoindole with Terminal Alkynes to give
the 11-Alkynylpyridyl Derivatives
We have previously found that BPI ligands are stable with
respect to the conditions of palladium catalyzed Sonoga-
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Multiple Functionalization of Bis(2-pyridylimino)isoindole (BPI) Ligands
shira type couplings. This opened up the possibility of an
“a posteriori” functionalization of the dendritic BPI deriva-
tives discussed above. The reaction of compound 5a with
Me3SiCCH, Ph3SiCCH and PhCCH using Sonogashira’s
[Pd(PPh3)4]/CuI catalyst [15] gave the highly functionalized
BPI ligand precursors 7a Ϫ 7c in good yields (Scheme 3).
The reaction products precipitated as orange (7a,b) and
red (7c) microcrystalline solids during the course of the con-
version. Their formulation as represented in Scheme 3 was
confirmed by elemental analysis, the observation of the mo-
lecular ion peaks in their FAB mass spectra, the ν(CC) in-
1
frared bands at 2135 Ϫ 2155 cmϪ1 as well as the H and
13C NMR data.
Synthesis of Highly Functionalized Dendritic BPI-
Palladium Complexes
The preparation of the dendrimer-functionalized square
planar palladium(II) complexes 8 Ϫ 11 was carried out by
reaction of the protioligands with [(PhCN)2PdCl2] as PdII
precursor in benzene and with triethylamine as an auxiliary
base (Scheme 4). The reaction products precipitated directly
Scheme 3 Alkynylation of a 1,4-bis{2-(4-bromopyridyl)imino}-
isoindole by Sonogashira coupling
Scheme 4 Synthesis of BPI-palladium(II) complexes with dendritic wedges attached to the ligand backbone.
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B. A. Siggelkow, L. H. Gade
from the reaction mixture as orange-red microcrystalline
solids which were isolated by filtration and were obtained
as analytically pure compounds after extraction from di-
chloromethane/water.
The stabilization of the hydrogenation catalyst upon go-
ing from 9a,b to 11 is also apparent in the hydrogenation
of 1-octene depicted in Figure 1.
The metallation was monitored by 1H-NMR spec-
troscopy, the most characteristic change being the coordi-
nation shift of the 6-pyridyl protons from ca. 8.4 ppm in
the protioligands to ca. 9.5 ppm in the palladium complexes
and the disappearance of the NH-resonance of the isoin-
dole unit. In all the dendrimer-functionalized complexes the
BPI-unit has lost the Cs-symmetry of the parent compound
leading to two sets of signals for the pyridyl-units and their
attached functional groups. The FAB mass spectra of all
the palladium(II) complexes displayed the characteristic
[M-Cl]ϩ fragment which, together with the elemental analy-
ses establishes the formulation of the compounds given in
Scheme 4. For the silylated complexes [(11-TMS-ethynyl)-
BPI-{(3,5)-G-1}PdCl] (10a) and [(11-Ph3Si-ethinyl)-BPI-
{(3,5)-G-1}PdCl] (10b) the 29Si NMR resonances (10a:
Ϫ22.1, 10b: Ϫ22.3 ppm) are shifted with respected to those
of the protioligands 7a and 7b (Ϫ16.9 and Ϫ28.5 ppm,
respectively).
Catalytic Hydrogenation of Styrene and 1-Octene
with the Dendron-Functionalized Palladium
Complexes 9b and 11
There is a substantial interest in the development of molec-
ular non-phosphine containing palladium catalysts for
homogeneous hydrogenations. Costa, Pelagatti et al. have
studied the hydrogenation activity of palladium(II) com-
plexes stabilized inter alia by polydentate NʝNʝS [16] and
NʝNʝN ligands [17]. In particular, the use of tridentate
nitrogen donor ligands gave rise to relatively efficient PdII-
hydrogenation catalysts. The activation of dihydrogen is
thought to involve the protonation of a basic site in the
polydentate N-ligand and this formally protonated site in
subsequently involved in the elimination of the saturated
reaction product. We have recently shown that some BPI-
palladium complexes hydrogenate alkenes without de-
composition provided they do not carry electron with-
drawing substituents at the pyridyl units [2].
Figure 1 Hydrogenation of 1-octene catalyzed by 9b (a) and 11 (b)
and the concomitant isomerization of the alkene to a mixture of
E- and Z-2-octene as followed by GC-MS.
A remarkable feature of both catalysts carrying the den-
dritic wedges is the rapid isomerization of 1-octene to 2-
octene which for the second generation dendrimer catalyst
11 leads initially to an almost complete shift of the CϭC
double bond (> 80 %) before the hydrogenation of the ole-
fin(s) leads to a steady generation of n-octane.
Conclusion
The latter is the case for [(11-Br)-BPI-PdCl] [2] which is
degraded during the course of catalytic hydrogenations un-
der atmospheric pressures of H2. In contrast to the unsub-
stituted complex, its dendrimer functionalized derivatives
[(11-Br)-BPI-[R-(3,5)-G-1]-PdCl] (R ϭ H: 9a, tBu : 9b) and
[(11-Br)-BPI-[(3,5)-G-2]-PdCl] (11) hydrogenate styrene
without decomposition (TOF ϭ 5 hϪ1 at T ϭ 295 K,
p(H2) ϭ 1 bar, 2 mol% cat.) and among these, catalyst 11,
carrying the second generation dendron displays sufficient
stability to be isolated at the end of a catalytic run and
reused several times. This behaviour is similar to that ob-
served for the stable BPI-derivatives which are alkylated at
the pyridyl units.
In this paper we have devised a straightforward strategy
which allows for the combination of the well established
BPI ligand systems with large structural building blocks
leading to the modular assembly of systems of greater com-
plexity. Such modifications may influence the reactive or Ϫ
as in the case at hand Ϫ catalytic properties of the coordi-
nation compounds. The observation of a greater stability of
the dendrimer-functionalized catalysts is in line with pre-
vious observations in dendrimer catalysis [18]. The key may
be small changes in catalyst solubility and solvation and
thus a modification of the microenviroment of the reactive
sites.
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Multiple Functionalization of Bis(2-pyridylimino)isoindole (BPI) Ligands
Experimental Part
All manipulations were performed under nitrogen. Solvents were
dried according to standard methods and saturated with nitrogen.
The deuterated solvents used for the NMR spectroscopic measure-
ments were degassed by three successive “freeze-pump-thaw” cycles
˚
and stored over 4-A molecular sieves. Solids were separated from
suspensions by filtration through dried Celite or by centrifugation.
1
The H, 13C and 29Si NMR spectra were recorded on Bruker AC
200, Bruker Avance 250 and Bruker AMX 400 FT-NMR spec-
trometers. Infrared spectra were recorded on a Nicolet Magna
IRTM 750 spectrometer. Elemental analyses were carried out by
the microanalytical service at the chemistry department at Stras-
bourg. [(PhCN)2PdCl2] [19] was prepared according to a published
procedure. All other chemicals used as starting materials were ob-
tained commercially and used without further purification.
1H-NMR (300.17 MHz, CDCl3, 295 K): δ ϭ 1.31 (s, 18 H, CH3), 4.97 (s,
4
4 H, H-14), 5.08 (s, 2 H, H-9), 6.59 (s, 3 H, H-11,13), 7.21 (dd, JHH
ϭ
3
4
2.8 Hz, JHH ϭ 8.8 Hz, 1 H, H-5), 7.29 (d, JHH ϭ 2.8 Hz, 1 H, H-3),
7.32Ϫ7.41 (m, 8 H, H-16,17), 7.67 (d, JHH ϭ 8.8 Hz, 1 H, H-6). {1H}13C-
3
NMR (75.48 MHz, CDCl3, 295 K): δ ϭ 31.1 (CH3), 34.6 (Cq), 70.1 (C-14),
70.9 (C-9), 101.8 (C-13), 106.2 (C-11), 107.6 (C-1), 115.2 (C-7,8), 117.4 (C-
2), 119.7 (C-3, 5), 120.0 (C-3, 5), 125.6 (C-Ph), 127.5 (C-Ph), 133.4 (C-10/
15), 135.2 (C-6), 136.8 (C-10/15), 151.8 (C-18), 160.5 (C-12), 161.6 (C-4). IR
(KBr): ν ϭ 3054 (w), 2959 (s), 2229(s), 1594 (s), 1504 (s), 1454 (s), 1412 (w),
1362 (s), 1319 (s), 1257 (s), 1166 (vs), 1030 (s), 857 (w), 817 (s), 544 (w),
Preparation of the phthalonitrile derivatives 1, 2a,b
and 3
The coupling of 4-nitrophthalonitrile with the dendritic alcohols
was carried out as described by McKeown et al. [13] who reported
the synthesis of 2a and 3. The analytical and spectroscopic data of
1 and 2b are given below. The yields refer to the preparation on a
5 mmol scale.
522(s) cmϪ1
.
General procedure for the preparation of the
functionalized bis(pyridylimino)isoindol ligands 4 ؊
6. (11-Br)-BPI-[G-1] (4)
4-[G-1]-phthalodinitrile (1)
The phthalodinitriles 1 Ϫ 3 (1.5 mmol), 2-amino-5-bromopyridine
(552 mg ϭ 2.3 mmol) and CaCl2 (70.0 mg ϭ 0.63 mmol) were
heated in 15 ml of n-hexanol under reflux (4, 5a: 24 h, 5b: 48 h,
6: 10 d). Upon cooling to room temperature, the respective BPI-
derivatives precipitated and were isolated by filtration. After extrac-
tion with ca 100 ml of water, the yellow solids were dried in a
dessiccator over P4O10.
Yield: 63 % (colourless oil). C25H22N2O3 (398.46 g.molϪ1):
calcd.: C 75.36, H 5.57, N 7.03; found: C 75.17, H 5.61,
N 6.76 %.
(11-Br)-BPI-[G-1] (4)
Yield: 53 %. M.p.: 88 °C. C35H29Br2N5O3 (727.45 g.molϪ1) calcd.:
C 57.79, H4.02, N 9.63; found: C 57.31, H 3.61, N 9.15 %.
1H-NMR (300.17 MHz, CDCl3, 295 K): δ ϭ 3.65Ϫ3.76 (m, 4 H, H-10), 4.53
(s, 4 H, H-11), 4.67Ϫ4.70 (m, 1 H, H-9), 7.24Ϫ7.36 (m, 12 H, H-Ph, H-3,5),
3
7.62 (d, JHH ϭ 8.8 Hz, 1 H, H-6). {1H}13C-NMR (100.61 MHz, CDCl3,
295 K): δ ϭ 69.1 (C-10,11), 73.0 (C-10, 11), 77.9 (C-9), 106.9 (C-1), 115.1
(C-7/8), 115.6 (C-7/8), 116.8 (C-2), 120.5 (C-3/5), 120.8 (C-3/5), 127.2 (C-
Ph), 127.7 (C-Ph), 128.3 (C-Ph), 134.8 (C-6), 137.2 (C-12), 161.6 (C-4). IR
(neat): ν ϭ 3063 (w), 2866 (s), 2601 (vw), 2230 (vs), 1722 (s), 1596 (s), 1562
(s), 1494 (s), 1453 (s), 1425 (w), 1366 (s), 1252 (vs), 1206 (s), 1097 (vs), 1027
(s) cmϪ1
.
1H-NMR (300.17 MHz, CDCl3, 295 K): δ ϭ 3.68Ϫ3.78 (m, 4 H, H-14), 4.57
(s, 4 H, H-15), 4.81 (m, 1 H, H-13), 7.21-7.48 (m, 13 H, Ph-H, H-5, H-9),
7.60 (s, 1 H, H-3), 7.79 (s, 2 H, H-10), 7.89 (s, 1 H, H-6), 8.56 (s, 2 H, H-12),
13.46 (s, 1 H, N-H). {1H}13C-NMR (100.61 MHz, CDCl3, 295 K): δ ϭ 69.2/
69.3 (C-14), 73.5/73.6 (C-15), 78.2 (CH), 108.6 (C-3), 116.0/116.3 (C-11),
119.9 (C-5), 124.2 (C-6), 124.4/124.6 (C-9), 127.6 (C-Ph), 127.9 (C-Ph), 128.5
(C-Ph), 137.3/137.5 (C-1,2), 137.8 (C-Ph), 140.5 (C-10), 148.4/148.5 (C-12),
153.6 (C-7), 158.7 (C-8), 161.9 (C-4). IR (KBr): ν ϭ 1718 (w), 1623 (s), 1560
4-[t-Bu-(3,5)-G-1]-phthalodinitrile (2b)
Yield: 89 %. M.p.: 149 °C. C37H38N2O3 (558.72 g.molϪ1): calcd.: C
79.54, H 6.85, N 5.01; found: C 79.27, H 6.96, N 4.65 %.
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B. A. Siggelkow, L. H. Gade
(vs), 1480 (w), 1449 (s), 1354 (w), 1324 (vw), 1265 (w), 1229 (s), 1090 (s),
1019 (w) cmϪ1
(11-Br)-BPI-[(3,5)-G-2] (6)
Yield: 8 %. M.p.: 57 °C. C67H53Br2N5O7 (1200.0 g.molϪ1): calcd.:
.
C 67.06, H 4.45, N 5.84; found: C 67.05, H 4.86, N 5.17 %.
(11-Br)-BPI-[(3,5)-G-1] (5a)
Yield: 97 %. M.p.: 224 °C. C39H29Br2N5O3 (775.50 g.molϪ1):
calcd.: C 60.40, H3.77, N 9.03; found: C 60.57, H3.95, N 8.70 %.
1H-NMR (300.17 MHz, CDCl3, 295 K): δ ϭ 4.95 (s, 2 H, H-13), 4.99 (s, 8 H,
H-23), 5.01 (s, 4 H, H-18), 6.55Ϫ6.67 (m, 9 H, H-15, 17, 20, 22), 7.07 (dd,
1H-NMR (300.18 MHz, CDCl3, 295 K): δ ϭ 5.03 (s, 4 H, H-18), 5.10 (s, 2 H,
H-13), 6.58 (s, 1 H, H-17), 6.70 (s, 2 H, H-15), 7.15 (d, JHH ϭ 8.4 Hz, 1 H,
H-5), 7.30-7.33 (pseudo-t, 2 H, H-9), 7.36Ϫ7.49 (m, 10 H, H-Ph), 7.52 (s,
3JHH ϭ 8.5 Hz, JHH ϭ 2.2 Hz, 1 H, H-5), 7.27 (d, JHH ϭ 8.5 Hz, 2 H, H-
9), 7.29Ϫ7.43 (m, 20 H, H-Ph), 7.44 (s, 1 H, H-3), 7.69 (m, 2 H, H-10), 7.80
(d, 1 H, H-6), 8.48 (m, 2 H, H-12), 13.42 (s, 1 H, N-H). {1H}13C-NMR
(100.61 MHz, CDCl3, 295 K): δ ϭ 69.9, 70.0, 70.2 (C-13/18/23), 101.5 (C-
22), 101.7 (C-17), 106.3 (C-20), 107.3 (C-3), 116.2/116.4 (C-11), 119.9 (C-5),
124.3/124.6 (C-9), 126.4 (C-6), 127.5 (C-Ph), 127.9 (C-Ph), 128.5 (C-Ph),
136.7 (C-19,24), 137.4 (C-1), 138.4 (C-14/15), 139.1 (C-14/15), 140.5 (C-10),
148.4 (C-12), 153.4/153.6 (C-7), 158.3 (C-8), 160.0 (C-16/21), 160.1 (C-16/
21), 162.2 (C-4).MS (FAB): 1199 [MϩH]ϩ. IR (KBr): ν ϭ 3294 (br), 2921
4
3
3
4
3
1 H, H-3), 7.80 (pseudo-t/d, JHH ϭ 2.2 Hz, 2 H, H-10), 7.90 (d, JHH
ϭ
4
8.4 Hz, 1 H, H-6), 8.54 (pseudo-dd, JHH ϭ 2.2 Hz, 2 H, H-12), 13.48 (s,
1 H, N-H). {1H}13C-NMR (75.48 MHz, CDCl3, 295 K): δ ϭ 70.2 (C-13/18),
70.4 (C-13/18), 101.7 (C-17), 106.3 (C-15), 107.2 (C-3), 116.0/116.4 (C-11),
119.9 (C-5), 124.1 (C-9), 124.6 (C-6), 127.5 C-Ph), 128.0 (C-Ph), 128.6 (C-
Ph), 136.7 (C-19), 137.6 (C-1,2), 138.5 (C-14), 140.5 (C-10), 148.5/148.6 (C-
12), 153.6 (C-7), 158.6/158.8 (C-8), 160.2 (C-16), 162.1 (C-4). IR (KBr): ν ϭ
3422 (br), 1625 (s), 1560 (s), 1489 (vw), 1448 (m), 1355 (w), 1292 (w), 1228
(w), 1735 (s), 1647 (s), 1595 (vs), 1451 (s), 1292 (w), 1155(s), 1028 (s) cmϪ1
.
(w), 1154 (w), 1089 (w), 1027 (w), 835 (w), 732 (vw), 526 (vw) cmϪ1
.
Preparation of alkynyl-substituted BPI ligands 7a؊c
The BPI-derivative 5a (0.5 mmol), 6 molar equivalents of
the substituted acetylene, 0.12 molar equivalents of CuI and
0.12 molar equivalents of tetrakis(triphenylphosphine)-pal-
ladium(0) were stirred in 10 ml of triethylamine at 60 °C.
The reaction time was 8 d for 7a, 5 d for 7b and 24 h for
7c. After cooling the reaction mixture to ambient tempera-
ture, the solvent was removed in vacuo. The residue was
redissolved in 10 ml of CH2Cl2 the solution extracted with
10 ml of water and then dried over magnesium sulfate. The
evaporation of the solvent in vacuo yielded the reaction
products as pure yellow microcristalline solids.
(11-Br)-BPI-[t-Bu-(3,5)-G-1] (5b)
Yield: 45 %. m.p.: 118 °C. C47H45Br2N5O3 (887.71 g.molϪ1): calcd.:
C 63.59, H 5.11, N 7.89; found: C 63.50, H 5.43, N 7.78 %.
(11-TMS-acetylen)-BPI-[(3,5)-G-1] (7a)
Yield: 72 %. M.p.: 153 °C. C49H47N5O3Si2 (810.12 g.molϪ1): calcd.:
C 75.26, H6.06, N8.96; found: C 75.13, H5.79, N 8.15 %.
1H-NMR (300.17 MHz, CDCl3, 295 K): δ ϭ 1.33 (s, 18 H, CH3), 5.01 (s,
4 H, H-18), 5.11 (s, 2 H, H-13), 6.61 (s, 1 H, H-17), 6.72 (s, 2 H, H-15), 7.16
(d, 3JHH ϭ 8.8 Hz, 1 H, H-5), 7.27Ϫ7.43 (m, 10 H, Ph-H, H-9), 7.53 (s, 1 H,
3
3
H-3), 7.79 (d, JHH ϭ 8.5 Hz, 2 H, H-10), 7.88 (d, JHH ϭ 8.8 Hz, 1 H, H-
6), 8.56 (s, 2 H, H-12), 13.46 (s, 1 H, N-H). {1H}13C-NMR (100.61 MHz,
CDCl3, 295 K): δ ϭ 31.3 (CH3), 34.6 (CCH3), 70.0 (C-13/18), 70.4 (C-13/
18), 101.7 (C-17), 106.3 (C-15), 107.3 (C-3), 116.1/116.4 (C-11), 120.1 (C-5),
124.4 (C-9), 124.6 (C-6), 125.5 (C-Ph), 127.6 (C-Ph), 133.6 (C-19), 137.6 (C-
1,2), 138.4 (C-14), 140.6 (C-10), 148.6 (C-12), 151.1 (C-22), 153.6 (C-7),
158.6 (C-8), 160.3 (C-16), 162.3 (C-4). IR (KBr): ν ϭ 2959 (w), 1624 (s),
1563 (s), 1448 (s), 1352 (w), 1228 (w), 1159 (w), 1028 (w), 831 (w) cmϪ1
.
2580
 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2005, 631, 2575Ϫ2584

Multiple Functionalization of Bis(2-pyridylimino)isoindole (BPI) Ligands
1H-NMR (300.18 MHz, CDCl3, 295 K): δ ϭ 5.04 (s, 4 H, H-18), 5.10 (s, 2 H,
1,2), 138.5 (C-14/10), 139.7 (C-14/10), 152.1 (C-12,7), 159.3 (C-8), 159.9 (C-
16), 161.2 (C-4). MS (FAB): 818 [MϩH]ϩ. IR (KBr): ν ϭ 3264 (br), 2961
(w), 2135 (vw), 1629 (s), 1567 (s), 1489 (s), 1469 (s), 1352 (w), 1261 (s), 1215
3
H-13), 6.58 (s, 1 H, H-17), 6.70 (s, 1 H, H-15), 7.16 (d, JHH ϭ 7.4 Hz, 2 H,
3
H-9), 7.25-7.40 (m, 11 H, Ph-H, H-5), 7.54 (s, 1 H, H-3), 7.76 (d, JHH
ϭ
3
7.4 Hz, 2 H, H-10), 7.88 (d, JHH ϭ 8.1 Hz, 1 H, H-6), 8.69 (s, 2 H, H-12),
13.66 (s, 1 H, N-H). {1H}13C-NMR (75.48 MHz, CDCl3, 295 K): δ ϭ 0.9
(CH3), 70.1 (C-13/18), 70.4 (C-13/18), 98.0 (CϵCSi),101.8 (C-17), 102.2
(CϵCSi), 106.4 (C-15), 107.1 (C-3), 116.1/116.3 (C-11), 119.9 (C-5), 122.4
(C-9), 124.0 (C-6), 127.5 (C-Ph), 128.0 (C-Ph), 128.6 (C-Ph), 136.7 (C-19),
137.7 (C-1,2), 138.5 (C-14), 140.8 (C-10), 151.0 (C-12), 153.7 (C-7), 159.2/
159.3 (C-8), 160.2 (C-16), 162.1 (C-4). 29Si-NMR (79.5 MHz, CDCl3,
295 K): δ ϭ Ϫ17.0. IR (KBr): ν ϭ 2948 (w), 2156 (s), 1623 (vs), 1565 (vs),
1485 (w), 1458 (w), 1379 (w), 1357 (w), 1218 (s), 1155 (s), 1062 (w), 1025
(w), 1101 (s), 1025 (s), 802 (w), 752 (vw), 689 (w) cmϪ1
.
General procedure for the preparation of the
palladium(II) complexes 8؊11
The bis(pyridyl)isoindole (BPI) derivative (in general
0.3 mmol) and together with 1.1 molar equivalents of
[PdCl2(PhCN)2] and 1.1 molar equivalents of NEt3 were
dissolved in benzene and stirred at room temperature for 2
days. Depending on the substitution pattern of the ligand,
the palladium complex precipitated directly from the reac-
tion mixture or remained in solution. In the case of com-
pound 10b direct precipitation of the reaction product was
observed and the resulting solid was separated by filtration.
The co-product [NEt3H]Cl was extracted from the solid by
extraction with 3 x 50 ml of water and the crude product
thus obtained was recrystallized from CH2Cl2/n-hexane.
For all other complexes the reaction product remained in
solution. After removal of the solvent and the volatiles in
vacuo, the solid residue was extracted with 10 ml of benzene
and the solvent of the extract evaporated in vacuo. After
washing with 3 x 50 ml of water and 10 ml of hexane, the
crude product thus obtained was recrystallized from
CH2Cl2/n-hexane. All compounds are deep yellow-range
crystalline solids.
(w) cmϪ1
.
(11-Ph3Si-acetylen)-BPI-[(3,5)-G-1] (7b)
Yield: 84 %. M.p.: 134 °C (dec.). C79H59N5O3Si2 (1182.54 g.molϪ1):
calcd.: C 80.24, H 5.03, N 5.03; found: C 80.67, H 4.94, N 4.94 %.
1H-NMR (300.17 MHz, CDCl3, 295 K): δ ϭ 5.05 (s, 4 H, H-18), 5.18 (s, 2 H,
H-13), 6.59 (s, 1 H, H-17), 6.71 (s, 2 H, H-15), 7.34Ϫ7.71 (m, 46 H, Ph-H,
3
H-5, H-9, H-3), 7.93 (d, JHH ϭ 7.0 Hz, 1 H, H-6), 8.80 (m, 2 H, H-12),
13.73 (s, 1 H, N-H). {1H}13C-NMR (100.61 MHz, CDCl3, 295 K): δ ϭ 70.2
(C-13/18), 70.4 (C-13/18), 82.2 (CϵCSi), 91.9 (CϵCSi), 101.8 (C-14), 106.4
(C-15), 107.1 (C-3), 116.1 (C-11), 120.1 (C-5), 122.6 (C-9), 126.9 (C-6), 127.5
(C-Ph), 128.1 (C-Ph), 128.5 (C-Ph), 130.0 (C-Ph), 130.2 (C-Ph), 132.1 (C-
Ph), 135.5 (C-Ph), 136.7 (C-19), 137.7 (C-1,2), 138.4 (C-14), 141.2 (C-10),
151.2 (C-12), 153.8 (C-7), 159.3 (C-8), 160.2 (C-16), 162.1 (C-4). 29Si-NMR
(79.5 MHz, CDCl3, 295 K): δ ϭ Ϫ28.5. MS (FAB): 1182 [MϩH]ϩ. IR
(KBr): ν ϭ 3062 (w), 3016 (w), 2153 (s), 1624 (s), 1565 (vs), 1483 (w), 1459
(s), 1428 (s), 1355 (w), 1323 (w), 1269 (w), 1221 (w), 1151 (vw), 1112 (vs),
[(11-Br)-BPI-[G-1]-PdCl] (8)
Yield: 58 %. M.p.: 147 °C (dec.). C35H28Br2ClN5O3Pd
(868.32 g.molϪ1): calcd.: C 48.41, H 3.25; N 8.07; found: C 47.94,
H 3.88, N 7.89 %.
1028 (s), 819 (s) cmϪ1
.
(11-Ph-acetylen)-BPI-[(3,5)-G-1] (7c)
Yield:75 %. M.p.: 188 °C. C55H39N5O3 (817.94 g.molϪ1): calcd.: C
80.76, H 4.81, N 8.56; found: C 80.27, H 4.64, N 9.07 %.
1H-NMR (300.17 MHz, CDCl3, 295 K): δ ϭ 3.78Ϫ3.79 (m, 4 H, H-14), 4.57
3
(s, 4 H, H-15), 4.79 (m, 1 H, H-13), 7.12 (d, JHH ϭ 8.5 Hz, 1 H, H-5),
7.26Ϫ7.37 (m, 12 H, H-Ph, H-9), 7.56 (s, 1 H, H-3), 7.79 (d, 3JHH ϭ 8.5 Hz,
1 H, H-6), 7.89 (m, 2 H, H-10), 9.95 (pseudo-d, 2 H, H-12). {1H}13C-NMR
(100.61 MHz, CDCl3, 295 K): δ ϭ 69.3 (C-14), 73.5 (C-15), 108.7 (C-3),
114.4/114.7 (C-11), 120.1 (C-5), 123.9 (C-6/9), 127.4 (C-6/9), 127.6 (C-Ph),
128.3 (C-Ph), 128.4 (C-Ph), 137.9 (C-1,2), 139.3 (C-Ph), 141.8 (C-10), 150.5
(C-7/8), 153.2 (C-7/8), 153.5/153.6 (C-12), 161.6 (C-4). MS (FAB): 832 [M-
Cl]ϩ. IR (KBr): ν ϭ 2962 (w), 2855 (w), 1602 (w), 1569 (s), 1515 (w), 1482
(s), 1451 (vs), 1360 (w), 1261 (s), 1219 (s), 1186 (s), 1105 (vs), 1068 (s), 1022
1H-NMR (400.13 MHz, CDCl3, 295 K): δ ϭ 5.03 (s, 4 H, H-18), 5.14 (s, 2 H,
H-13), 6.57 (s, 1 H, H-17), 6.70 (s, 2 H, H-15), 7.24-7.55 (m, 26 H, Ph-H, H-
5, H-9, H-3), 7.85 (s(br), 1 H, H-6), 8.78 (s(br), 2 H, H-12), 13.93 (s, 1 H, N-
H). {1H}13C-NMR (100.61 MHz, CDCl3, 295 K): δ ϭ 69.3 (C-13,18), 79.0
(CϵCSi), 92.8 0 (CϵCSi), 100.9 (C-14), 106.5 (C-15), 108.1 (C-3), 115.5 (C-
11), 118.4 (C-5/9), 119.6 (C-5/9), 125.5 (C-6), 126.7 (C-Ph), 126.9 (C-Ph),
127.3 (C-Ph), 127.6 (C-Ph), 135.7 (C-Ph/C-19), 136.5 (C-Ph/C-19), 137.9 (C-
(s) cmϪ1
.
Z. Anorg. Allg. Chem. 2005, 631, 2575Ϫ2584
zaac.wiley-vch.de
 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
2581

B. A. Siggelkow, L. H. Gade
[(11-Br)-BPI-[(3,5)-G-1]-PdCl] (9a)
[(11-TMS-acetylen)-BPI-[(3,5)-G-1]-PdCl] (10a)
Yield: 43 %. M.p.: 85 °C. C39H28Br2ClO3N5Pd (917.37 g.molϪ1):
calcd.: C 51.12, H 3.08, N 7.64; found: C 50.98, H 3.88, N 7.33 %.
Yield: 34 %. M.p.: 108 °C (dec.). C49H46ClN5O3PdSi2
(950.98 g.molϪ1): calcd.: C 61.89, H 4.88, N 7.36; found: C 61.27,
H 4.31, N 7.17 %.
1H-NMR (300.18 MHz, CDCl3, 295 K): δ ϭ 5.04 (s, 4 H, H-18), 5.09 (s, 2 H,
1H-NMR (300.17 MHz, CDCl3, 295 K): δ ϭ 0.26 (s, 18 H, CH3), 5.04 (s,
4 H, H-18), 5.13 (s, 2 H, H-13), 6.59 (s, 1 H, H-17), 6.70 (s, 2 H, H-15), 7.13
(d, 3JHH ϭ 8.1 Hz, 1 H, H-5), 7.39Ϫ7.47 (m, 12 H, H-Ph, H-9), 7.54 (s, 1 H,
3
H-13), 6.59 (s, 1 H, H-17), 6.71 (s, 2 H, H-15), 7.07 (dd, JHH ϭ 8.4 Hz,
4JHH ϭ 2.2 Hz, 1 H, H-5), 7.11Ϫ7.39 (m, 13 H, H-Ph, H-3, H-9), 7.76 (d,
3JHH ϭ 8.4 Hz, 2 H, H-10), 7.83 (d, 3JHH ϭ 8.4 Hz, 1 H, H-6), 9.90 (pseudo-
3
3
4
ϭ
1.8 Hz, 2 H, H-12). {1H}13C-NMR (75.48 MHz, CDCl3,
H-3), 7.80 (d, JHH ϭ 8.5 Hz, 2 H, H-10), 7.89 (d, JHH ϭ 8.1 Hz, 1 H, H-
6), 9.92 (pseudo-d, 2 H, H-12). {1H}13C-NMR (100.61 MHz, CDCl3, 295 K):
δ ϭ 1.0 (CH3), 70.1 (C-13/18), 70.3 (C-13/18), 84.6 (CϵC), 99.8 (CϵC),
101.7 (C-17), 106.4 (C-15), 107.5 (C-3), 116.4 (C-11), 119.1 (C-5), 123.9 (C-
9), 125.8 (C-6), 127.5 (C-Ph), 128.3 (C-Ph), 128.6 (C-Ph), 136.7 (C-19), 138.5
(C-1,2/14), 139.7 (C-1,2/14), 141.4 (C-10), 150.8 (C-12), 153.9 (C-7), 156.6
(C-8), 160.2 (C-16), 162.0 (C-4). 29Si-NMR (79.5 MHz, CDCl3, 295 K): δ ϭ
Ϫ22.1. MS (FAB): 914 [M-Cl]ϩ. IR (KBr): ν ϭ 2962 (s), 2160 (w), 1596 (w),
1560 (w), 1459 (w), 1384 (w), 1363 (w), 1331 (vw), 1261 (s), 1098 (vs), 1023
d/d, JHH
295 K): δ ϭ 70.2 (C-13,18), 101.6 (C-17), 106.4 (C-15), 107.4 (C-3), 114.4/
114.7 (C-11), 119.1 (C-5), 122.0 (C-6,9), 123.9 (C-6,9), 127.5 (C-C-Ph), 128.0
(C-Ph), 128.6 (C-Ph), 136.7(C-1,2/14/19), 138.5(C-1,2/14/19), 139.4 (C-1,2/
14/19), 141.7 (C-10), 150.4/150.5 (C-12), 153.2(C-7/8), 153.6 (C-7/8), 160.8
(C-16), 162.0 (C-4). MS (FAB): 880 [M-Cl]ϩ. IR (KBr): ν ϭ 3405 (br), 2932
(w), 2676 (w), 1725 (vw), 1641 (vw), 1602 (s), 156 (s), 1517 (w), 1485 (w),
1451 (s), 1360 (w), 1324 (vw), 1282 (vw), 1218 (w), 1139 (w), 1107 (s), 1067
(s), 833 (w) cmϪ1
.
(vs) cmϪ1
.
[(11-Br)-BPI-[t-Bu-(3,5)-G-1]-PdCl] (9b)
[(11-Ph3Si-acetylen)-BPI-[(3,5)-G-1]-PdCl] (10b)
Yield: 38 %. M.p.: 111 °C. C47H44Br2ClN5O3Pd (1028.58 g.molϪ1):
calcd.: C 54.88, H 4.31, N 6.80; found: C 54.74, H 4.65, N 6.53 %.
Yield: 61 %. M.p.: 156 °C (dec.). C79H58ClN5O3PdSi2
(1320.38 g.molϪ1): calcd.: C 71.70, H 4.42, N 5.30; found: C 71.25,
H 3.81, N 4.97 %.
1H-NMR (300.17 MHz, CDCl3, 295 K): δ ϭ 1.31 (s, 9 H, CH3), 4.99 (s, 4 H,
H-18), 5.09 (s, 2 H, H-13), 6.59 (s, 1 H, H-17), 6.70 (s, 2 H, H-15), 7.07 (d,
3JHH ϭ 8.4 Hz, 1 H, H-5), 7.29Ϫ7.44 (m, 13 H, H-Ph, H-3, H-9), 7.74 (d,
3JHH ϭ 8.4 Hz, 1 H, H-6), 7.81 (d, 3JHH ϭ 8.8 Hz, 2 H, H-10), 9.90 (pseudo-
d, 2 H, H-12). {1H}13C-NMR (100.61 MHz, CDCl3, 295 K): δ ϭ 31.3 (CH3),
34.6 (CCH3), 70.0 (C-13/18), 70.3 (C-13/18), 101.6 (C-17), 106.3 (C-15),
107.4 (C-3), 114.4 (C-11), 119.1 (C-5), 123.8 (C-6, 9), 124.5 (C-6,9), 125.5
(C-Ph), 126.5 (C-Ph), 127.5 (C-Ph), 133.6 (C-19), 138.4 (C-1,2/14), 139.4 (C-
1,2/14), 141.7 (C-10), 150.5 (C-7/8), 151.1 (C-7/8), 153.3/153.6 (C-12), 160.3
(C-16), 161.9 (C-4). MS(FAB): 991 [M-Cl]ϩ. IR (KBr): ν ϭ 3086 (w), 2959
(vs), 2855 (vw), 1601 (s), 1573 (s), 1517 (w), 1486 (w), 1452 (s), 1361 (s),
1329 (w), 1283 (w), 1218 (w), 1186 (w), 1153 (w), 1107 (s), 1073 (w), 1016
1H-NMR (300.17 MHz, CDCl3, 295 K): δ ϭ 5.04 (s, 4 H, H-18), 5.15 (s, 2 H,
H-13), 6.59 (s, 1 H, H-17), 6.71 (s, 2 H, H-15), 7.16-7.71 (m, 44 H, H-Ph, H-
3, H-5, H-9), 7.91-7.94 (m, 3 H, H-6, H-10), 10.10 (pseudo-d, 2 H, H-12).
{1H}13C-NMR (100.61 MHz, CDCl3, 295 K): δ ϭ 70.2 (C-13/18), 70.5 (C-
13/18), 82.2 (CϵC), 92.0 (CϵC), 101.8 (C-14), 104.5 (C-15), 106.4 (C-3),
119.5 (C-5), 125.9 (C-9), 127.5 (C-6), 128.6 (C-Ph), 129.9 (C-Ph), 130.3 (C-
Ph), 132.2 (C-Ph), 132.8 (C-Ph), 136.0 (C-Ph), 136.5 (C-Ph), 136.7 (C-19),
138.5 (C-1,2), 141.7 (C-10), 150.9/151.2 (C-12), 154.2 (C-7), 157.1 (C-8),
159.1 (C-16), 160.2 (C-4). 29Si-NMR (79.5 MHz, CDCl3, 295 K): δ ϭ Ϫ22.3.
MS (FAB): 1286 [M-Cl]ϩ. IR (KBr): ν ϭ 3201 (vw), 2959 (w), 2071 (s), 1586
(w), 1560 (s), 1458 (s), 1428 (vs), 1385 (w), 1359 (w), 1258 (w), 1183 (w),
(vw) cmϪ1
.
1113 (vs), 1056 (w) cmϪ1
.
2582
 2005 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2005, 631, 2575Ϫ2584

Multiple Functionalization of Bis(2-pyridylimino)isoindole (BPI) Ligands
[(11-Ph-acetylen)-BPI-[(3,5)-G-1]-PdCl] (10c)
Catalyst Testing of 9b and 11
Yield:
55 %.
M.p.:
108 °C
(dec.).
C55H38ClN5O3Pd
The catalyst tests were carried out in thf at 1 bar H2 pressure using
2 mol% of palladium catalyst (the catalyst concentration being ca.
1.5 µmol.mLϪ1). The course of the catalytic hydrogenations was
monitored by GC/MS-spectrometry performed with a Shimadzu
GC-17A/GCMS-QP5050A. Column: SGE BPX5, 5 % phenyl, po-
lysilyphenylene-siloxane, nonpolar, 30 m, 0.22 mm, carrier gas He.
The products were analyzed by comparison of the recorded mass
spectra and retention times with those of authentic samples. The
measured relative ratio of the products was calibrated by compara-
tive measurements with known substance ratios using pure sub-
stances. The data displayed are average values of two runs.
(958.81 g.molϪ1): calcd.: C 68.90, H 3.99, N 7.30; found: C 68.63,
H 3.41, N 6.82 %.
GC/MS-parameters (styrene hydrogenation): T (start) ϭ 50 °C, T
(injector) ϭ 250 °C, T (interface) ϭ 280 °C, 30.0 m (0.22 mm),
0.7 ml/min He (flow rate), 66.3 kPa (column pressure), temperature
program: 5.0 min, 50 °C; 2 °C.minϪ1, 80 °C; 20 °C.minϪ1, 250 °C;
retention times: tR (ethyl benzene) ϭ 7.84 min, tR (styrene) ϭ
9.12 min,
1H-NMR (300.17 MHz, CDCl3, 295 K): δ ϭ 5.01 (s, 4 H, H-18), 5.09 (s, 2 H,
H-13), 6.57 (s, 1 H, H-17), 6.69 (s, 2 H, H-15), 7.05 (s, 1 H, H-5), 7.33Ϫ7.51
(m, 22 H, H-Ph, H-9), 7.51 (s, 1 H, H-3), 7.83 (s, 2 H, H-10), 7.98 (s, 1 H,
H-6), 10.06 (s, 2 H, H-12). {1H}13C-NMR (100.61 MHz, CDCl3, 295 K): δ ϭ
70.0 (C-12, 14), 85.2 (CϵC), 94.0(CϵC), 101.6 (C-17), 106.3 (C-15), 107.1
(C-3), 116.5 (C-11), 119.0 (C-5), 122.3 (C-9), 125.4 (C-6), 127.5 (C-Ph), 128.0
(C-Ph), 128.1 (C-Ph), 128.3 (C-Ph), 128.5 (C-Ph), 128.7 (C-Ph), 130.1 (C-
Ph), 131.7 (C-Ph), 136.6 (C-19), 138.5 (C-1,2/14), 139.7 (C-1,2/14), 140.4 (C-
10), 150.6 (C-12), 153.2 (C-7), 156.1 (C-8), 160.1 (C-16), 161.7 (C-4). MS
(FAB): 922 [M-Cl]ϩ. IR (KBr): ν [Ϫ1] ϭ 2959 (w), 2217 (vw), 1594 (s), 1560
(s), 1486 (s), 1460 (s), 1378 (w), 1354 (w), 1261 (s), 1187 (w), 1100 (vs),
1019 (vs).
GC/MS-parameters (1-octene hydrogenation): T (start) ϭ 35 °C, T
(injektor) ϭ 250 °C, T (interface) ϭ 280 °C, 30.0 m (0.22 mm),
1.5 ml/min He (flow rate), 133.2 kPa (column pressure), tempera-
ture program: 8.0 min, 35 °C; 30 °C.minϪ1, 250 °C; tR (1-octene) ϭ
5.62 min, tR (n-octane) ϭ 5.93 min, tR ((cis/trans)-2-octene) ϭ
6.35 min.
We thank the Deutsche Forschungsgemeinschaft, the CNRS, and
the Institut Universitaire de France for funding.
[(11-Br)-BPI-[(3,5)-G-2]-PdCl] (11)
Yield: 46 %. M.p.: 66 °C. C67H52Br2ClN5O7Pd (1340.86 g.molϪ1):
References
calcd.: C 60.02, H 3.91, N 5.22; found: C 60.87, H 4.83, N 4.81 %.
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1H-NMR (300.17 MHz, CDCl3, 295 K): δ ϭ 4.95 (s, 2 H, H-13), 4.98 (s, 8 H,
´
´
G. Speier, M. Reglier, M. Giorgi, E. Kuzmann, A. Vertes, Eur.
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H-23), 5.01 (s, 4 H, H-18), 6.53-6.97 (m, 9 H, H-15, 17, 20, 22), 7.18 (dd,
4
3JHH ϭ 8.8 Hz, JHH ϭ 3.7 Hz, 1 H, H-5), 7.28Ϫ7.38 (m, 20 H, H-Ph), 7.52
3
(s, 1 H, H-3), 7.63 (d, JHH ϭ 8.1 Hz, 2 H, H-10), 7.72 (m, 1 H, H-6), 9.83
(m, 2 H, H-12). {1H}13C-NMR (100.61 MHz, CDCl3, 295 K): δ ϭ 70.0 (C-
13,18,23), 101.5 (C-22), 101.7 (C-17), 106.3 (C-20), 107.4 (C-3), 114.4 (C-
11), 119.1 (C-5), 126.5 (C-6/9), 126.9 (C-6/9), 127.5 (C-Ph), 127.9 (C-Ph),
128.5 (C-Ph), 136.7 (C-19,24), 138.5 (C-1), 139.1 (C-14/15), 139.4 (C-14/15),
141.7 (C-10), 150.5 (C-12), 153.2 (C-7/8), 153.5 (C-7/8), 160.1 (C-16,21),
161.8 (C-4). MS (FAB): 1304 [MϩH]ϩ. IR (KBr): ν [Ϫ1] ϭ 3024 (vw), 2921
(vw), 1595 (vs), 1451 (s), 1369 (w), 1317 (w), 1288 (w), 1262 (w), 1213 (vw),
1152 (vs), 1104 (s), 1050 (s), 1027 (s), 828 (s).
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