Synthesis of Arylpalladium(II) Complexes Derived from Benzyl Alcohol, Reactivity toward Alkyl Halides, and Synthesis of Dinuclear Arylpalladium(II) Complexes

Article abstract of DOI:10.1021/acs.organomet.5b00309

The aryl palladium complexes [PdI(C₆H₄CH₂OH-2)(N^{^}N)] (N^{^}N = bpy = 2,2′-bipyridyl (1a), tbbpy = 4,4′-di-tert-butyl-2,2′-bipyridine (1b), tmeda = N,N,N′,N′-tetramethylethylenediamine (1c)) were synthesized by oxidative addition of 2-iodobenzyl alcohol to one equivalent of "[Pd(dba)₂]" (dba = dibenzylideneacetone) in the presence of the N N ligands. By reaction of 1a with three equivalents of XyNC (Xy = 2,6-dimethylphenyl) the insertion complex trans-[PdI{C(-NXy)(C₆H₄CH₂OH-2)}(CNXy)₂] (2) was formed. The reaction of 1a with KO^tBu resulted in the formation of the chelate complex [Pd(κ²-C,O-C₆H₄CH₂O-2)(bpy)] (3), which crystallizes as pairs of molecules bridged by hydrogen bonds to water of crystallization. Complex 3 reacts with XyNC, forming the cyclic imidate N-(2,6-dimethylphenyl)-2-benzofuran-1(3H)-imine (4). By reaction of 3 with various primary alkyl halides RCH₂X, the complexes [PdX(C₆H₄CH₂OCH₂R-2)(bpy)] (X = I, R = H (5a), X = Br, R = Ph (5b), p-C₆H₄CH₂Br (5c), p-C₆H₄Br (5d), and p-C₆H₄I (5e)) were obtained. When the reaction of 3 with p-C₆H₄(CH₂Br)₂ was carried out in a 2:1 ratio, the dinuclear arylpalladium complex [{(bpy)BrPd(C₆H₄CH₂OCH₂-2)}₂(C₆H₄-1,4)] (6) formed. An halide exchange reaction on 5e, using AgOTf and an excess of NaI, afforded [PdI{C₆H₄(CH₂OCH₂(C₆H₄I-4))-2}(bpy)] (5f), which by oxidative addition to [Pd(dba)₂] in the presence of bpy formed another dinuclear arylpalladium complex, [(bpy)IPd(C₆H₄CH₂-2)O(CH₂C₆H₄-4)PdI(bpy)] (7). All the complexes have been extensively characterized by NMR spectroscopy. The crystal structures of 1a, 3·H₂O, and 5e were determined by X-ray diffraction studies.

Full text of DOI:10.1021/acs.organomet.5b00309

Article
pubs.acs.org/Organometallics
Synthesis of Arylpalladium(II) Complexes Derived from Benzyl
Alcohol, Reactivity toward Alkyl Halides, and Synthesis of Dinuclear
Arylpalladium(II) Complexes
́ ́ ́
María-Jose Fernandez-Rodríguez, Eloísa Martínez-Viviente,* and Jose Vicente
Grupo de Química Organometal
́ ́
ica, Departamento de Química Inorganica, Facultad de Química, Universidad de Murcia, Apartado
4021, 30071, Murcia, Spain
Peter G. Jones*
Institut fu
Germany
̈
̈
r Anorganische und Analytische Chemie der Technischen Universitat Braunschweig, Postfach 3329, 38023, Braunschweig,
*
S Supporting Information
ABSTRACT: The aryl palladium complexes [PdI-
∧
∧
(
C H CH OH-2)(N N)] (N N = bpy = 2,2′-bipyridyl (1a),
6
4
2
tbbpy = 4,4′-di-tert-butyl-2,2′-bipyridine (1b), tmeda =
N,N,N′,N′-tetramethylethylenediamine (1c)) were synthesized
by oxidative addition of 2-iodobenzyl alcohol to one equivalent
of “[Pd(dba) ]” (dba = dibenzylideneacetone) in the presence
2
∧
of the N N ligands. By reaction of 1a with three equivalents of
XyNC (Xy = 2,6-dimethylphenyl) the insertion complex trans-
[
PdI{C(NXy)(C H CH OH-2)}(CNXy) ] (2) was
6
4
2
2
t
formed. The reaction of 1a with KO Bu resulted in the
formation of the chelate complex [Pd(κ -C,O-C H CH O-
2
6
4
2
2
)(bpy)] (3), which crystallizes as pairs of molecules bridged
by hydrogen bonds to water of crystallization. Complex 3
reacts with XyNC, forming the cyclic imidate N-(2,6-dimethylphenyl)-2-benzofuran-1(3H)-imine (4). By reaction of 3 with
various primary alkyl halides RCH X, the complexes [PdX(C H CH OCH R-2)(bpy)] (X = I, R = H (5a), X = Br, R = Ph (5b),
2
6
4
2
2
p-C H CH Br (5c), p-C H Br (5d), and p-C H I (5e)) were obtained. When the reaction of 3 with p-C H (CH Br) was
6
4
2
6
4
6
4
6
4
2
2
carried out in a 2:1 ratio, the dinuclear arylpalladium complex [{(bpy)BrPd(C H CH OCH -2)} (C H -1,4)] (6) formed. An
6
4
2
2
2
6
4
halide exchange reaction on 5e, using AgOTf and an excess of NaI, afforded [PdI{C H (CH OCH (C H I-4))-2}(bpy)] (5f),
6
4
2
2
6
4
which by oxidative addition to [Pd(dba) ] in the presence of bpy formed another dinuclear arylpalladium complex,
2
[
(bpy)IPd(C H CH -2)O(CH C H -4)PdI(bpy)] (7). All the complexes have been extensively characterized by NMR
6 4 2 2 6 4
spectroscopy. The crystal structures of 1a, 3·H O, and 5e were determined by X-ray diffraction studies.
2
INTRODUCTION
electron-donating ability of this group, however, played a
■
1
2,14
crucial role in the reactivity toward nitriles,
carbodii-
Pd(II) aryl complexes have acquired a great relevance in
organometallic chemistry, because of their involvement in
carbon−carbon and carbon−heteroatom bond-forming reac-
1
3,14
14
mides,
and isothiocyanates, which afforded the first
examples of the insertion of these molecules into a C−M
bond of a late transition metal. In view of these results, we
decided to extend our research to ortho-palladated hydroxy-
methylphenyl complexes, to investigate how the methylene link
in the alcoholic substituent would affect the reactivity of the
complexes. 2-Hydroxymethylphenyl palladium complexes with
a dppf ligand (dppf = 1,1′-bis(diphenylphosphino)ferrocene)
have been used as catalysts to build end-functionalized
1
tions of great synthetic importance. We have been especially
interested in the synthesis of ortho-substituted arylpalladium
2
−8
complexes,
as the substituent in ortho position may
participate in the reactions with unsaturated organic molecules,
forming new ligands and/or organic compounds.
often, the ortho substitution also results in the formation of
cyclopalladated complexes.
2
−6,8−15
Very
2
,3,6−8,10,12−15
17
polyacetylenes. There has also been a report on oxapallada-
Within this line of research, our group has previously
18
cycles derived from 2-hydroxymethylbenzene and their use as
reported on the synthesis and reactivity of ortho-palladated
5
,12−14,16
phenol derivatives.
Their reactions with CO, iso-
cyanides, alkenes, alkynes, and allenes did not involve the
Received: April 13, 2015
5
,16
interaction with the OH group in ortho position.
The
©
XXXX American Chemical Society
A
DOI: 10.1021/acs.organomet.5b00309
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Organometallics
Article
19
precatalysts in Heck and cross-coupling reactions. However,
the reactivity of these complexes toward unsaturated molecules
has not been systematically investigated. In this paper we report
our first results in this area, which involve the synthesis of a
family of Pd complexes derived from benzyl alcohol, one of
them a chelate complex resulting from the deprotonation of the
alcohol. This chelate complex has shown an interesting
chemistry toward alkyl halides, involving the nucleophilic
attack of the coordinated oxygen on the alkyl group and
resulting in the opening of the chelate ring and the formation of
new aryl palladium complexes with larger substituents on the
aryl ring. We have found no precedent in the literature for this
type of reactivity in a C,O-cyclometalated aryl group
coordinated to a late transition metal. The reaction works
very well for a variety of primary alkyl halides and can be a
useful chemical tool to build ligands on a pre-existing complex,
as in 6 and 7.
Scheme 1
Reactivity of [PdI(C H CH OH-2)(bpy)] (1a). We have
6
4
2
Dinuclear Pd complexes have attracted considerable interest
in the literature. There are examples where the two [Pd]
investigated the reactivity of complex 1a toward unsaturated
molecules such as alkynes, alkenes, nitriles, cyanamides, allenes,
and carbon monoxide, with and without the addition of TlOTf,
but we were not able to obtain clean insertion (C−Pd bond) or
19−24
moieties are attached to the same aryl ring,
as well as
examples where the two Pd atoms are linked by other
8
,23,25−33
ligands.
These dinuclear complexes have in some
28
addition (O−H bond) products, in contrast to our previous
cases been used as catalysts, e.g., for Heck, Hartwig−
5,16
observations with ortho-palladated phenol derivatives.
We
3
2
33
25,31
Buchwald, Hiyama, and Suzuki−Miyaura reactions.
had already proposed that the OH group directly bonded to the
The presence of two Pd atoms can improve the efficiency
and selectivity of a catalyst, promote reactions that are difficult
to achieve with a mononuclear complex, and result in the
aryl ligand played a crucial role in the insertion reactions with
12,14
13,14
14
nitriles,
carbodiimides,
and isothiocyanates, via a
resonance form that locates the negative charge on the ipso
3
0,31
formation of unexpected compounds.
The dinuclear
12,14
carbon.
It now seems that the methylene link is detrimental
complexes that we report in this paper are quite novel in that
they are bis(arylpalladium) complexes, for which there are very
even in the reactions with other molecules such as alkynes,
alkenes, and CO, where the OH group did not seem to be
8
,23,26,29
few precedents in the literature.
Moreover, they are the
5,16
involved. We have been successful only in the reaction of 1a
first examples where the aryl groups are ortho-substituted. Their
with three equivalents of XyNC (Xy = 2,6-dimethylphenyl),
which, when carried out in cold THF, instantaneously formed
the insertion complex trans-[PdI{C(NXy)(C H CH OH-
8
26
reactivity in insertion or coupling reactions can afford
interesting and novel compounds, and we plan to pursue this
subject.
6
4
2
2
)}(CNXy) ] (2, Scheme 1), which had to be isolated
2
We also report in this paper the result of the reactions with
XyNC of the complexes derived from benzyl alcohol, where a
previously unknown cyclic imidate has been isolated and
characterized. Five-membered cyclic imidates are of interest
because they are expected to have potential bioactivities similar
to those of their structurally similar isoindolin-1-one counter-
immediately to avoid decomposition. Complex 2 is the result
of the insertion of one isocyanide molecule into the C−Pd
bond and the displacement of the bpy ligand by two other
molecules. The compound is stable in the solid state, but it
decomposes in solution to form [Pd I (CNXy) ], which is
easily identified by its H NMR resonance at 2.53 ppm. Pd
complexes similar to 2, with other functional groups in the aryl
2
2
2
1
3
4
parts.
ring, have been previously prepared in a similar manner, mainly
RESULTS AND DISCUSSION
5,6,8,10,11,35
■
(
by our research group.
dinuclear analogues, prepared by oxidative addition or by a
double insertion reaction.
The reaction of complex 1a with KO Bu resulted in the
abstraction of the alcoholic proton and the coordination of the
oxygen to Pd, displacing the iodo ligand and forming the
We have also described a few
∧
∧
22
Synthesis of [PdI(C H CH OH-2)(N N)] (N N = bpy
6
4
2
8,24
1a), tbbpy (1b), tmeda (1c)). Complexes 1a−c were
obtained by oxidative addition of 2-iodobenzyl alcohol to one
t
equivalent of [Pd(dba) ] in the presence of bpy, tbbpy, and
2
tmeda (Scheme 1). We have similarly prepared the related
2
complex [PdI(C H CH OH)-2}(PPh ) ] (I) (see the Support-
neutral chelate complex [Pd{κ -C,O-C H (CH O)-2}(bpy)]
6
4
2
3 2
6
4
2
ing Information), which had already been prepared using
(3, Scheme 1), which crystallizes as a dinuclear aqua-bridged
18
[
Pd(PPh ) ] as the oxidative addition substrate. In the
species (see below).
3
4
∧
∧
2
synthesis of 1b (N N = tbbpy) and 1c (N N = tmeda) the
Reactions of [Pd(κ -C,O-C H CH O-2)(bpy)] (3) with
6
4
2
reactants were used in stoichiometric amounts, while in the
synthesis of 1a (N N = bpy) and I 50% excess alcohol was used
XyNC and CO. The reaction of 3 with XyNC resulted in the
formation of N-(2,6-dimethylphenyl)-2-benzofuran-1(3H)-
imine (4) (Scheme 2), which was isolated as a yellowish oil
and characterized by NMR spectroscopy and high-resolution
mass spectroscopy (see the Experimental Section). The cyclic
imidate 4 had not been described before, although the related
∧
to obtain either a better yield (1a) or a clean product (I).
∧
Complexes 1b,c decompose in solution to form [PdI (N N)]
2
∧
(
N N = tbbpy, tmeda), which are identified by their
characteristic H NMR resonances at 9.84 ppm (dd) for
PdI (tbbpy)] (which also has a characteristic red color) or
1
t
[
compound with a Bu group instead of Xy had been prepared
2
2
.95 ppm (s) for [PdI (tmeda)]. Attempts to prepare
by reaction of a dimeric oxapalladacycle phosphine complex
with BuNC. The synthesis of other five-membered imidates
by Pd-catalyzed reaction of 2-bromobenzyl alcohol and several
2
t
18
complexes similar to 1a−c with a Br ligand instead of I,
starting from 2-bromobenzyl alcohol, were unsuccessful.
B
DOI: 10.1021/acs.organomet.5b00309
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Organometallics
Article
Scheme 2
result of the nucleophilic attack of 3 on both methylene groups
of the substrate.
We also attempted to prepare a dinuclear complex by
oxidative addition of the C−X bond in 5d (X = Br) or 5e (X =
I) to [Pd(dba) ] in the presence of bpy. However, with 5d (X =
2
Br) there was no oxidative addition, and with 5e (X = I) we
obtained a mixture of two complexes, probably as a
consequence of the partial substitution by I of the Br ligand
attached to Pd. We decided then to fully replace this Br ligand
by I before the oxidative addition, by reaction of 5e with AgOTf
and a large excess of NaI, obtaining complex [PdI{C H -
6
4
(
CH OCH (C H I-4))-2}(bpy)] (5f, Scheme 3). By reaction
2 2 6 4
3
6
37
isocyanides (not XyNC) or by other, unrelated methods
of 5f with [Pd(dba) ] and bpy (1:1:1 ratio) we cleanly obtained
the dinuclear Pd complex [(bpy)IPd(C H CH -2)O-
(
7
although now only one of them is ortho-substituted.
NMR and IR Data. All the complexes reported in this paper
were extensively studied by NMR spectroscopy (1D and 2D
2
has also been reported. The reaction of 3 with CO resulted in
the decomposition of the complex to give 1(3H)-isobenzofur-
anone (phthalide) (Scheme 2). Both cyclic compounds
reasonably form through a XyCN or CO insertion reaction
into the C−Pd bond followed by a C−O coupling reaction. A
6
4
2
CH C H -4)PdI(bpy)] (7, Scheme 3). Similarly to 6, complex
2 6 4
shows a bridging organic chain with two aryl−Pd bonds,
3
8
CO insertion into the O−Pd bond would also be possible.
2
Reactions of [Pd(κ -C,O-C H CH O-2)(bpy)] (3) with
1
6
4
2
experiments), allowing an almost full assignment of the H and
Alkyl Halides. By reaction of complex 3 with an excess of
various primary alkyl halides of general formula RCH X (X =
Br, I), the complexes [PdX(C H CH OCH R-2)(bpy)] (X = I,
R = H (5a), X = Br, R = Ph (5b), p-C H CH Br (5c), p-
13
C resonances. To facilitate comparison, the data are collected
2
in Table S.1 in the Supporting Information, together with a
more extended discussion. We also include the data of complex
I, which had been reported but not fully assigned.
6
4
2
2
6
4
2
18
C H Br (5d), and p-C H I (5e)) were obtained (Scheme 3).
6
4
6
4
The methylenic protons of the CH OH groups are
2
These complexes result from the nucleophilic attack of the
coordinated oxygen in 3 at the alkyl group of the halide,
followed by the coordination of the halide to the Pd atom and
the opening of the chelate ring. We have found no precedent
for this type of reaction in an arylpalladium complex. A 5-fold
excess of RCH X was enough for the synthesis of 5d,e in good
yield, while for 5a−c a 10-fold excess was required (see the
Experimental Section). Similar reactions with PhI or PrI did
not result in the formation of analogous complexes, suggesting
that the success of the nucleophilic substitution requires a
primary halide as substrate.
diastereotopic in complexes 1a−c but equivalent in complex
I, which has a symmetry plane. In the chelate complex 3 the
methylenic protons are also equivalent, an indication that the
molecule has a symmetry plane in solution (even in the solid
state the molecule is almost planar, as shown by the X-ray
structure below). The OH proton of I is strongly shifted to
lower frequency (0.02 ppm) with respect to 1a−c (2.66−3.00
2
39
i
ppm), as a consequence of the anisotropic effect of the PPh
3
ligands. Another peculiarity of complex I is the shift of the aryl
ipso carbon to higher frequency (158.6 ppm) with respect to
the complexes with N,N-donor ligands, 1a−c (143.7−146.3
ppm). A similar trend has been observed previously by some of
us for other aryl palladium complexes
explained in terms of simplistic resonance or induction effects,
Synthesis of Dinuclear Palladium Complexes. When
the reaction of 3 with p-C H (CH Br) was carried out in a 2:1
6
4
2
2
3,21
ratio, we obtained the dinuclear Pd complex [{(bpy)BrPd-
C H CH OCH -2)} (C H -1,4)] (6, Scheme 3), which is the
and cannot be
(
6
4
2
2
2
6
4
Scheme 3
C
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Organometallics
Article
1
3
as C chemical shifts are mainly determined by the
40
paramagnetic contribution to the shielding constant. A single
3
1
P resonance for the PPh complex I (at 22.6 ppm) confirms
3
the trans geometry of the complex.
In the tbbpy (complex 1b) and bpy ligands (complexes 1a,
5
a−f, 6, and 7), the ortho hydrogen atoms of the pyridyl ring cis
to the aryl group (H16 in our numbering system) are strongly
shielded (7.33−7.69 ppm) with respect to those of the pyridyl
ring trans to aryl (H16′, 9.33−9.66 ppm). This is a common
3
,21,24
observation in aryl palladium complexes
and is a
consequence of the anisotropic effect of the aryl group on
the closest hydrogen of the bpy or tbbpy ligand. For the chelate
complex 3, in contrast, this effect is not observed (δ = 9.03 ppm
for H16′ and 9.18 ppm for H16), because the aryl group is
forced to be almost coplanar with the bpy ligand.
Figure 1. Thermal ellipsoid plot (50% probability level) of 1a.
Selected bond lengths (Å) and angles (deg): Pd(1)−C(1) = 2.003(2),
Pd(1)−N(12) = 2.1364(16), Pd(1)−N(22) = 2.0649(16), Pd(1)−
I(1) = 2.5810(2), C(7)−O(1) = 1.423(2), C(2)−C(7) = 1.505(3),
C(1)−C(2) = 1.399(3); C(1)−Pd(1)−N(22) = 93.36(7), C(1)−
Pd(1)−I(1) = 88.53(5), N(12)−Pd(1)−N(22) = 78.80(6), N(12)−
Pd(1)−I(1) = 99.48(5), C(1)−Pd(1)−N(12) = 171.18(7), N(22)−
Pd(1)−I(1) = 177.02(5), C(2)−C(7)−O(1) = 110.69(17), C(1)−
C(2)−C(7) = 119.46(18), C(2)−C(1)−Pd(1) = 119.08(15).
1
13
In the tmeda complex (1c) the presence of four H and C
resonances for the Me groups of the tmeda indicates that the
rotation around the Ar−Pd bond is hindered by the presence of
the CH OH substituent in ortho position.
2
For the dinuclear complex 6 we expected that both halves of
the molecule would be equivalent in solution, but this is not the
1
13
case, as we observe two sets of H and C resonances that are
1
almost coincident, with a few exceptions in the H spectrum
(
see the Supporting Information). The molecule seems to be
too bulky to adopt a completely symmetric structure in
solution. The four central C H protons appear as a single
6
4
sharp doublet with J = 4 Hz. Most probably these protons form
an AA′BB′ system (as in 5c−f) where A and B are isochronous
(but not equivalent, so that they are coupled with each other).
The p-[PdI(bpy)] fragment in 7 hinders the rotation of the
C H group, so that the two ortho protons and the two meta
6
4
protons are not equivalent, and they form an ABMN system,
3
3
i.e., four (slightly broad) doublets with J = J = 8 Hz.
AB
MN
The structure of the cyclic imidate 4 is confirmed by the
1
13
H, C-HMBC spectrum, where the expected two- and three-
1
13
bond H, C correlations are observed. In the IR spectrum, the
−1
CN band appears at 1693 cm .
Figure 2. Thermal ellipsoid plot (50% probability level) of 3·H O; two
2
Finally, for complex 2, resulting from the reaction of 1a with
adjacent molecules of 3 are connected by two water molecules, each of
which lies on a 2-fold axis. Only the asymmetric unit is numbered.
Selected bond lengths (Å) and angles (deg): Pd−O(1) = 1.9916(12),
Pd−C(1) = 1.9968(17), Pd−N(21) = 2.0379(15), Pd−N(11) =
2.1039(15), C(7)−O(1) = 1.419(2), C(2)−C(7) = 1.498(3), C(1)−
C(2) = 1.409(2); C(1)−Pd-N(21) = 103.50(6), O(1)−Pd-C(1) =
82.54(6), O(1)−Pd−N(11) = 95.34(6), N(21)−Pd−N(11) =
13
XyNC, we have no C NMR data, as the complex decomposes
1
too rapidly in solution. In the H NMR spectrum we observe
the expected 1:2 Me resonances corresponding, respectively, to
the inserted and the two (equivalent) coordinated XyNC
−
1
groups. These groups give characteristic IR bands at 2182 cm
−1
for the coordinated CNXy groups and at 1606 cm for the
79.21(6), C(1)−Pd−N(11) = 173.15(6), O(1)−Pd−N(21) =
172.22(6), C(7)−O(1)−Pd = 111.32(10), O(1)−C(7)−C(2) =
109.73(15), C(1)−C(2)−C(7) = 115.65(15), C(2)−C(1)−Pd =
111.49(12).
inserted CNXy group.
X-ray Structure Determinations. The crystal structures of
the complexes 1a (Figure 1), 3·H O (Figures 2 and 3), and 5e
2
(Figure 4) were determined by X-ray diffraction studies (see
Table S.2 for experimental details). The three structures show
somewhat distorted square planar coordination around the Pd
atoms. Mean deviations from the best plane through Pd and the
trans to aryl (2.1364(16) Å in 1a, 2.1039(15) Å in 3·H O, and
2
2.1362(17) Å in 5e) > Pd−N trans to I (2.0649(16) Å in 1a) >
Pd−N trans to Br (2.0563(17) Å in 5e) > Pd−N trans to O
four donor atoms are 0.05 Å for 1a, 0.08 Å for 3·H O, and 0.04
2
Å for 5e. For 3·H O, the distortion arises from the steric
(2.0379(15) Å in 3·H O). From the three Pd−N bond
2
2
pressure between the two ligands, which are forced to be
approximately coplanar with a short contact H6···H26 2.14 Å;
N21 lies 0.34 Å out of the plane of Pd and the other three
ligand donor atoms. The lesser distortion for the other two
structures might be a consequence of the chelating nature of
the bpy ligand. The Pd−C bond distances are very similar for
the three complexes (2.003(2) Å for 1a, 1.9968(17) Å for 3·
distances trans to aryl we can observe that in the chelate
complex 3·H O the trans influence of the aryl ligand is lower
2
than for 1a and 5e.
The five-membered chelate ring in 3·H O displays an
2
approximate envelope conformation, whereby the Pd atom
lies 0.55 Å out of the plane of the other four atoms (mean
deviation 0.08 Å); the aryl ring is forced to an angle of only 26°
with the plane defined by the bpy fragment, as opposed to the
almost perpendicular disposition in 1a (88°) and 5e (87°).
Within the chelate ring, the O−Pd bond distance is 1.9916(12)
H O, and 1.9903(19) Å for 5e) and in the range expected for
2
3
,21
Pd−C bonds trans to a N-donor ligand.
distances follow the expected order of trans influence: Pd−N
The Pd−N bond
41
D
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Article
Figure 3. Packing diagram of 3·H O viewed perpendicular to the bc plane. Hydrogen bonds O−H···O and C−H−O are drawn as dashed bonds.
2
Adjacent chains of molecules overlap in this view direction, but are not connected.
2
4
R (8). The (3·H O) dimers are further connected by three-
2
2
center interactions H23···O1W,O2W to form ribbons of
molecules parallel to the short b axis (Figure 3).
Conclusion. We have synthesized new aryl Pd complexes
derived from benzyl alcohol, one of them a chelate complex
resulting from the deprotonation of the alcohol. The reactivity
of these complexes toward XyNC has resulted in an insertion
complex and a cyclic imidate. The chelate complex reacts with
primary alkyl halides via a nucleophilic attack of the
coordinated oxygen on the alkyl group, resulting in the
opening of the chelate ring and the formation of new aryl
palladium complexes with larger substituents on the aryl ring.
Two novel dinuclear bis(arylpalladium) complexes have been
prepared, either by reaction with an alkyl dihalide or by a
secondary oxidative addition to one of the new complexes.
EXPERIMENTAL SECTION
■
The H and 13C resonances were assigned with the help of 2D NMR
1
Figure 4. Thermal ellipsoid plot (50% probability level) of 5e.
Selected bond lengths (Å) and angles (deg): Pd(1)−C(31) =
experiments (see Chart 1 for the numbering system). All experiments
1
2
.9903(19), Pd(1)−N(22) = 2.0563(17), Pd(1)−N(12) =
.1362(17), Pd(1)−Br(1) = 2.4226(3), C(44)−I(1) = 2.097(2),
Chart 1
C(37)−O(1) = 1.432(2), C(38)−O(1) = 1.423(2), C(31)−C(32) =
1
.398(3), C(32)−C(37) = 1.498(3), C(38)−C(41) = 1.501(3);
C(31)−Pd(1)−N(22) = 93.59(7), C(31)−Pd(1)−Br(1) = 90.12(6),
N(12)−Pd(1)−Br(1) = 97.49(5), N(22)−Pd(1)−N(12) = 78.86(7),
C(31)−Pd(1)−N(12) = 172.34(7), N(22)−Pd(1)−Br(1) =
1
=
74.97(5), C(32)−C(37)−O(1) = 108.19(16), C(37)−O(1)−C(38)
110.84(15), O(1)−C(38)−C(41) = 108.10(16).
Å, slightly shorter than the O−Pd distance (2.048(3) Å) found
in a related 2-hydroxymethylphenyl chelate complex that is a
1
8
dimer with a PPh ligand trans to O and two Pd−O bridges.
3
The C−O bond distance in 3·H O (1.419(2) Å) is slightly
2
shorter than the C−O bond distances in 1a (1.423(2) Å) and
were conducted under a N atmosphere using Schlenk techniques.
2
5
e (1.432(2) and 1.423(2) Å), and the Ar−CH bond distances
THF, CH Cl , hexane, and Et O were distilled before use. [Pd-
2
2
2
2
4
2
are similar (all in the range 1.498−1.505 Å), indicating that the
formation of the chelate ring does not involve a weakening of
the bonds within the ring.
(dba)2] and trans,trans-2,5-distyryl-1,4-dibromobenzene were pre-
pared according to literature procedures. TlOTf was prepared by
reaction of Tl CO and triflic acid (1:2) in water and recrystallized
2
3
from acetone/Et O.
Synthesis of [PdI(C H CH OH-2)(bpy)] (1a). 2-Iodobenzyl
2
The packing of 1a involves O−H···I hydrogen bonds that
6
4
2
connect the molecules via the n glide planes. The chelate
alcohol (183 mg, 0.782 mmol) was added to a suspension of
Pd(dba) ] (300 mg, 0.521 mmol) and bpy (81.4 mg, 0.521 mmol) in
complex 3·H O (Figure 2) crystallizes with two molecules of
2
[
2
water, both lying with the oxygen atom on a crystallographic 2-
fold axis, which are hydrogen-bonded to the oxygen in the
chelate ring, forming dimeric units (3·H O) bridged by two
dry degassed toluene (20 mL) under N . The resulting mixture was
2
stirred in an ice bath for ca. 90 min until the dark red color of
2
2
[Pd(dba) ] was no longer observed. The brownish suspension was
2
water molecules. The central ring belongs to the graph set
then concentrated in vacuo, and the residue was extracted with
E
DOI: 10.1021/acs.organomet.5b00309
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
CH Cl (20 mL). The extract was filtered over Celite, and the orange
2.75−2.45 (several m, 3H, CH tmeda), 2.72, 2.69, 2.48, and 2.12 (s,
2
2
2
3H, Me tmeda). 13C{ H} NMR (100.6 MHz, CDCl ): 145.0 (C2
1
solution was evaporated to dryness. Et O (20 mL) was added, and the
2
3
resulting pale pink suspension was filtered off, washed with Et O (3 ×
aryl), 143.7 (C1 aryl), 135.6 (CH6 aryl), 128.4 (CH3 aryl), 126.2
(CH5 aryl), 123.7 (CH4 aryl), 69.1 (CH ), 62.4 (CH tmeda), 58.5
2
5
mL), and dried in vacuo to give 1a as a pale reddish solid, which is
2
2
soluble in CH Cl , CHCl , and acetone. Yield: 124 mg (48%). Mp:
(CH tmeda), 51.2 and 50.7 (Me tmeda), 49.0 (2C, Me tmeda). Anal.
2
2
3
2
−
1
1
2
9
8
29 °C dec. IR (cm ): ν(OH) 3430. H NMR (600 MHz, CD Cl ):
Calcd for C H IN OPd: C, 34.19; H, 5.08; N, 6.13. Found: C, 34.54;
2
2
13 23
2
3
4
5
.46 (ddd, 1H, J = 5 Hz, J = 2 Hz, J = 1, H16′ bpy), 8.06−
H, 5.02; N, 5.94.
HH
HH
HH
3
4
.02 (m, 2H, H13,13′ bpy), 7.98 (td, 1H, J = 8 Hz, J = 2 Hz,
Synthesis of trans-[PdI{C(NXy)(C H CH OH-2)}(CNXy) ] (2).
HH
HH
6
4
2
2
3
4
H14′ bpy), 7.94 (td, 1H, J = 8 Hz, J = 2 Hz, H14 bpy), 7.53
XyNC (159 mg, 1.21 mmol) was added to a solution of 1a (200 mg,
HH
HH
3
3
4
(
(
dd, J = 8 Hz, J = 5 Hz, J = 2 Hz, 1H, H15′ bpy), 7.39−7.36
0.403 mmol) in dry degassed THF (20 mL), under N and in an ice
HH
HH
HH
2
3
4
5
m, 1H, H6 aryl), 7.33 (ddd, J = 5 Hz, J = 2 Hz, J = 1 Hz,
bath. The solvent was immediately evaporated in vacuo, and Et O (20
HH
HH
HH
2
H16 bpy), 7.27−7.23 (m, 1H, H15 bpy), 7.13−7.10 (m, 1H, H3 aryl),
mL) was added under N , forming a yellow suspension, which was
2
2
3
6
.93−6.89 (m, 2H, H5,H4 aryl), 4.99 (dd, J = 12 Hz, J = 3 Hz,
filtered off, washed with Et O (3 × 5 mL), and dried in vacuo to give 2
HH
HH
2
2
3
1
H, CH ), 4.48 (dd, J = 12 Hz, J = 10 Hz, 1H, CH ), 2.66 (dd,
as a yellow solid, which is soluble in CH Cl , CHCl , and acetone.
2
HH
HH
2
2
2
3
3
3
13
1
−1
JHH = 10 Hz, J = 3 Hz, 1H, OH). C{ H} NMR (150.9 MHz,
Yield: 147 mg (50%). Mp: 130 °C. IR (cm ): ν(OH) 3311, ν(CN)
HH
1
3
CD Cl ): 156.6 (C12 bpy), 154.4 (C12′ bpy), 153.1 (CH16′ bpy),
2182, ν(CN) 1606. H NMR (300 MHz, CDCl ): 8.56 (d, J = 8
2
2
3
HH
1
50.4 (CH16 bpy), 146.3 (C1 aryl), 145.4 (C2 aryl), 139.6 (CH14
Hz, 1H, aryl), 7.56−7.48 (m, 1H, aryl), 7.41−7.37 (m, 2H, aryl),
co 3 co
bpy), 139.5 (CH14′ bpy), 136.6 (CH6 aryl), 128.8 (CH3 aryl), 127.6
7.26−7.18 (m, 2H, Xy ), 7.06 (d, J = 8 Hz, 4H, Xy ), 6.95 (br s,
HH
i
n
3
3
(
CH15′ bpy), 127.2 (CH15 bpy), 126.8 (CH5 aryl), 124.3 (CH4
3H, Xy ), 5.12 (t, J = 7 Hz, 1H, OH), 4.70 (2, J = 7 Hz, 2H,
HH HH
in
co
13
aryl), 122.8 (CH13 bpy), 122.4 (CH13′ bpy), 68.7 (CH ). Anal. Calcd
CH ), 2.192 (s, 6H, Me Xy ), 2.186 (s, 12H, Me Xy ). No C NMR
2
2
for C H IN OPd: C, 41.11; H, 3.04; N, 5.64. Found: C, 40.98; H,
data are available because the complex decomposes rapidly in solution.
Anal. Calcd for C H IN OPd: C, 55.64; H, 4.67; N, 5.72. Found: C,
17
15
2
3
.06; N, 5.70. Single crystals of 1a were grown by liquid diffusion of
34
34
3
Et O into a solution of 1a in CH Cl .
55.57; H, 4.80; N, 5.64.2
2
2
2
t
Synthesis of [PdI(C H CH OH-2)(tbbpy)] (1b). 2-Iodobenzyl
Synthesis of [Pd(κ -C,O-C H CH O-2)(bpy)] (3). KO Bu (361
6
4
2
6
4
2
alcohol (122 mg, 0.521 mmol) was added to a suspension of
Pd(dba) ] (300 mg, 0.521 mmol) and tbbpy (140 mg, 0.521 mmol)
mg, 3.22 mmol) was added to a solution of 1a (400 mg, 0.805 mmol)
[
in CH Cl2 (20 mL) under N , whereby the color changed from
2
2
2
in dry degassed toluene (20 mL) under N . The resulting mixture was
reddish to yellow. The mixture was stirred for 15 min at room
2
stirred in an ice bath for 2 h until the dark red color of [Pd(dba) ] was
temperature and then filtered over Celite. The resulting yellow
2
no longer observed. The brownish suspension was then concentrated
in vacuo, and the residue was extracted with CH Cl (20 mL). The
solution was evaporated to dryness, and Et O (20 mL) was added to
2
2
2
precipitate a solid, which was filtered off, thoroughly washed with Et O
2
extract was filtered over Celite, and the orange solution was evaporated
to dryness. Warm hexane (20 mL) was added, and the resulting yellow
suspension was filtered off, washed with warm hexane (3 × 5 mL), and
dried in vacuo to give 1b as a pale yellow solid, which is soluble in
CH Cl , CHCl , acetone, and Et O (partially). Yield: 133 mg (42%).
(3 × 5 mL), and dried in vacuo to give 3 as a yellow solid, which is
soluble in CH Cl , CHCl , and acetone. Yield: 227 mg (77%). Mp:
2
2
3
1
3
129 °C dec. H NMR (400 MHz, CD Cl ): 9.18 (d, J = 5 Hz, 1H,
2
2
HH
3
4
5
H16 bpy), 9.03 (ddd, J = 5 Hz, J = 1 Hz, J = 1 Hz, 1H, H16′
HH
HH
HH
2
2
3
2
bpy), 8.08−7.96 (m, 4H, H13,13′,14,14′ bpy), 7.59−7.52 (m, 2H,
H15,15′ bpy), 7.23−7.19 (m, 1H, H6 aryl), 7.04−6.97 (m, 3H, H3,4,5
−1
1
Mp: 217 °C dec. IR (cm ): ν(OH) 3490. H NMR (400 MHz,
3
13
1
CDCl ): 9.46 (d, J = 6 Hz, 1H, H16′ tbbpy), 7.98 (s, 1H, H13
aryl), 5.21 (s, 2H, CH ). C{ H} NMR (100.6 MHz, CD Cl ): 166.2
2 2 2
3
HH
3
4
tbbpy), 7.97 (s, 1H, H13′ tbbpy), 7.53 (dd, J = 6 Hz, J = 2 Hz,
(C2 aryl), 156.6 (C12 bpy), 153.4 (C12′ bpy), 152.0 (CH16 bpy),
151.0 (C1 aryl), 149.9 (CH16′ bpy), 138.8 (CH14′ bpy), 138.1
(CH14 bpy), 131.7 (CH6), 126.6 (CH15 bpy), 126.3 (CH15′ bpy),
124.0 (CH4 aryl), 123.6 (CH5 aryl), 122.5 (CH13 bpy), 121.1
HH
HH
3
4
1
7
H, H15′ tbbpy), 7.50 (dd, J = 7 Hz, J = 2 Hz, 1H, H6 aryl),
HH
HH
3
3
4
.33 (d, J = 6 Hz, 1H, H16 tbbpy), 7.28 (dd, J = 6 Hz, J = 2
HH
HH
HH
3
4
Hz, 2H, H15 tbbpy), 7.20 (dd, J = 7 Hz, J = 2 Hz, 1H, H3 aryl),
HH
HH
3
4
7
.02−6.93 (m, 2H, H5,H4 aryl), 5.21 (dd, J = 12 Hz, J = 3 Hz,
(CH13′ bpy), 119.1 (CH3 aryl), 78.4 (CH ). Anal. Calcd for
HH
HH
2
1
H, CH ), 4.66 (app t, J = 10 Hz, 1H, CH ), 2.92−2.86 (m, 1H,
C H N OPd: C, 55.37; H, 3.83; N, 7.60. Found: C, 55.12; H, 3.74;
2
HH
2
17 14
2
t
t
13
1
OH), 1.43 (s, 9H, Bu′ tbbpy), 1.38 (s, 9H, Bu tbbpy). C{ H} NMR
100.6 MHz, CDCl ): 163.62 (C14 tbbpy), 163.58 (C14′ tbbpy),
N, 7.43. Single crystals of 3·H O were grown by liquid diffusion of
2
(
hexane into a solution of 3 in CH Cl .
3
2
2
1
(
56.2 (C12 tbbpy), 154.0 (C12′ tbbpy), 152.6 (CH16′ tbbpy), 149.7
Synthesis of N-(2,6-Dimethylphenyl)-2-benzofuran-1(3H)-
imine (4). XyNC (35.6 mg, 0.271 mmol) was added to a solution
CH16 tbbpy), 146.3 (C1 aryl), 144.8 (C2 aryl), 136.2 (CH6 aryl),
1
28.6 (CH3 aryl), 126.6 (CH5 aryl), 124.2 (CH15′ tbbpy), 123.93
of 3 (100 mg, 0.271 mmol) in THF (20 mL) under N . The mixture
was stirred for 2 h in an ice bath, whereby the color changed from
2
(
CH4 aryl), 123.91 (CH15 tbbpy), 118.7 (CH13 tbbpy), 118.2
(
CH13′ tbbpy), 68.8 (CH ), 35.74 (CMe tbbpy), 35.70 (CMe ′
yellow to black. It was then filtered over MgSO , and the resulting
2
3
3
4
tbbpy), 30.6 (CMe ′ tbbpy), 30.5 (CMe tbbpy). Anal. Calcd for
yellow solution was evaporated to dryness, leaving a yellow oil. This oil
was washed with cold hexane (10 mL), to eliminate the bpy ligand,
and then dried in vacuo to give 4 as a yellow oil, which is soluble in
3
3
C H IN OPd: C, 49.32; H, 5.13; N, 4.60. Found: C, 49.43; H, 5.11;
2
5
31
2
N, 4.68.
Synthesis of [PdI(C H CH OH-2)(tmeda)] (1c). 2-Iodobenzyl
−
1
6
4
2
Et O, CH Cl , CHCl , and acetone. Yield: 29.0 mg (45%). IR (cm ):
2
2
2
3
1
alcohol (122 mg, 0.521 mmol) was added to a suspension of
Pd(dba) ] (300 mg, 0.521 mmol) and tmeda (78.2 μL, 0.521 mmol)
ν(CN) 1693. Mp: 129 °C dec. H NMR (400 MHz, CDCl ): 8.05
3
3
3
3
[
(d, J = 7 Hz, 1H, H7), 7.59 (t, J = 7 Hz, 1H, H5), 7.53 (t, J
2
HH HH HH
3
3
in dry degassed toluene (20 mL) under N . The resulting mixture was
= 7 Hz, 1H, H6), 7.41 (d, J = 7 Hz, 1H, H4), 7.05 (d, J = 7 Hz,
HH HH
2
3
stirred in an ice bath for 4 h until the dark red color of [Pd(dba) ] was
no longer observed. The brownish suspension was then concentrated
in vacuo, and the residue was extracted with CH Cl (20 mL). The
extract was filtered over Celite, and the reddish solution was
evaporated to dryness. Et O (20 mL) was added, and the resulting
2H, m-H Xy), 6.93 (7, J = 7 Hz, 1H, p-H Xy), 5.31 (s, 2H, CH2),
2
HH
2.16 (s, 6H, Me Xy). 13C{ H} NMR (100.6 MHz, CDCl ): 158.1
1
3
2
2
(CN), 145.4 (i-C Xy), 143.9 (C3), 132.1 (CH5), 129.9 (C8), 128.9
Xy
(CH6), 128.4 (2C, o-C Xy), 127.8 (2C, m-CH ), 124.4 (CH7), 123.3
2
(p-CH Xy), 121.7 (CH4), 72.6 (CH ), 18.5 (2C, Me Xy). HR ESI+
2
pale pink suspension was filtered off, washed with Et O (3 × 5 mL),
TOF MS: calcd for C H NO, m/z 238.1226, found 238.1226, Δ =
2
16 15
and dried in vacuo to give 1c as an orange solid, which is soluble in
CH Cl , CHCl , and acetone. Yield: 140 mg (59%). Mp: 105 °C. IR
0.00 ppm.
2
2
3
Reaction of 3 with CO. CO was bubbled for 5 min through a
−1
1
3
(
cm ): ν(OH) 3305. H NMR (400 MHz, CDCl ): 7.29 (dd, J
Hz, J = 2 Hz, 1H, H6 aryl), 7.11 (dd, J = 7, J = 2 Hz, 1H,
=
solution of 3 (100 mg, 0.271 mmol) in CH Cl (20 mL), whereby
3
HH
2
2
4
3
4
7
extensive decomposition was observed. The mixture was stirred for 1 h
HH
HH
HH
3
H3 aryl), 6.93−6.84 (m, 2H, H5,H4 aryl), 5.43 (dd, J = 11 Hz,
in a CO atmosphere. Then it was filtered over MgSO , and the
HH
4
4
J
= 3 Hz, 1H, CH ), 4.68 (app t, J = 11 Hz, 1H, CH ), 3.00 (dd,
resulting yellow solution was evaporated to dryness, whereby a reddish
color appeared in the residue. This residue was extracted with cold
HH
2
HH
2
3J = 10 Hz, J = 3 Hz, 1H, OH), 2.95−2.86 (m, 1H, CH tmeda),
3
HH
HH
2
F
DOI: 10.1021/acs.organomet.5b00309
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
Et O (10 mL), and the resulting yellowish solution was filtered over
dried in vacuo to give 5c as a yellow solid, which is soluble in CH Cl ,
2
2
2
1
Celite and then dried in vacuo to give a solid (45 mg), which is shown
CHCl , and acetone. Yield: 104 mg (61%). Mp: 103 °C dec. H NMR
3
3 4 5
1
by H NMR spectroscopy to be a clean mixture of 1(3H)-
(400 MHz, CDCl ): 9.39 (ddd, J = 5 Hz, J = 1 Hz, J = 1 Hz,
3 HH HH HH
1
3
isobenzofuranone (phthalide) and bpy in a 1:1 ratio. H NMR (400
1H, H16′ bpy), 8.03−7.99 (m, 2H, H14′,13′ bpy), 7.94 (d, J = 8
HH
3
3
3 4
MHz, CDCl ): 8.69 (d, J = 5 Hz, 2H, bpy), 8.40 (d, J = 8 Hz,
Hz, 1H, H13 bpy), 7.85 (td, J = 8 Hz, J = 2 Hz, 1H, H14 bpy),
3
HH
HH
HH HH
3
3
3
4
5
2
H, bpy), 7.94 (d, JHH = 8 Hz, 1H, phthalide), 7.83 (td, J = 8 Hz,
JHH = 2 Hz, 2H, bpy), 7.69 (td, J = 7 Hz, J = 1 Hz, 1H,
7.62 (ddd, J = 5 Hz, J = 2 Hz, J = 1, 1H, H16 bpy), 7.59−
HH
HH
HH
HH
4
3
4
7.54 (m, 1H, H15′ bpy), 7.53−7.48 (m, 1H, H6 aryl), 7.32−7.27 (m,
HH
HH
3
4
3 3 4
phthalide), 7.54 (td, J = 7 Hz, J = 1 Hz, 1H, phthalide), 7.50
1H, H3 aryl), 7.14 (ddd, JHH = 8 Hz, JHH = 5 Hz, JHH = 1 Hz, 1H,
HH
HH
3
4
3
3
(
dt, J = 8 Hz, J = 1 Hz, 1H, phthalide), 7.32 (ddd, J = 8 Hz,
JHH = 5 Hz, J = 1 Hz, 2H, bpy), 5.33 (s, 2H, phthalide).
H15 bpy), 7.07 (A part of AB system, JHH = 8 Hz, 2H, m-H C
6
H
4
),
), 7.03−6.99
m, 2H, H4,5 aryl), 5.28 and 4.85 (AB system, J = 11 Hz, 2H, CH -
HH
HH
HH
4
4
3
7.01 (B part of AB system, JHH = 8 Hz, 2H, o-H C H
HH
6 4
2
(
7
Synthesis of [PdI(C H CH OMe-2)(bpy)] (5a). MeI (169 μL,
.71 mmol) was added to a solution of 3 (100 mg, 0.271 mmol) in
HH
2
6
4
2
1
3
1
), 4.53 (s, 2H, CH -8), 4.41 (s, 2H, CH Br). C{ H} NMR (100.6
2
2
2
MHz, CDCl ): 155.7 (C12 bpy), 153.7 (C12′ bpy), 151.4 (CH16
CH Cl (20 mL) under N . The mixture was stirred in the dark for 4 h
3
2
2
2
at room temperature, whereby the yellow color darkened. It was then
filtered over Celite, and the resulting yellow solution was concentrated
bpy), 150.7 (CH16′ bpy), 150.2 (C1 aryl), 141.8 (C2 aryl), 139.7 (i-C
C
C
H
H
CH
CH
Br), 139.0 (CH14′ bpy), 138.5 (CH14 bpy), 136.3 (p-C
6
4
2
in vacuo to a volume of ca. 1 mL. Et O (15 mL) was added to
6
4
2
Br), 135.0 (CH6 aryl), 128.8 (2C, m-CH C
CH Br), 126.8 (CH5 aryl),
126.7 (CH15′ bpy), 126.5 (CH15 bpy), 123.8 (CH4 aryl), 122.0
(CH13 bpy), 121.6 (CH13′ bpy), 76.2 (CH -7), 72.0 (CH -8), 34.0
(CH Br). Anal. Calcd for C25 OPd: C, 47.46; H, 3.50; N,
4.43. Found: C, 47.47; H, 3.78; N, 4.30.
Synthesis of [PdBr{C (CH OCH (C
Bromobenzyl bromide (340 mg, 1.36 mmol) was added to a solution
of 3 (100 mg, 0.271 mmol) in CH Cl (20 mL) under N . The
H CH Br),
6 4 2
2
precipitate a solid, which was filtered off, thoroughly washed with Et O
128.1 (CH3 aryl), 127.8 (2C, o-CH C
6
H
4
2
2
(
3 × 5 mL), and dried in vacuo to give 5a as a yellow solid, which is
soluble in CH Cl , CHCl , and acetone. Yield: 101 mg (73%). Mp:
2
2
2
2
3
1
3
4
2
2
8
02 °C. H NMR (400 MHz, CDCl ): 9.66 (ddd, J = 5 Hz, J =
2
H22Br N
2 2
3
HH
HH
5
Hz, J = 1 Hz, 1H, H16′ bpy), 8.09−8.04 (m, 2H, H13,13′ bpy),
HH
3
4
3
.01 (td, J = 8 Hz, J = 2 Hz, 1H, H14′ bpy), 7.98 (td, J = 8
6
H
4
2
2
H Br-4))-2}(bpy)] (5d). 4-
6 4
HH
HH
HH
4
3
3
Hz, J = 2 Hz, 1H, H14 bpy), 7.57 (ddd, J = 8 Hz, J = 5 Hz,
HH
HH
HH
4
3
4
5
JHH = 1 Hz, 1H, H15′ bpy), 7.53 (ddd, J = 6 Hz, J = 2 Hz, J
2
2
2
HH
HH
HH
3
mixture was stirred for 4 h at room temperature, whereby the color
changed from yellow to orange. It was then filtered over Celite, and
the resulting yellow solution was concentrated in vacuo to a volume of
=
8
1 Hz, 1H, H16 bpy), 7.50−7.45 (m, 1H, H6 aryl), 7.32 (ddd, J
Hz, J = 6 Hz, J = 1 Hz, 1H, H15 bpy), 7.26−7.22 (m, 1H, H3
=
HH
3
4
HH
HH
2
aryl), 7.02−6.95 (m, 2H, H4,5 aryl), 5.00 and 4.77 (AB system, J
1
=
HH
1
3
1
ca. 1 mL. Et O (15 mL) was added to precipitate a solid, which was
1 Hz, 2H, CH ), 3.32 (s, 3H, Me). C{ H} NMR (100.6 MHz,
2
2
filtered off, thoroughly washed with Et O (3 × 5 mL), and dried in
CDCl ): 155.9 (C12 bpy), 153.9 (C12′ bpy), 153.2 (CH16′ bpy),
2
3
vacuo to give 5d as a yellow solid, which is soluble in CH Cl , CHCl ,
1
50.6 (CH16 bpy), 145.3 (C1 aryl), 142.2 (C2 aryl)), 138.74 (CH14′
bpy), 138.69 (CH14 bpy), 136.1 (CH6 aryl)), 127.08 (CH3 aryl)),
27.05 (CH15′ bpy), 126.6 (CH15 bpy), 126.3 (CH5 aryl)), 123.8
CH4 aryl)), 121.9 (CH13 bpy), 121.6 (CH13′ bpy), 78.5 (CH ),
2
2
3
1
and acetone. Yield: 145 mg (87%). Mp: 185 °C. H NMR (300 MHz,
3
CDCl ): 9.39 (d, J = 5 Hz, 1H, H16′ bpy), 8.05−8.01 (m, 2H,
1
3
HH
3
3
H13′,14′ bpy), 7.98 (d, J = 8 Hz, 1H, H13 bpy), 7.89 (td, J = 8
(
5
HH
HH
2
4
3
Hz, J = 2 Hz, 1H, H14 bpy), 7.62 (d, J = 6 Hz, 1H, H16 bpy),
8.5 (Me). Anal. Calcd for C H IN OPd: C, 42.34; H, 3.36; N, 5.49.
HH
HH
18
17
2
7
.61−7.53 (m, 1H, H15′ bpy), 7.51−7.46 (m, 1H, H6 aryl), 7.26−7.21
Found: C, 41.97; H, 3.23; N, 5.53.
Synthesis of [PdBr(C H CH OCH Ph-2)(bpy)] (5b). PhCH Br
3 3 4
(m, 1H, H3 aryl), 7.17 (ddd, J = 8 Hz, J = 6 Hz, J = 1 Hz,
HH HH HH
6
4
2
2
2
3
1
H, H15 bpy), 7.11 (A part of AB system, J = 8 Hz, 2H, m-H
HH
(
322 μL, 2.71 mmol) was added to a solution of 3 (100 mg, 0.271
C H Br), 7.04−6.98 (m, 2H, H4,5 aryl), 6.95 (B part of AB system,
mmol) in CH Cl (20 mL) under N . The mixture was stirred for 4 h
6
4
2
2
2
3
2
J
= 8 Hz, 2H, o-H C H Br), 5.28 and 4.85 (AB system, J = 11
at room temperature with no significant change in color. It was then
filtered over Celite, and the resulting yellow solution was concentrated
HH
6 4 HH
2
Hz, 2H, CH
-7), 4.52 and 4.46 (AB system, JHH = 12 Hz, 2H, CH
-
2
2
8). 13C{ H} NMR (75.4 MHz, CDCl
1
): 155.8 (C12 bpy), 153.6 (C12′
in vacuo to dryness. Cold Et O (15 mL) was added to precipitate a
3
2
solid, which was filtered off, thoroughly washed with cold Et O (3 × 5
bpy), 151.5 (CH16 bpy), 150.8 (CH16′ bpy), 149.9 (C1 aryl), 141.6
(C2 aryl), 139.0 (CH14′ bpy), 138.4 (CH14 bpy), 138.2 (i-C
2
mL), and dried in vacuo to give 5b as a pale yellow solid, which is
soluble in CH Cl , CHCl , and acetone and partially soluble in Et O.
C H Br), 135.0 (CH6 aryl), 131.1 (2C, m-CH C H Br), 129.5 (2C, o-
6 4 6 4
2
2
3
2
1
Yield: 122 mg (83%). Mp: 171 °C. H NMR (400 MHz, CDCl ): 9.43
CH C
bpy), 126.5 (CH15 bpy), 123.9 (CH4 aryl), 121.8 (CH13 bpy), 121.5
(CH13′ bpy), 120.8 (p-C C Br), 76.1 (CH -7), 71.8 (CH -8). Anal.
Calcd for C24 OPd: C, 46.59; H, 3.26; N, 4.53. Found: C,
46.51; H, 3.23; N, 4.36.
Synthesis of [PdBr{C
Iodobenzyl bromide (404 mg, 1.36 mmol) was added to a solution of
3 (100 mg, 0.271 mmol) in CH Cl (20 mL) under N . The mixture
6 4
H Br), 128.1 (CH3 aryl), 126.82 (CH5 aryl), 126.76 (CH15′
3
3
4
5
(
7
ddd, J = 5 Hz, J = 1 Hz, J = 1 Hz, 1H, H16′ bpy), 8.06−
HH
HH
HH
3
.99 (m, 2H, H14′,13′ bpy), 7.97 (d, J = 8 Hz, 1H, H13 bpy), 7.88
6
H
4
2
2
HH
3
4
3
(
td, J = 8 Hz, J = 2 Hz, 1H, H14 bpy), 7.69 (ddd, J = 6 Hz,
H20Br N
2 2
HH
HH
HH
4
5
JHH = 2 Hz, J = 2 Hz, 1H, H16 bpy), 7.62−7.57 (m, 1H, H15′
HH
bpy), 7.53−7.47 (m, 1H, H6 aryl), 7.32−7.27 (m, 1H, H3 aryl), 7.17
H (CH OCH (C H I-4))-2}(bpy)] (5e). 4-
6 4 2 2 6 4
3
3
4
(
7
ddd, J = 8 Hz, J = 6 Hz, J = 1 Hz, 1H, H15 bpy), 7.12−
HH
HH
HH
.05 (m, 5H, Ph), 7.05−6.98 (m, 2H, H4,5 aryl), 5.31 and 4.89 (AB
2
2
2
2
2
system, J = 11 Hz, 2H, CH -7), 4.56 and 4.52 (AB system, J =
was stirred for 4 h at room temperature with no significant change in
color. It was then filtered over Celite, and the resulting yellow solution
HH
2
HH
1
3
1
1
2 Hz, 2H, CH -8). C{ H} NMR (100.6 MHz, CDCl ): 155.9 (C12
2
3
bpy), 153.7 (C12′ bpy), 151.7 (CH16 bpy), 150.9 (CH16′ bpy), 149.7
was concentrated in vacuo to a volume of ca. 1 mL. Et
added to precipitate a solid, which was filtered off, thoroughly washed
with Et O (3 × 5 mL), and dried in vacuo to give 5e as a pale yellow
solid, which is soluble in CH Cl , CHCl , and acetone. Yield: 167 mg
(93%). Mp: 173 °C. H NMR (400 MHz, CDCl
Hz, 1H, H16′ bpy), 8.05−8.01 (m, 2H, H13′,14′ bpy), 7.97 (d, JHH =
2
O (15 mL) was
(
(
C1 aryl), 141.9 (C2 aryl), 139.2 (i-C Ph), 138.9 (CH14′ bpy), 138.4
CH14 bpy), 135.0 (CH6 aryl), 128.13 (CH3 aryl), 128.12 (2C, m-
2
CH Ph), 127.7 (2C, o-CH Ph), 127.1 (p-CH Ph), 126.74 (CH15′
2
2
3
1
3
bpy), 126.71 (CH5 aryl), 126.6 (CH15 bpy), 123.9 (CH4 aryl), 121.8
): 9.40 (d, JHH = 5
3
3
(
CH13 bpy), 121.3 (CH13′ bpy), 76.0 (CH -7), 72.6 (CH -8). Anal.
2
2
3
4
Calcd for C H BrN OPd: C, 53.40; H, 3.92; N, 5.19. Found: C,
8 Hz, 1H, H13 bpy), 7.89 (td, JHH = 8 Hz, JHH = 2 Hz, 1H, H14
24
21
2
3
3
4
5
3.65; H, 4.04; N, 5.42.
Synthesis of [PdBr{C H (CH OCH (C H CH Br-4))-2}(bpy)]
bpy), 7.62 (d, JHH = 6 Hz, 1H, H16 bpy), 7.58 (td, JHH = 5 Hz, JHH
= 3 Hz, 1H, H15′ bpy), 7.51−7.46 (m, 1H, H6 aryl), 7.30 (A part of
6
4
2
2
6
4
2
3
(5c). p-Xylylene dibromide (715 mg, 2.71 mmol) was added to a
AB system, J = 8 Hz, 2H, m-H C H I), 7.25−7.20 (m, 1H, H3
HH
6
4
3
3
4
solution of 3 (100 mg, 0.271 mmol) in CH Cl (20 mL) under N .
aryl), 7.17 (ddd, J = 8 Hz, J = 6 Hz, J = 1 Hz, 1H, H15 bpy),
7.04−6.98 (m, 2H, H4,5 aryl), 6.81 (B part of AB system, J = 8 Hz,
2H, o-H C H I), 4.84 and 5.28 (AB system, J = 11 Hz, 2H, CH -
2
2
2
HH HH HH
3
The mixture was stirred for 4 h at room temperature, whereby the
color changed from yellow to orange. It was then filtered over Celite,
and the resulting yellow solution was concentrated in vacuo to a
HH
2
6
4
HH
2
2
13
1
7), 4.51 and 4.46 (AB system, J = 12 Hz, 2H, CH -8). C{ H}
HH
2
volume of ca. 1 mL. Et O (15 mL) was added to precipitate a solid,
NMR (150.9 MHz, CDCl ): 155.8 (C12 bpy), 153.6 (C12′ bpy),
2
3
which was filtered off, thoroughly washed with Et O (3 × 5 mL), and
151.5 (CH16 bpy), 150.8 (CH16′ bpy), 150.0 (C1 aryl), 141.7 (C2
2
G
DOI: 10.1021/acs.organomet.5b00309
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
aryl), 138.99 (CH14′ bpy), 138.96 (i-C C H I), 138.4 (CH14 bpy),
no longer observed. The brownish suspension was then concentrated
in vacuo, and the residue was extracted with CH Cl (20 mL). The
6
4
1
37.1 (2C, m-CH C H I), 135.0 (CH6 aryl), 129.7 (2C, o-CH C H I),
6
4
6
4
2
2
1
28.1 (CH3 aryl), 126.83 (CH5 aryl), 126.76 (CH15′ bpy), 126.5
extract was filtered over Celite, and the orange solution was evaporated
(
CH15 bpy), 123.9 (CH4 aryl), 121.8 (CH13 bpy), 121.5 (CH13′
to dryness. Et O (20 mL) was added, and the resulting orange
2
bpy), 92.5 (p-C C H I), 76.1 (CH -7), 71.9 (CH -8). Anal. Calcd for
suspension was filtered off, washed with Et O (3 × 5 mL), and dried in
6
4
2
2
2
C H BrIN OPd: C, 43.30; H, 3.03; N, 4.21. Found: C, 43.41; H,
3
Et O into a solution of 5e in CH Cl .
vacuo to give 7 as an orange solid, which is soluble in CH Cl , CHCl ,
2
4
20
2
2
2
3
1
.03; N, 4.42. Single crystals of 5e were grown by liquid diffusion of
and acetone. Yield: 55.0 mg (56%). Mp: 153 °C. H NMR (300 MHz,
3 4 5
CDCl ): 9.61 and 9.57 (ddd, J = 5 Hz, J = 2 Hz, J = 1, 1H,
2
2
2
3
HH
HH
HH
Synthesis of [PdI{C H (CH OCH (C H I-4))-2}(bpy)] (5f).
H16′,26′ bpy), 8.17−8.02 (several m, 4H, H13,13′,23,23′ bpy), 8.02−
6
4
2
2
6
4
3
AgOTf (38.5 mg, 0.150 mmol) and an excess of NaI (2250 mg,
5.0 mmol) were added to a solution of 5e (100 mg, 0.150 mmol) in
CH Cl (20 mL) under N . A suspension formed immediately, which
7.92 (several m, 4H, H14′,24′ and H14 or H24 bpy), 7.87 (td, JHH =
4
1
8 Hz, JHH = 2 Hz, 1H, H24 or H14 bpy), 7.59−7.53 (m, 2H, H6 aryl
and H15′ or 25′ bpy), 7.48−7.36 (m, 3H, H16,26, H25′or 15′ bpy),
2
2
2
3
3
4
was stirred for 1 h at room temperature. Then it was filtered over
7.35 (ddd, JHH = 7 Hz, JHH = 6 Hz, JHH = 1 Hz, 1H, H15 or 25 bpy),
3
4
3
MgSO , and the resulting orange solution was concentrated in vacuo
7.21 (dd, JHH = 7 Hz, JHH = 2 Hz, 1H, H3 aryl), 7.11 (ddd, JHH = 7
Hz, JHH = 6 Hz, JHH = 1 Hz, 1H, H25 or 15 bpy), 7.02 (td, JHH = 7
Hz, JHH = 2 Hz, 1H, H5 aryl), 6.96 (td, JHH = 7 Hz, JHH = 1 Hz, 1H,
H4 aryl), 7.03 and 6.85 (br, A part of AB system, 1H, JHH = 8 Hz, m-
4
3
4
3
to a volume of ca. 1 mL. Et O (25 mL) was added to precipitate a
2
4
3
4
solid, which was filtered off, thoroughly washed with Et O (3 × 5 mL),
2
3
and dried in vacuo to give 5f as an orange solid, which is soluble in
1
3
CH Cl , CHCl , and acetone. Yield: 51.0 mg (48%). Mp: 145 °C. H
H C
Hz, o-H C
CH -7), 4.48 and 4.40 (AB system,
6
H
4
[Pd]), 6.57 and 6.42 (br, B part of AB system, 1H, JHH = 8
2
2
3
3
4
5
2
NMR (300 MHz, CDCl ): 9.61 (ddd, J = 5 Hz, J = 1 Hz, J
6 4
H [Pd]), 5.22 and 4.62 (AB system, JHH = 11 Hz, 2H,
3
HH
HH
HH
2
=
(
2
2 Hz, 1H, H16′ bpy), 8.04−8.00 (m, 2H, H13′,14′ bpy), 7.97−7.85
2
J
HH = 11 Hz, 2H, CH
C{ H} NMR (75.4 MHz, CDCl ): 155.7 and 155.2 (C12,22 bpy),
3
2
-8).
13
1
m, 2H, H13,14 bpy), 7.58−7.52 (m, 1H, H15′ bpy), 7.50−7.42 (m,
3
H, H6 aryl, H16 bpy), 7.28 (A part of AB system, J = 8 Hz, 2H,
154.5 and 153.9 (C12′,22′ bpy), 153.0 and 152.4 (C16′,26′ bpy),
150.6 and 150.0 (CH16,26 bpy), 148.8 (C1 aryl), 143.9 (p-C
C H [Pd]), 142.3 (C2 aryl), 138.89, 138.86, 138.8, and 138.5
HH
m-H C H I), 7.25−7.17 (m, 2H, H3 aryl, H15 bpy), 7.01−6.95 (m,
6
4
3
2
H, H4,H5 aryl), 6.79 (B part of AB system, J = 8 Hz, 2H, o-H
C H I), 5.14 and 4.79 (AB system, J = 11 Hz, 2H, CH -7), 4.49
and 4.44 (AB system, J = 12 Hz, 2H, CH -8). C{ H} NMR (75.4
HH
6
4
2
(CH14,14′,24,24′ bpy), 136.3 (CH6 aryl), 135.8 and 135.6 (m-CH
6
4
HH
2
2
13
1
C H [Pd]), 133.8 (i-C C H [Pd]), 128.6 (CH3 aryl), 126.94, 126.92,
HH
2
6
4
6
4
MHz, CDCl ): 155.6 (C12 bpy), 153.6 (C12′ bpy), 153.1 (CH16′
and 126.86 (CH15′,25′ and CH5 bpy), 126.5 and 126.4 (o-CH
3
bpy), 150.5 (CH16 bpy), 146.8 (C1 aryl), 142.0 (C2 aryl), 139.0 (i-C
C H I), 138.7 (CH14′ bpy), 138.4 (CH14 bpy), 137.1 (2C, m-CH
C H [Pd]), 126.4 and 125.9 (CH15,25 bpy), 123.4 (CH4 aryl), 122.9,
6
4
122.4, 122.0, and 121.7 (CH13,13′,23,23′ bpy), 77.6 (CH -7), 72.6
6
4
2
C H I), 136.3 (CH6 aryl), 129.7 (2C, o-CH C H I), 128.0 (CH3
(CH -8). Anal. Calcd for C34H I N OPd : C, 41.87; H, 2.89; N, 5.74.
2 28 2 4 2
6
4
6
4
aryl), 127.0 (CH15′ bpy), 126.7 (CH5 aryl), 126.4 (CH15 bpy), 123.7
CH4 aryl), 121.7 (CH13 bpy), 121.6 (CH13′ bpy), 92.5 (p-C
C H I), 77.1 (CH -7), 71.9 (CH -8). Anal. Calcd for C H I N OPd:
Found: C, 41.80; H, 3.23; N, 5.53.
(
6
4
2
2
24 20 2
2
ASSOCIATED CONTENT
Supporting Information
■
C, 40.45; H, 2.83; N, 3.93. Found: C, 40.20; H, 2.68; N, 4.00.
Synthesis of [{(bpy)BrPd(C H CH OCH -2)} (C H -1,4)] (6). p-
*
S
6
4
2
2
2
6 4
Experimental details for the synthesis of complex I. NMR data
tables of complexes 1a−c, I, 3, 5a−f, 6, and 7. Extended
comments on the NMR data. X-ray crystallographic data,
structure refinement details, and CIF files for compounds 1a, 3·
Xylylene dibromide (35.9 mg, 0.136 mmol) was added to a solution of
(100 mg, 0.271 mmol) in CH Cl (20 mL) under N . The mixture
3
2
2
2
was stirred for 4 h at room temperature with no significant change in
color. It was then filtered over Celite, and the resulting yellow solution
was concentrated in vacuo to a volume of ca. 1 mL. Et O (15 mL) was
H O, and 5e. The Supporting Information is available free of
2
2
added to precipitate a solid, which was filtered off, thoroughly washed
charge on the ACS Publications website at DOI: 10.1021/
acs.organomet.5b00309.
with Et O (3 × 5 mL), and dried in vacuo to give 6 as a yellow solid,
2
which is soluble in CH Cl , CHCl , and acetone. Yield: 115 mg (85%).
2
2
3
1
Mp: 137 °C. H NMR (400 MHz, CDCl ): 9.36−9.33 (m, 2H,
3
AUTHOR INFORMATION
Corresponding Authors
*Correspondence regarding the synthesis and properties of
compounds: eloisamv@um.es (E. Martinez-Viviente). Web:
■
H16′,16′ bpy), 8.06−8.03 (m, 2H, H14′,13′ bpy), 8.00−7.97 (m, 3H,
3
4
H13′,13,13 bpy), 7.89 and 7.88 (td, J = 8 Hz, J = 2 Hz, 1H,
HH
HH
3
4
H14,14′ bpy), 7.78 (td, J = 8 Hz, J = 2 Hz, 1H, H14 bpy),
HH
HH
́
7
.58−7.53 (m, 3H, H16,16,15′ bpy), 7.53−7.48 (m, 3H, H6,6 aryl and
H15′ bpy), 7.28−7.24 (m, 1H, H3 aryl), 7.23−7.19 (m, 1H, H3 aryl),
http://www.um.es/gqo/.
*Correspondence regarding the X-ray diffraction studies: p.
jones@tu-bs.de (P. G. Jones).
7
(
2
4
.17−7.11 (m, 2H, H15,15 bpy), 7.06−6.98 (m, 4H, H5,5,4,4), 6.77
3
2
d, J = 4 Hz, 4H, C H ), 5.20 and 4.87 (AB system, J = 11 Hz,
HH 6 4 HH
2
H, CH -7), 5.20 and 4.80 (AB system, J = 11 Hz, 2H, CH -7),
2 HH 2
13
1
Notes
.45−4.37 (m, 4H, CH -8, CH -8). C{ H} NMR (150.9 MHz,
2
2
The authors declare no competing financial interest.
CDCl ): 155.96 and 155.93 (C12 bpy), 153.79 and 153.71 (C12′
3
bpy), 151.32 and 151.30 (CH16 bpy), 150.58 and 150.57 (CH16′
ACKNOWLEDGMENTS
We thank the Ministerio de Educacion
FEDER (Project CTQ2011-24016), and Fundacion
bpy), 149.99 and 149.96 (C1 aryl), 142.05 and 142.01 (C2 aryl),
■
1
1
39.23 and 139.16 (CH14′ bpy), 138.74 and 138.66 (CH14 bpy),
́
y Ciencia (Spain),
Seneca
37.76 and 137.75 (i-C C H ), 135.23 and 135.20 (CH6 aryl), 128.08
6
4
́
́
and 128.01 (CH3 aryl), 127.40 and 127.35 (2C, CH C H ), 126.75
6
4
(
04539/GERM/06) for financial support. M.J.F.-R. is grateful
and 126.69 (CH5 aryl), 126.66 and 126.62 (CH15′ bpy), 126.53 and
́
to the Ministerio de Educacion y Ciencia (Spain) for a grant.
1
1
(
26.49 (CH15 bpy), 123.81 and 123.77 (CH4 aryl), 122.39 and
22.32 (CH13 bpy), 121.91 and 121.85 (CH13′ bpy), 75.78 and 75.63
CH -7), 72.41 and 72.30 (CH -8). Anal. Calcd for
REFERENCES
2
2
■
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H
DOI: 10.1021/acs.organomet.5b00309
Organometallics XXXX, XXX, XXX−XXX

Organometallics
Article
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