Self-Assembled, Highly Positively Charged, Allyl–Pd Crowns: Cavity-Pocket-Driven Interactions of Fluoroanions

Article abstract of DOI:10.1002/chem.202000316

A series of dodecanuclear highly positively charged homo- and heterometallamacrocycles [{Pd(η³-2-Me-C₃H₄)}₆(4-PPh₂py)₁₂{M₂(tpbz)}₃]¹⁸⁺ (M=Pd, Pt; tpbz=1,2,4,5-tetrakis(diphenylphosphanyl)benzene were synthesized by the quantitative self-assembly of {Pd(η³-2-Me-C₃H₄)}⁺, {M₂(tpbz)}⁴⁺ and 4-PPh₂py moieties in 2:1:4 molar ratio. The cationic assemblies were obtained as salts of different fluorinated anions with diverse sizes and electronic properties, namely BF₄^?, PF₆^?, SbF₆^? and CF₃SO₃^?. The new crown-like metallamacrocycles showed remarkable differences in their NMR spectra due to the presence of the different counteranions. On the basis of the observed variations, the metallacycles have been tested as catalytic precursors in allylic alkylation reactions. The anion-dependent activity and selectivity has been analysed and compared with that of the corresponding monometallic allylic corners [Pd(η³-2-Me-C₃H₄)(4-PPh₂py)₂]X (X=BF₄^?, PF₆^?, SbF₆^?, CF₃SO₃^?). DFT calculations have been employed in order to help to the interpretation of the experimental data and to model the anion–crown interactions.

Full text of DOI:10.1002/chem.202000316

A Journal of
Accepted Article
Title: Self-Assembled Highly Positively Charged Allyl-Pd Crowns:
Cavity-Pocket Driven Interactions of Fluoroanions.
Authors: Montserrat Ferrer, Albert Gallen, Albert Gutiérrez, Manuel
Martínez, Eliseo Ruiz, Yvonne Lorenz, and Marianne Engeser
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To be cited as: Chem. Eur. J. 10.1002/chem.202000316
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10.1002/chem.202000316
Chemistry - A European Journal
Self-Assembled Highly Positively Charged Allyl-Pd Crowns:
Cavity-Pocket Driven Interactions of Fluoroanions.
Montserrat Ferrer,a,* Albert Gallen,a Albert Gutiérrez,a Manuel Martínez,a Eliseo Ruiz,a, b
Yvonne Lorenzc and Marianne Engeserc
a Departament de Química Inorgànica i Orgànica, Secció de Química Inorgànica.
Universitat de Barcelona, c/ Martí i Franquès 1-11 08028 Barcelona, Spain.
bInstitut de Química Teòrica i Computacional, Universitat de Barcelona, c/ Martí i
Franquès 1-11, 08028 Barcelona, Spain
c Kekulé-Institute for Organic Chemistry and Biochemistry, University of Bonn,
Gerhard-Domagk-Str. 1, 53121 Bonn, Germany
Abstract
A
series
of
dodecanuclear
highly
positively
charged
homo-
and
heterometallamacrocycles [{Pd(η3-2-Me-C3H4)}6(4-PPh2py)12{M2(tpbz)}3]18+ (M = Pd,
Pt; tpbz = 1,2,4,5-tetrakis(diphenylphosphanylbenzene) were synthesized by the
quantitative self-assembly of {Pd(η3-2-Me-C3H4)}+, {M2(tpbz)}4+ and 4-PPh2py
moieties in 2:1:4 molar ratio. The cationic assemblies were obtained as salts of different
fluorinated anions that display diverse sizes and electronic properties, namely BF4-, PF6-,
SbF6- and CF3SO3-. The new crown-like metallamacrocycles showed remarkable
differences in their NMR spectra due to the presence of the different counteranions. On
the basis of the observed variations, the metallacycles have been tested as catalytic
precursors in allylic alkylation reactions. The anion-dependent activity and selectivity
has been analysed and compared with that of the corresponding monometallic allylic
corners [Pd(η3-2-Me-C3H4)(4-PPh2py)2]X (X = BF4-, PF6-, SbF6-, CF3SO3-). DFT
calculations have been employed in order to help to the interpretation of the
experimental data and to model the anion-crown interactions.
Introduction
Coordination-driven assembly of organic ligands and metal ions plays a key role in the
construction of nanoscale molecular well-defined architectures.[1] Particularly,
1
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10.1002/chem.202000316
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supramolecular metallamacrocycles self-assembled from many components often bear
specific functionalities, conferring them unique properties that account for their
potential applications. The properties of these macro assemblies can be modulated by
the rational choice of both the specific functionalities in the constituent organic
frameworks and the metal ions. In this way, the constructed supramolecules can be
involved in host–guest chemistry,[2] or present photophysical,[3] redox[4] and/or catalytic
activity,[5] among others features.[6]
Apart from the directing elements imposed by the building blocks, the outcome of the
self-assembly reactions is also controlled by other factors such as reagents
concentration, solvent, or counteranions. The ability of anions to operate as templates
(or guests) and have a significant influence on the course of the assembly process
through noncovalent interactions is well documented.[7] Furthermore, the establishment
of this kind of weak interactions can exert a subtle control of the catalyst behaviour that
could depend on the nature of the counteranion.[8]
We recently reported the self-assembly of a series of tetranuclear homo- and
heterometallamacrocycles that incorporate the allyl-palladium function {Pd(η3-2-Me-
C3H4)}+.[9] Since this organometallic fragment is well known for its relevance as precursor
of the catalytically active species in several metal-catalysed organic transformations,[10]
we studied the allylic alkylation of the 3-acetoxy-phenyl-1-propene catalysed by the
polymetallic architectures [{Pd(η3-2-Me-C3H4)(4-PPh2py)2}2{M(dppp)}2](CF3SO3)6
(M=Pd, Pt) (dppp= 1,3-bis(diphenylphosphino)propane) in comparison with that of the
corresponding active monometallic complex [Pd(η3-2-Me-C3H4)(4-PPh2py)2](CF3SO3).
In spite of the crowded environment around the active catalytic fragment in the
supramolecular species, we did not observe significant differences on the
regioselectivity of the metallamacrocycles compared with that of the unassembled
catalytically active precursor.
These disappointing results lead us to investigate the effect of the increase of the
nuclearity and hence the size of the metallacycles in order to induce a change in the
environment of the allyl-palladium moiety that could definitively modify the catalytic
outcome of the supramolecular compound. We considered thus the use of a
bis(chelating)tetraphosphane as a spacer, which should give rise to the formation of two
equivalent square-planar entities connected by a phenyl ring. In this respect, even
though extensive research has been conducted over the past decades, examples of
2
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10.1002/chem.202000316
Chemistry - A European Journal
supramolecular metallamacrocycles containing polyphosphane ligands as linkers are
relatively scarce. Due to the free rotation around the P–C bond, different orientations of
the lone pair of electrons of the phosphanes are possible, resulting in a poor
predictability of the assembled species.[11] Hence, in order to force a pre-designed self-
assembly, steric constraints have to be introduced into the polyphosphane backbone. In
general, then, the cage compounds that are held together by polyphosphanes contain
rigid benzene[12] or benzene-like units.[13]
With all these considerations in mind, we succeeded in obtaining in a selective way a
set of highly charged dodecametallic crown-like [{M(η3-2-Me-C3H4)}6(4-
PPh2py)12M’6(tpbz)3]+18 (M = Pd, M’= Pd, Pt) architectures by means of a three-
component self-assembly process between the PdII or PtII derivatives of the tetratopic
1,2,4,5-tetrakis(diphenylphosphino)benzene (tpbz), {Pd(η3-2-Me-C3H4)}+ and the
14]
ambidentate 4-PPh2py ligand, specifically designed[9a,
to induce a favoured
coordination to the metal centres according to the antisymbiotic effect.
Given the high positive charge of the obtained polymetallic species, and the
concomitant presence of an important number of anions as charge-balance components,
we have synthesized a series of derivatives with different fluoroanions i. e. BF4-, PF6-,
SbF6- and CF3SO3- and studied its behaviour in solution by multinuclear NMR
spectroscopy. The obtained results strongly confirmed the keystone influence of the
counteranions on the self-assembly process. Although this effect is usually associated
with the coordinating ability of the anions,[15] other factors including, the size,[16]
shape,[17] or even the solubility of the corresponding salt in a specific solvent can not be
ruled out. Finally, as indicated above, the activity of the assemblies as homogeneous
catalysts in the allylic alkylation process has been undertaken.
Results and discussion
With the aim of preparing allyl-Pd metallamacrocycles having higher nuclearities than
those reported before by our group,[9a, 14] the previous synthesis and full characterization
of the required building blocks was carried out.
Synthesis and Characterization of 1,2,4,5-tetrakis(diphenylphosphino)benzene
(tpbz) bimetallic building blocks.
3
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The bimetallic compounds [M2(tpbz)(solvent)4]X4 (M = Pd; X = BF4-, 2Pd, PF6-, 3Pd,
SbF6-, 4Pd; M = Pt; X = BF4-, 2Pt, PF6-, 3Pt, SbF6-, 4Pt, PF2O2-, 5Pt) were synthesized
following a modified procedure from that described for the CF3SO3- derivatives by
Dalcanale et al.[18] The reaction of the silver salt of the chosen anion with [M2(tpbz)Cl4]
in 4:1 molar ratio in a dichloromethane/acetonitrile mixture (1:1 in volume) at RT for 12
h resulted in a suspension that after filtration, concentration and precipitation upon
addition of dimethylether afforded the desired compounds as a solvato complexes.
While four molecules of either acetonitrile (2Pd-3Pd) or water (4Pd) are coordinated to
the PdII centre, in the case of the PtII species (2Pt-4Pt) the complex second order P
31
NMR spectra (Figures S12, S16 and S21) are indicative of the coexistence of two
molecules of both acetonitrile and water in the coordination sphere of the metallic
cation. Only for the PF2O2- derivative the anions appear coordinated to the PtII centre,
producing a much more insoluble compound. All attempts to obtain the analogous
BArF- (tetrakis[3,5-bis(trifluoromethyl)phenyl]borate) derivatives were unsuccessful.
Synthesis and Characterization of [Pd(η3-2-Me-C3H4)(4-PPh2py)]X (X = BF4- (2a),
PF6- (3a), SbF6- (4a), BArF- (5a)) ditopic building blocks.
Although the obtention of our crown-like metallamacrocycles was effective by a three-
component self-assembly, an alternative synthetic pathway that only involves two
building blocks provided comparable results (Scheme 1). For this purpose, the
preliminary synthesis of the allyl palladium donor [Pd(η3-2-Me-C3H4)(4-PPh2py)2]- with
the studied anions was conducted. As described in the literature for the triflate
derivative,[9a] the addition of 4-PPh2py to a dichloromethane solution of the suitable
[Pd(η3-2-Me-C3H4)(cod)]X (X = BF4-, PF6-, SbF6-, BArF-) in 2:1 molar ratio gave the
desired products (2a-5a) in good yields. Distinctive variations in the allyl region of the
1H NMR of the mononuclear complexes as a function of the counteranion were
observed (Figure S51 and Table S1 in Supporting Information). Although in the case of
BF4-, PF6-, CF3SO3- and BArF- derivatives two singlets due to the syn and anti protons of
the allyl ligand respectively, are observed, only one broad signal of intermediate
chemical shift is obtained for the SbF6- species. In this respect, the noticeable
progressive decrease (BArF- > CF3SO3- > BF4- > PF6- ) in the δsyn- δanti value indicates an
increase of the dynamic exchange rate of the allyl ligand depending on the
counteranion. The observed trend concerning fluxionality rates does not agree with the
4
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10.1002/chem.202000316
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coordinating ability of the different fluoroanions utilised, thus suggesting the prevalence
of weak interactions involving the terminal fluoro atoms and the allyl-Pd building
block.[8] Clearly, this differential behaviour could have a decisive influence on the self-
assembly process of the metallamacrocycles, as described below.
Self-Assembly of [{Pd(ηη3-2-Me-C3H4)}6(4-PPh2py)12{M2(tpbz)}3]X18 dodecanuclear
crown-like metallamacrocycles.
Having in mind our design strategy, we proceeded with the combination of the triflate
salts of [M2(tpbz)(solvent)4]4+ (M = Pd, Pt) and {Pd(η3-2-Me-C3H4)}+ and the 4-PPh2py
ligand in a 1:2:4 molar ratio. In principle, the attempted self-assembly might be
compatible with the formation of different cyclic assemblies i. e. [3+6+12], [4+8+16] or
even higher nuclearity systems that could be polymeric. Moreover, due to both the large
number of assembled units and/or their flexibility, the obtention of an equilibrium
mixture among different possible architectures could not be ruled out.
The 31P{1H} NMR spectra (Figures S26 for M = Pd and S29 for M = Pt) of the solutions
obtained after stirring in CH2Cl2 a mixture of the above indicated species for 2 hours at
room temperature, showed a singlet associated with the P atom of the 4-PPh2py unit
(25.6 ppm for the Pd derivative 1a61Pd3 and 26.0 ppm for the Pt derivative 1a61Pt3) and
another of the tpbz ligand (55.2 ppm for 1a61Pd3 and 29.1 ppm for 1a61Pt3: the latter
2
flanked with the expected 195Pt satellites J(31P-195Pt) = 3245 Hz). Thus, despite the
possibility of formation of several cages, the assembly of a single discrete, highly
symmetric species is exclusively observed. Identical results were obtained when the
preformed donor moiety [Pd(η3-2-Me-C3H4)(4-PPh2py)2]CF3SO3 was treated with either
the palladium or the platinum acceptor [M2(tpbz)(solvent)4](CF3SO3)4 (M = Pd, Pt) in
2:1 molar ratio under the same conditions (Scheme 1). Concentration of the resulting
solutions and addition of diethyl ether lead to the isolation of the metallasupramolecular
species as pale yellow solids in good yields.
5
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Chemistry - A European Journal
X–
+
Ph2
P
Ph2
P
18 X–
18+
X–
+
Pd
Pd
6
Pd
6
N
N
N
Ph2P
PPh2
M
PPh2
M
N
Ph2P
X- = CF3SO3-, 1a
Pd
PPh2
Ph2P
P
P
-
Ph2
Ph2
BF4-
,
,
2a
3a
4a
PPh2
N
N
Ph2P
+
PF6
Self-assembly
Self-assembly
Ph2P
-
M
PPh2
SbF6
,
M
Ph2P
N
12
BArF-,
5a
N
N
N
PPh2
Ph2P
Pd
Ph2P
N
Pd
N
PPh2
Ph2
+
Ph2P
PPh2
+
4 X–
4+
4+
Pd
4 X–
Ph2
P
Ph2
P
Ph2
P
Ph2
P
Pd
solvent
solvent
solvent
Ph
solvent
solvent
2 N
P
PPh2
Ph2P
P
3
N
3
M
M
M
M
N
M
solvent
M
solvent
solvent
P
P
P
P
Ph2
Ph2
Ph2
Ph2
PPh2
PPh2
M = Pd
M = Pd
M = Pt
X- = CF3SO3-, 1Pd
X- = CF3SO3-, 1a61Pd3
X- = CF3SO3-, 1a61Pt3
-
BF4-
,
,
2Pd
3Pd
4Pd
-
-
BF4-
,
,
2a62Pd3
3a63Pd3
4a64Pd3
BF4-
,
,
2a62Pt3
———
4a64Pt3
PF6
SbF6
-
PF6
PF6
,
-
-
SbF6
,
SbF6
,
PF6/PF2O2-, 3a65Pt3
M = Pt
X- = CF3SO3-, 1Pt
-
BF4-
,
,
2Pt
3Pt
4Pt
5Pt
PF6
SbF6
PF2O2
-
,
-
,
Scheme 1. Self-assembly pathways for the formation of the different crown-like
metallamacrocycles.
1
The formation of a single product was further confirmed using H DOSY NMR, which
gives a single set of peaks (Figure 1) with a diffusion coefficient of 4.3 10 -10 m2 s-1 from
which a hydrodynamic radius of 1.5 nm can be estimated using the Stokes-Einstein
relationship, which is consistent with the crystal structure data (see below).
D (cm2/s)
ppm
Figure
1.
1H
DOSY
NMR
spectrum
of
[{Pd(η3-2-Me-C3H4)}6(4-
PPh2py)12{Pd2(tpbz)}3](CF3SO3)18 (1a61Pd3) in acetone-d6 at 298 K.
6
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10.1002/chem.202000316
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The exact nuclearity of the assemblies was determined unambiguously by High
Resolution ESI Mass Spectrometry. The presence of signals at m/z = 2324.55, 1830.80
and 1499.88, corresponding to [1a61Pd3-4CF3SO3]4+, [1a61Pd3-5CF3SO3]5+ and
[1a61Pd3-6CF3SO3]6+ ions, respectively in the case of the Pd metallacycle (Figure 2) and
at 1936.12, [1a61Pt3-5CF3SO3]5+; 1588.61 [1a61Pt3-6CF3SO3]6+; 1340.37 [1a61Pt3-
7CF3SO3]7+ for the heterometallic PdPt derivative (Figure S30) are in agreement with
the formation of [3+6+12] [M2(tpbz)]4+:{Pd(η3-2-Me-C3H4)}+:4-PPh2py species.
Experimental isotopic patterns centred on these m/z values suitably correlated with the
theoretical isotopic distributions calculated for the detected ions (Figures 2 and S30).
2324.5553
2323.8052
exp.:
1499.8847
1500.7229
exp.:
2325.8091
2325.8066
2324.5563
2323.8062
calc.:
1499.8867
1500.7203
calc.:
1496
m/z
1500
2320
2325
m/z
500
1000
1500
m/z
2000
2500
Figure 2. ESI(+)-HRMS spectrum of the metallamacrocycle [{Pd(η3-2-Me-C3H4)}6(4-
PPh2py)12{Pd2(tpbz)}3](CF3SO3)18 (1a61Pd3). The insets show the concordance between
the measured and calculated isotope patterns of the prominent signals [1a61Pd3-
4CF3SO3]4+ and [1a61Pd3-6CF3SO3]6+.
At this point, the scope of our investigations was subsequently expanded to the study of
the self-assembly reactions in the presence of other anions with different size, shape or
coordination characteristics such as BF4-, PF6-, SbF6- and BArF-. While BF4- and SbF6-
display a coordinating ability intermediate between CF3SO3- and PF6-, BArF- is a very
weakly coordinating species;[19] moreover, the size of PF6- is intermediate between the
7
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10.1002/chem.202000316
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large SbF6-, BArF- and CF3SO3- and the small BF4-. Obvious differences in shape among
the used anions could also be taken into account.
All the self-assembly reactions with participation of BF4- and SbF6- building blocks
converged into a single species in a similar way than the observed for the CF3SO3-
compounds. Characterization data (see an exhaustive set of 1H, 31P, 19F NMR and High-
Resolution ESI Mass Spectrometry spectra in Supporting Information)[20] are in
agreement with the exclusive formation of [3+6+12] [M2(tpbz)]4+:{Pd(η3-2-Me-
C3H4)}+:4-PPh2py (M = Pd, Pt) architectures. As for the self-assembly reaction of the
suitable hexafluorophosphate building blocks only the targeted Pd metallacycle
[{Pd(η3-2-Me-C3H4)}6(4-PPh2py)12{Pd2(tpbz)}3](PF6)18 (3a63Pd3) was obtained.
Unexpectedly, however, the presence of the PF2O2- anion was observed in the case of
the heterometallic “3a63Pt3” derivative most probably due to the PF6- hydrolysis by
adventitious moisture during some stage of the process. The hydrolysis of PF6- is a
common feature in coordination chemistry,[21] and it is known to occur even in AgPF6,
which
we
used
to
prepare
[Pd2(tpbz)(solvent)4](PF6)4
(3Pd)
and
[Pt2(tpbz)(solvent)4](PF6)4 (3Pt) derivatives. A careful analysis of the assembled units
revealed that PF6- had undergone an accidental hydrolysis during the formation of the
tpbz derivative and that [Pt2(tpbz)(PF2O2)4](5Pt) had been the actual building block
instead of 3Pt, thus allowing the formation of 3a65Pt3.
Unexpectedly, the self-assembly of [Pt2(tpbz)(solvent)4](PF6)4 (3Pt) (obtained by
reaction between [Pt2Cl4(tpbz)] and AgPF6 under strictly dry conditions), [Pd(η3-2-Me-
C3H4)(COD)]PF6 (3a) and 4-PPh2py did not give the expected heterometallic
macrocycle “3a63Pt3” in spite of numerous attempts. In the case of BArF- analogues, the
failure of the preparation of the [M2(tpbz)(solvent)4](BArF)4 acceptor building blocks
precluded the formation of the metallamacrocycles even though several alternative
strategies were attempted.
All these experiments represent a further evidence of the influence of the counteranions
on self-assembly processes in a similar way to that reported by some authors in the
literature for other self-assembled architectures. In particular, the presence of certain
anions like BF4-[22] or CF3SO3-[16a] has been shown to preclude the self-assembly process
giving rise to the formation of oligomers instead.
Unfortunately, most attempts to obtain single crystals for X-ray characterization of the
new compounds proved to be unsuccessful. Surprisingly, we only managed to grow
8
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suitable crystals for the [{Pd(η3-2-Me-C3H4)}6(4-PPh2py)12{Pt2(tpbz)}3](PF6)6(PF2O2)12
metallamacrocyle (3a65Pt3), obtained by accidental hydrolysis of the PF6- of the tpbz
building block, as indicated above.
X-Ray Crystallography
Crystals of [{Pd(η3-2-Me-C3H4)}6(4-PPh2py)12{Pt2(tpbz)}3](PF6)6(PF2O2)12 (3a65Pt3) were
grown by slow diffusion of diethyl ether in a dichloromethane solution of the complex at
room temperature. Despite the easy efflorescence of the crystals and severe disorder of
solvent molecules, the quality of X-ray structural data (Table S2 in Supporting
Information) is sufficient to establish the connectivity of the structure.
Figure 3. Two representations of the molecular structure obtained by X-ray diffraction of
the [{Pd(η3-2-Me-C3H4)}6(4-PPh2py)12{Pt2(tpbz)}3](PF6)6(PF2O2)12 metallamacrocycle.
The discrete crown-like structure (Figure 3) consists of three tetranuclear Pt2Pd2 butterfly
shaped moieties, similar to that closely related tetranuclear metallamacrocycles recently
reported by us, connected between each other by the tetraphosphane (tpbz). The PtII
centres are in a square planar environment determined by two phosphorus atoms of the
bridging tpbz and to two pyridyl nitrogen atoms of the 4-PPh2py ligands. A distorted
square planar configuration around the Pd atoms is achieved by the coordination of one
allyl ligand in a η3-fashion and two phosphorus atoms of the ditopic 4-PPh2py ligands.
The distance between the farthest atoms in the metallamacrocycle is approximately 30 Å,
which is in agreement with the calculated value of hydrodynamic radius from DOSY
9
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10.1002/chem.202000316
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NMR experiments (15 Å). The disorder due to the high number of counteranions and the
consequent limited quality of crystallographic data implies that the location of some of
the anions could not be determined. However, as can be seen in Figures 3 and S53 three
PF6- and three PF2O2- are located in the cylindrical cavity whose dimension can be
estimated to be rbase ≈ 10 Å and h ≈ 9 Å.
1H NMR Spectroscopy Studies in Solution
As we recently reported, the closely related square allyl metallacycles [{Pd(η3-2-Me-
C3H4)}2(4-PPh2py)4{M(dppp)}2](CF3SO3)6 feature a complex dynamic behaviour due to
an exchange process with their building blocks in solution. The rate of this process was
found to be dependent both on the solvent and on the electronic and/or steric nature of
the different building blocks.[9a]
Similarly, the crown-like macrocyclic species described in this work [{Pd(η3-2-Me-
C3H4)}6(4-PPh2py)12{M2(tpbz)}3](X)18 also display such an exchange with the {Pd(η3-2-
Me-C3H4)(4-PPh2py)2}2- units (see NOESY showing the dynamic exchange between
3a63Pd3 and 3a in Figure S50), implying the concomitant cleavage of the Pd or Pt –
pyridine bond. In this case, the rate of exchange is faster than that observed in the
square-like metallacycles. All the synthesized assemblies showed broad or very broad
signals for α-pyridine proton nuclei, their shape and shift being dependent on the
counteranion and metal centre (Figure 4 and Table 1 for M = Pd and Figure 5 and Table
2 for M = Pt). Given the low symmetry of the system, in the slow exchange regime, two
different 1H NMR peaks should be observed for both the α and β pyridine protons.
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Ph2P
Hβ
Hα
Hsyn
Pd
Hanti
–
Pd
N
SbF6
–
PF6
–
BF4
–
CF3SO3
9.0 8.8 8.6 8.4 8.2 8.0 7.8 7.6 7.4 7.2 7.0 6.8 6.6 3.8 3.6 3.4 3.2 3.0 2.8 2.6 2.4 2.2 2.0 1.8
δ (ppm)
1
Figure 4. H NMR spectra of the [{Pd(η3-2-Me-C3H4)}6(4-PPh2py)12{Pd2(tpbz)}3]18+
crown metallamacrocycles with different counteranions in CD2Cl2 at room temperature.
Pd Crown
Counteranion
δ(ppm)Hα
δ(ppm)Hsyn allyl
δ(ppm) Hanti allyl
-py
1a61Pd3
2a62Pd3
3a63Pd3
CF3SO3–
BF4–
8.88
8.69
8.58
8.56
3.51
3.66
3.74
3.77
2.27
2.13
1.99
2.01
PF6–
4a64Pd3
SbF6–
1
Table 1. H NMR molecular shifts of the significant resonances of the [{Pd(η3-2-Me-
C3H4)}6(4-PPh2py)12{Pd2(tpbz)}3]18+ crown-like metallamacrocycles with different
counteranions in CD2Cl2 at room temperature.
A first inspection of the spectra in figures 4 and 5 clearly indicates that the
homometallic Pd12 species display a faster dynamic process than the closely related
heterometallic Pt6Pd6 metallacycles, which is in agreement with the higher lability of the
PdII centre. In fact, as it can be observed in the expansion in Fig. 5, the α-pyridine
protons of heterometallic species appear as very broad peaks (in the case of SbF6-
species the signal seems to be near to the coalescence temperature).
11
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Ph2P
Hβ
Hα
Hsyn
Pd
Hanti
Pd
–
SbF6
N
–
–
PF6 /PF2O2
–
BF4
–
CF3SO3
9.0 8.8 8.6 8.4 8.2 8.0 7.8 7.6 7.4 7.2 7.0 6.8 6.6 6.4 6.2 3.8 3.62.6 2.4 2.2 2.0 1.8
δ (ppm)
1
Figure 5. H NMR spectra of the [{Pd(η3-2-Me-C3H4)}6(4-PPh2py)12{Pt2(tpbz)}3]18+
crown metallamacrocycles with different counteranions in CD2Cl2 at room temperature.
Pt Crown
Counteranion
δ(ppm)Hα
δ(ppm)Hsyn allyl
δ(ppm) Hanti allyl
-py
1a61Pt3
2a62Pt3
3a63Pt3
4a64Pt3
CF3SO3–
BF4–
8.89
8.69
8.95
3.62
3.75
3.77
3.84
2.25
2.10
1.90
2.01
PF6–/PF2O2-
SbF6–
9.00-8.40
1
Table 2. H NMR chemical shifts of the significant resonances of the [{Pd(η3-2-Me-
C3H4)}6(4-PPh2py)12{Pt2(tpbz)}3]18+ crown metallamacrocycles with different
counteranions in CD2Cl2 at room temperature
From the data it is clear that the nature of the counteranion has a dramatic effect on both
the chemical shifts and the broadness of the α-py signals. The narrowest resonance is
observed for the BF4- compounds (indicative of a faster exchange), and a noticeable
downfield shift is observed for the CF3SO3- derivatives. Interestingly, in spite of the
fluxionality of the unassembled allyl-Pd unit, very little differences in the shape or
value of chemical shifts of the allyl signals are observed once incorporated in the
metallomacrocycles, which is in line with the lack of involvement of the allyl-Pd bond
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of the assemblies in their dynamic process. This behaviour has been also found in the
closely related tetranuclear allylic assemblies reported by us.[9a]
19F NMR Spectroscopy Studies in Solution
In order to investigate the existence of weak interactions between the fluorinated anions
and the reported assemblies that could contribute to account for the observed differences,
19
the study of their F NMR spectra of at 298K was carried out (see Figures 6 and S52).
For [{Pd(η3-2-Me-C3H4)}6(4-PPh2py)12{M2(tpbz)}3](BF4)18 (M = Pd, 2a62Pd3; Pt,
2a62Pt3), the spectra showed two different resonances at δ ≈ -151 and -147 ppm ascribed
to free and enclosed BF4- anions.[16a, 23] Hexafluorophosphate derivatives [{Pd(η3-2-Me-
C3H4)}6(4-PPh2py)12{Pd2(tpbz)}3](PF6)18 (3a63Pd3) and [{Pd(η3-2-Me-C3H4)}6(4-
PPh2py)12{Pt2(tpbz)}3](PF6)6(PF2O2)12 (3a65Pt3) also display two 19F NMR signals at δ ≈ -
72 (less intense) and -68 ppm with a J(31P-19F) ≈ 714 Hz, thus indicating a similar
situation. For both BF4- and PF6- assemblies the low intensity resonances are downfield
shifted by ∆δ ≈ 4 ppm, which is indicative of the existence of enclosed anions interacting
with the crown metallacyclophane edges. The F NMR spectra of the SbF6- derivatives
19
4a64Pd3 and 4a64Pt3 showed two poorly defined (most probably due to the very large
NMR line widths arising from the quadrupole relaxation of the Sb nuclei and/or the
interacting and free anion exchange) signals δ ≈ -121 and -114 ppm.[22]
Figure 6. 19F NMR spectra of the [{Pd(η3-2-Me-C3H4)}6(4-PPh2py)12{Pd2(tpbz)}3]18+
crown metallamacrocycles with different counteranions in CD2Cl2 at room temperature.
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19
In contrast, the triflate derivatives 1a61Pd3 and 1a61Pt3 exhibited only a single F NMR
resonance at δ ≈ -78 ppm that does not suffer any variation on performing NMR variable-
temperature experiments. Analogously, only one signal at -81.2 ppm (J(31P-19F)= 962 Hz)
is observed for the oxygen-containing PF2O2- anion in the 3a65Pt3 compound. These
observations could be compatible either with a very fast enclosed/free exchange
equilibrium process or with the fact that these anions are not confined within the cavity of
the metallacycles.
Other NMR Studies
After the amazing impossibility of obtaining the PF6- heterometallic “3a63Pt3”
metallamacrocycle in spite of the close similarity with other anions used in this work,
we decided to further investigate the effect of the presence of a mixture of anions on the
self-assembly process. For this purpose, a series of small-scale self-assembly reactions
combining some of the available building blocks i. e. [{Pd(η3-2-Me-C3H4)(4-
PPh2py)2}2]X (X = BF4-, PF6-, SbF6-, CF3SO3-, BArF-) and [M2(tpbz)(solvent)4]X4 (M =
Pd, Pt; (X = BF4-, PF6-, SbF6-, CF3SO3-) were performed. The reactions were monitored
1
31
by H and P{1H} NMR spectroscopy after mixing the appropriate quantities of the
precursors in CD2Cl2 at room temperature. A summary of the results is indicated below:
a) The mixtures do not produce a single symmetrical species when each of the building
blocks has a different counteranion.
b) When the PF6- salt of the allyl-Pd moiety is combined with [M2(tpbz)(solvent)4](BF4)
a mixture of a limited number of assemblies is obtained that can not be ascribed to any
of the above reported crown-like macrocyclic species. Experiments involving [{Pd(η3-
2-Me-C3H4)(4-PPh2py)2}2]BF4 and [M2(tpbz)(solvent)4](SbF6)4 gave analogous results.
c) All the attempts to use the PF6- salt of the PtII acceptor moiety
[Pt2(tpbz)(solvent)4](PF6)4 as a building block only lead to the formation of oligomeric
mixtures as observed in the self-assembly reaction using only hexafluorophosphate as
counteranion under strictly dry conditions (see above).
Given the surprising fact that PF6- precludes the self-assembly of the PtII crown
supramolecules, we studied the reaction of a mixture of [Pd(η3-2-Me-C3H4)(4-
PPh2py)2]PF6 and [Pt2(tpbz)(solvent)4](PF6)4 with a 5 fold excess of Bu4NBF4 in CD2Cl2
at room temperature. The monitoring of the reaction by P{1H} NMR spectroscopy
31
during 2 days showed no changes in the recorded spectra, thus evidencing that the BF4-
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compound had not been assembled even in the presence of a large excess of the latter
anion. Likewise, the mirror experiment was also conducted, i. e. a 5 fold excess of
Bu4NPF6 was added to a CD2Cl2 solution of [Pd(η3-2-Me-C3H4)(4-PPh2py)2]BF4 (2a)
and [Pt2(tpbz)(solvent)4](BF4)4 (2Pt) in a 2:1 molar ratio. In this case, in spite the
presence of the PF6- anion, the BF4- metallamacrocyle 2a62Pt6 was obtained, as could be
evidenced by NMR spectroscopy. Adding up, the results reported here reinforce the
determining role of the nature of counteranions in the course of self-assembly processes.
Related observations have been reported for Dunbar and col. when studying the self-
assembly between different M(II) cations and the 3,6-bis(2-pyridyl)-1,2,4,5-tetrazine
ligand (bptz).[16a, 23]
Theoretical Studies
DFT calculations have been employed to study the intermolecular interaction in the
above reported crown-like complexes (see Computational details in Supp. Information for
a description of the employed methodology). The first step was to analyse the
electrostatic potential of the empty [{Pd(η3-2-Me-C3H4)}6(4-PPh2py)12{Pt2(tpbz)}3]18+
crown (see Figure 7). The electrostatic potential shows that the high positive charge of
this crown-like structure is mainly localized in the internal part of the crown. Hence, this
internal region is specially appropriated for the establishment of interaction with anions.
The number of anions within the cavity is limited to six due to the cavity size inferred
from the X-ray diffraction structure of 3a65Pt3. Interestingly, an inspection of the
representation of the electrostatic potential shows the existence of six “ positive pockets”
inside the cavity, appropriate to accommodate them. Moreover, a larger number of anions
will result in huge anion-anion repulsions.
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Figure 7. Representations of the electrostatic potential of the empty [{Pd(η3-2-Me-
C3H4)}6(4-PPh2py)12{Pt2(tpbz)}3]18+ crown calculated at B3LYP level.
The optimized structures for the Pt systems with four different counteranions (6 BF4-, 6
PF6-, 3 PF6-/3 PF2O2- and 6 CF3SO3-) are represented in Figure 8. In agreement with the X-
ray data of 3a65Pt3 (see Figure 6) the six anions are placed close to the PtII and PdII
cations. In the case of PF2O2- and CF3SO3-, the negative charge is mainly localized on the
oxygen atoms that are closer to the crown metal centers than the fluorine atoms. In all
cases, the six enclosed anions are quite close to the metal cations with fluorine-metal and
oxygen-metal distances being around 2.4-2.5 and 2.7-2.8 Å, respectively. The calculated
anion-crown interaction energies at B3LYP level are collected in Table 3. The results
indicate that the interactions with the homometalllic Pd12 systems are slightly stronger
than those of the corresponding Pd6Pt6 metallamacrocycles. The average anion-crown
interactions involving anions without oxygen atoms (BF4- and PF6-) are stronger than that
of PF2O2- and CF3SO3-, being the strongest interaction with PF6-. On the other hand, the
repulsion energies between the anions (see Table 3) are relatively similar independently
of the nature of the anion being the weakest ones those corresponding to CF3SO3-
systems.
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a
b
c
d
Figure 8. Representation of the four optimized crown structures of [{Pd(η3-2-Me-
C3H4)}6(4-PPh2py)12{Pt2(tpbz)}3]18+ with (a) 6 BF4-, (b) 6 PF6-, (c)3 PF6-·3 PF2O2- and (d) 6
CF3SO3- anions using the GFN2-xTB method (see Computational details). Gray and blue
sphere correspond to PtII and PdII centers and pink, gray, blue, red, light blue, orange and
yellow wires represent boron, carbon, nitrogen, oxygen, fluorine, phosphorus and sulphur
atoms. Cartesian coordinates of equivalent structure only with PdII cations are provided as
SI.
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M and anion-type
Erep
Eint
Pd BF4-
45.4
46.4
45.8
43.2
45.4
46.0
45.0
43.6
-54.8
-66.8
-49.7
-51.0
-53.6
-58.7
-47.0
-49.0
Pd PF6-
Pd PF6- PF2O2-
Pd CF3SO3-
Pt BF4-
Pt PF6-
Pt PF6- PF2O2-
Pt CF3SO3-
Table 3. Interaction energies (in kcal/mol) at B3LYP level for the [{Pd(η3-2-Me-
C3H4)}6(4-PPh2py)12{M2(tpbz)}3]18+ (X: PdII and PtII) crown metallamacrocycles with 6
BF4-, 6 PF6-, 3 PF6-/3 PF2O2- and 6 CF3SO3- anions. The repulsion energy (Erep) between
the six anions calculated as the energy difference between the system with six anions
together and the six isolated molecules while the average crown-anion interactions per
anion (Eint) are obtained as the energy difference between the total system with respect to
the crown and the isolated anions.
The fact that the anions without oxygen atoms have the strongest anion-crown interaction
energies is in agreement with the 19F NMR spectra where signals arising from both
enclosed and free BF4-, PF6- and SbF6- anions can be clearly seen (Figure 5). On the
contrary, the less tightly bound PF2O2- and CF3SO3- are involved faster in-out equilibria
giving rise to a single peak even in the presence of a perfluorinated anion (compound
3a65Pt3). Moreover, the observed difference between the type of interactions involving
oxygen fluoroanions and that of the anions without oxygen atoms could explain the
1
difference in the chemical shifts observed in the H NMR spectra (Figures 3 and 4) for
the close to metal α-pyridine protons.
Preliminary Catalytic Studies
Phosphanes are excellent ligands in palladium-catalysed allylic substitution
reactions.[10a] Although this reaction has been widely studied for a large variety of PdII-
based catalysts, it is well known that the activity is strongly dependent on several
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parameters including the structure of the allylic substrate, the nucleophile, and even the
solvent used.[10c, 24] In contrast, the regioselectivity of the allylic alkylation is mainly
controlled by the nature of the ligands. Hence, in general symmetrical diphosphanes
favour the substitution at the terminal carbon atom, leading to the linear (achiral)
substituted product,[25] while the use of bulkier ligands switch the selectivity towards the
branched product.[26]
Supramolecular assemblies containing catalytically active allyl-PdII units represent a
promising approach for the study of the regioselectivity of these transformations.
Despite that each metallic centre contains monodentate ligands, the geometry and the
rigidity of the system confers properties usually associated to bidentate chelating
systems.[27]
In this respect, we previously reported the preparation of a square allyl-cornered
metallacycle that proved active in the allylic alkylation reaction of cinnamyl acetate.[9a]
In our efforts to increase the nuclearity and regarding the possibility of cooperative
effects that might lead to unexpected activities and selectivities,[28] we have studied the
catalytic behaviour of the supramolecular crowns prepared in this work in the allylic
alkylation reaction of 3-acetoxy-1-phenyl-1-propene with CH2(COOMe)2 as nucleophile
in CH2Cl2 under the well-known Trost conditions (AG1) using N,O-
bis(trimethylsilyl)acetamide (BSA) and potassium acetate. The reaction has been
performed at room temperature and with a 0.5 mol% of concentration level of catalyst
(Scheme 2). A blank study by using the corresponding mononuclear palladium corners
has also been conducted for comparative purposes. Results have been collected in Table
4.
O
O
OMe
MeO
OMe
[Pd]
OAc
O
+
MeO
OMe
MeO
O
O
O
BSA, KOAc
CH2Cl2, RT
Linear
Branched
Scheme 2. Pd-catalysed allylic alkylation of 3-acetoxy-1-phenyl-1-propene.
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Table 4. Catalytic results of the allylic alkylation of 3-acetoxy-1-phenyl-1-propene
according to Scheme 2.[a]
Entry
Precursor
Time
1 h
Conversion [%] Branched/Linear
1
2
1a
>99
70
1:8
All linear
All linear
1:6
1a61Pd3
1a61Pt3
2a
24 h
24 h
1 h
3
20
4
>99
80
5
2a62Pd3
2a62Pt3
3a
24 h
24 h
1 h
All linear
All linear
1:12
6
<1
7
>99
>99
nd[b]
>99
>99
50
8
3a63Pd3
3a65Pd3
4a
24 h
24 h
1 h
All linear
nd
9
10
11
12
13
1:7
4a64Pd3
4a64Pt3
5a
24 h
24 h
1 h
All linear
1:27
10
All linear
[a] Catalytic conditions: 1 mmol substrate, 3 mmol dimethyl malonate, 3 mmol BSA,
0.01 mmol KOAc, 4 mL CH2Cl2, RT. Conversion and branched:linear ratio determined
by GC.
[b]. No determined. The crown contained a mixture of PF6– and PO2F2– anions.
Complete conversions and branched/linear product ratios of the alkylation ranging from
1:6 to 1:99 were obtained after one hour of reaction when the mononuclear corners were
used as catalytic precursors, as found for analogous allylic compounds[25] [Pd(η3-
C3H5)(PPh3)2]+. Interestingly, the increase of the bulkiness of the fluorinated
counteranion affects the regioselectivity of the reaction leading to the linear product
exclusively, as observed for the BArF- corner.
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Our previous catalytic studies of this reaction using square allyl-cornered metallacycles
showed that the presence of the nitrogen donor in the phosphane ligands did not play
any relevant role neither on the regioselectivity nor on the activity of the alkylation, a
trend also observed with the supramolecular assemblies described in this work.
However, the prepared crowns displayed a better regioselectivity compared to its related
metallacyclic squares, affording exclusively the linear alkylated product after 24 h, a
fact that might be attributed to the more rigid environment in the supramolecular
assembly. On moving to the results for the conversions of the Pd/Pd and Pd/Pt crowns,
some differences are observed. Whereas the Pd/Pd catalysts have a more similar activity
compared to its related mononuclear counterparts, heterometallic assemblies displayed
lower activities, which paralleled to the behaviour observed for the previously studied
tetranuclear species. Hence, the allylic fragment is less prone to a nucleophilic attack or
an oxidative addition of the substrate than in the unassembled form, which in agreement
with the less labile nature of the py-Pt bonds.
Conclusions
We have demonstrated that the self-assembly of {Pd(η3-2-Me-C3H4)}+, {M2(tpbz)}4+ (
M = Pd, Pt) and 4-PPh2py moieties in 2:1:4 molar ratio produces quantitatively the
highly positively charged crown-like metallacycles [{Pd(η3-2-Me-C3H4)}6(4-
PPh2py)12{M2(tpbz)}3]18+. These assemblies have been obtained in combination with
different fluorinated counteranions that have conduced to the formation of single
species having the same nuclearity than the indicated above. The presence of mixtures
of anions in the self-assembly process does not allow the formation of single species
and uncharacterizable mixtures are obtained, instead. The obtained metallamacrocycles
are stereochemically non-rigid and their dynamic process that involves a coordination-
decoordination of the M-py bond have, in addition to the higher lability of the PdII
cation, a remarkable dependence on the counteranion present in solution.
The large cavity of the synthesized metallacycles (evidenced by DFT and X-ray
diffraction studies) has a high positive electrostatic potential in its centre whose
representation displays six “pockets” where the accommodation of six anions is
expected to fit. These six anions are involved in weak interactions with the metal
centres through either their oxygen or fluorine atoms. DFT calculations have shown that
the perfluorinated anions BF4- and PF6- interact more strongly with the metallic centres
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than the anions that bear oxygen atoms (CF3SO3-, PF2O2-). These differences in strength
and/or character of the anion-crown interactions are in agreement with relevant facts
evidenced by NMR spectroscopy.
The experiments carried out clearly supports the contention that the anions play a
decisive role in the formation and stability of complex architectures and provide
unequivocal proof of a template effect only in the presence of specific anions.
Although the new palladium crown-like metallamacrocycles are active catalysts in the
allylic alkylation reaction of 3-acetoxy-phenyl-1-propene, the regioselectivity of the
catalytic process do not show significant differences in comparison with that of the
related catalytically active species of lesser nuclearity. Moreover, the increase of the
bulkiness of the fluorinated counteranion affects the regioselectivity of the reaction
leading to the linear product exclusively.
Finally, the construction of bigger and more complicated metallamacrocycles bearing
larger cavities that can establish interactions with a wide range of anions through the
design of new ligands is currently under investigation.
Experimental Section
General Methods
All manipulations were performed under prepurified N2 using standard Schlenk
techniques. Solvents were dried by standard methods and distilled under nitrogen
immediately prior to use, or alternatively from a Solvent Purification System
(Innovative Technologies).
Infrared spectra were recorded on an FT-IR 5700 Nicolet spectrophotometer. P{1H}-
31
NMR (δ(85% H3PO4) = 0.0 ppm), 1H-NMR (δ(TMS) = 0.0 ppm) and 19F-NMR (δ(CFCl3)
= 0.0 ppm) spectra were obtained at 400 or 500 MHz with Varian and Bruker
spectrometers at 25 ºC unless otherwise stated. Elemental analyses of C, H, N and S were
carried out at the Centres Científics i Tecnològics (Universitat de Barcelona). ESI mass
spectra were recorded on a Bruker APEX IV Fourier-transform ion cyclotron resonance
mass spectrometer with a 7.05 T magnet and an Apollo electrospray ion source, a Q/TOF
mass spectrometer (micrOTOF-Q from Bruker), a Thermo FisherScientific Orbitarp XL
or on a LC/MSD-TOF instrument from Agilent Technologies. Unless otherwise state,
acetone solutions of the analysed compounds (0.1-0.2 mM) were used with flow rates of
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3-4 or 10 µLmin-1 depending on the spectrometer used. In each case, ESI parameters were
tuned for optimal signal intensities in order to minimize in source fragmentation.
The compounds [Pd(µ-Cl)(η3-2-Me-C3H4)]2,[29] [Pd(η3-2-Me-C3H4)(COD)]X (X= BF4-,
OTf-, PF6-, SbF6-, BArF),[30] [Pd(η3-2-Me-C3H4)(4-PPh2py)2](CF3SO3),[9a] [M2Cl4(tpbz)] (
M = Pd, Pt),[12c] [M2(tpbz)(CF3SO3)4] (M=Pd, Pt),[12c] 4-PPh2py[31] and tpbz[32] were
prepared as described previously. All other reagents were obtained from commercial
suppliers and used as received.
X-Ray structure determination
Crystal data for complex 3a65Pt3 are presented in the ESI (Table S1).
Data were collected at 100 K on a Bruker-Nonius FR591 KappaCCD2000 rotating anode
diffractometer employing Cu Kα radiation (λ = 1.54178 Å) monochromated using a
multilayer confocal mirror. Data collection was done using the program Collect (Bruker
AXS BV, 1997-2004) and data reduction was undertaken with HKL DENZO and
SCALEPACK programs.[33] The structure was solved by direct methods (SHELXL) and
refined by constrained full least-squares on F2 with SHELXL-2012.(SHELXL2) The
contribution of the disordered solvent molecules within the unit cells of the complex to
the structure factors was taken into account by back-fourier transformation using the
SQUEEZE algorithm(PG07) as implemented in PLATON.[34]
CCDC 1951512 contains the crystallographic data along with specific details pertaining
to the refinement.
Computational details
The structure of the crown complexes was optimized by using the GFN2-xTB approach
proposed by Grimme and coworkers.[35] The cartesian coordinates of the eight optimized
structures are provided as SI. In the triflate systems, the interaction of the anions with the
crown complexes was considered through the fluorine and oxygen atoms of such anion
being more stable the interaction with the SO3 group. The interaction energies were
calculated with those optimized structures by using the B3LYP exchange correlation
functional[36] implemented in the Gaussian09 code[37] with the LanL2DZ basis set
including pseudopotentials for the metal centres. The solvent effects (dichloromethane)
were included with the polarizable conductor calculation model.[38] The interaction
energies were calculated using the energy of the full system with the six anions and the
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10.1002/chem.202000316
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energies of each isolated anion and the crown complex. For one of the complexes
Pd12·6BF4 the basis set superposition error was estimated performing the calculations
without the solvent contribution being around 3% of the total interaction. Such error is
rather small because the anion···crown complex is relatively strong due to a large
electrostatic contribution.
Synthesis and characterization
Synthesis of [Pd(η3-2-Me-C3H4)(4-PPh2py)2]BF4 (2a)
Solid 4-PPh2py (100 mg, 0.38 mmol) was added to a dichloromethane solution (10 mL)
of [Pd(η3-2-Me-C3H4)(COD)]BF4 (68 mg, 0.19 mmol) at room temperature. After 30 min
of stirring, the reaction mixture was filtered, concentrated to ca. half volume under
vacuum and precipitated with diethyl ether. An off-white crystalline solid was obtained in
80% yield (118 mg). 1H NMR (400 MHz, CDCl3): δ = 8.43 (dd, J1 = 4.3 Hz, J2 = 1.9 Hz,
4H, Hα ), 7.52-7.36 (m, 20H, Ph), 6.98 (d, J= 4.3 Hz, 4H, Hβ ), 3.96 (s br, 2Hsyn, Me-
-py
-py
C3H4), 3.72 (s, 2Hanti, Me-C3H4), 1.87 (s, 3H, Me-C3H4). P{1H} NMR (161.9 MHz,
31
CDCl3): δ = 22.5 (s). 19F NMR (376 MHz, CDCl3): δ = 151.2 (s, 10BF4), 151.3 (s,11BF4).
!
ν
= 1573, 1479, 1436, 1083, 1060, 1034. ESI(+) LC/MSD-TOF m/z:
IR (KBr disk):
687.1316 [2a-BF4]+; calcd: 687.1319; 424.0454 [2a-4-PPh2py-BF4]+ ; calcd: 424.0455.
Compounds 3-5a were synthesized following an analogous procedure to that described
for compound 2a.
Synthesis of [Pd(η3-2-Me-C3H4)(4-PPh2py)2]PF6 (3a)
From (80 mg, 0.19 mmol) of [Pd(η3-2-Me-C3H4)(COD)]PF6 compound 3a was obtained
as a white crystalline solid in 87% yield (140 mg). 1H NMR (400 MHz, CDCl3): δ = 8.43
(m, 4H, Hα ), 7.53-7.38 (m, 20H, Ph), 6.93 (d, J= 5.9 Hz, 4H, Hβ ), 3.82 (s br, 2Hsyn,
-py
-py
Me-C3H4), 3.72 (s, 2Hanti, Me-C3H4), 1.89 (s, 3H, Me-C3H4). P{1H} NMR (161.9 MHz,
31
CDCl3): δ = 22.6 (s, PPh2py), -144.3 (sept, J(31P-19F)= 714 Hz, PF6). F NMR (376
19
MHz, CDCl3): δ = -72.17 (d, J(31P-19F)= 714 Hz, PF6). IR (KBr disk):
!
ν
= 1575, 1480,
1435, 1100, 842. ESI(+) LC/MSD-TOF m/z: 687.1315 [3a-PF6]+; calcd: 687.1319;
424.0448 [3a-4-PPh2py-PF6]+ ; calcd: 424.0455.
Synthesis of [Pd(η3-2-Me-C3H4)(4-PPh2py)2]SbF6 (4a)
From (95 mg, 0.19 mmol) of [Pd(η3-2-Me-C3H4)(COD)]SbF6 compound 4a was obtained
as pale yellow crystalline solid in 85% yield (150 mg). 1H NMR (400 MHz, CDCl3): δ =
24
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Chemistry - A European Journal
8.43 (s br, 4H, Hα ), 7.52-7.36 (m, 20H, Ph), 6.92 (s br, 4H, Hβ ), 3.73 (s br,
-py -py
2Hsyn+2Hanti, Me-C3H4), 1.90 (s, 3H, Me-C3H4). P{1H} NMR (161.9 MHz, CDCl3): δ =
31
!
ν
= 1575, 1480, 1438, 1100, 659. ESI(+) LC/MSD-TOF m/z:
24.9 (s). IR (KBr disk):
687.1307 [4a-SbF6]+; calcd: 687.1319; 424.0455 [4a-4-PPh2py-SbF6]+ ; calcd: 424.0455.
Synthesis of [Pd(η3-2-Me-C3H4)(4-PPh2py)2]BArF (5a)
From (215 mg, 0.19 mmol) of [Pd(η3-2-Me-C3H4)(COD)]BArF compound 5a was
1
obtained as pale yellow crystalline solid in 70% yield (205 mg). H NMR (400 MHz,
CDCl3): δ = 8.42 (s br, 4H, Hα ), 7.70 (m, 8H, HBArF), 7.52-7.50 (m, 8H, HBArF+ Hp-Ph),
-py
7.36 (m, 8H, Hm-Ph), 7.26 (m, 8H, Ho-Ph), 6.79 (m, 4H, Hβ ), 3.75 (s br, 2Hsyn, Me-C3H4),
-py
3.24 (m, 2Hanti, Me-C3H4), 1.87 (s, 3H, Me-C3H4). P{1H} NMR (161.9 MHz, CDCl3):
31
19
δ = 23.4 (s). F NMR (376 MHz, CDCl3): δ = -62.41 (s, BArF). IR (KBr disk):
!
ν
=
1587, 1482, 1440, 1356, 1279, 1125. ESI(+) LC/MSD-TOF m/z: 687.1329 [5a-BArF]+;
calcd: 687.1319; 424.0452 [5a-4-PPh2py-BArF]+ ; calcd: 424.0455.
Synthesis of [Pd2(tpbz)(solvent)4] (BF4)4 (2Pd)
Solid AgBF4 (80 mg, 0.41 mmol) was added to a dichloromethane/acetonitrile (20:20ml)
suspension of [Pd2Cl4(tpbz)] (116 mg, 0.10 mmol) at room temperature. After stirring in
the dark overnight, the reaction mixture was filtered, concentrated to 5 ml under vacuum
and precipitated with 30 ml of diethyl ether. A white solid was obtained in 68% yield
1
(105 mg) (considering the isolation of [Pd2(tpbz)(CH3CN)4](BF4)4). H NMR (400 MHz,
CD3NO2): δ = 8.34 (m, 2H, C6H2P4), 7.83-7.74 (m, 24H, Ph), 7.65-7.60 (m, 16H, Ph).
31P{1H} NMR (161.9 MHz, CD3NO2): δ = 66.0 (s). 19F NMR (376 MHz, CD3NO2): δ = -
10 11
154.9 (s, BF4), -155.0 (s, BF4). IR (KBr disk):
!
ν
= 2315, 2289,1482, 1438, 1083,
1060, 995. ESI(+) Orbitrap m/z: 590.02 [2Pd-2CH3CN+2Cl-4BF4]2+; calcd: 590.01;
395.37 [2Pd-CH3CN+Cl-4BF4]3+; calcd: 395.36; 387.69 [2Pd-2CH3CN+H2O+Cl-4BF4]3+;
calcd: 387.69; 381.69 [2Pd-2CH3CN+Cl-4BF4]3+; calcd: 381.69; 292.04 [2Pd-4BF4]4+;
calcd: 298.04.; 298.28 [2Pd-CH3CN+H2O-4BF4]4+; calcd: 292.28.
Compounds 3Pd-4Pd and 2Pt-5Pt were synthesized following an analogous procedure to
that described for compound 2Pd.
Synthesis of [Pd2(tpbz)(solvent)4](PF6)4 (3Pd)
From 100 mg (0.40 mmol) of AgPF6 and 116 mg (0.10 mmol) [Pd2Cl4(tpbz)] compound
3Pd was obtained as white solid in 73% yield (130 mg) (considering the isolation of
1
[Pd2(tpbz)(CH3CN)4](PF6)4). H NMR (400 MHz, CD3CN): δ = 7.94 (br, 2H, C6H2P4),
25
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7.70-7.65 (m, 24H, Ph), 7.53-7.49 (m, 16H, Ph). 31P{1H} NMR (161.9 MHz, CD3CN): δ
= 64.0 (s br, tpbz), -144.6 (sept, J(31P-19F) = 706 Hz, PF6). 19F NMR (376 MHz, CD3CN):
δ = -72.95 (d, J(31P-19F) = 706 Hz, PF6). IR (KBr disk):
!
ν
= 2325, 2295, 1482, 1438,
1099, 837. ESI(+) Orbitrap m/z: 590.02 [3Pd-2CH3CN+2Cl-4PF6]2+; calcd: 590.01;
578.51 [3Pd-3CH3CN+H2O+2Cl-4PF6]2+; calcd: 578.50; 569.50 [2Pd-3CH3CN+2Cl-
4PF6]2+; calcd: 569.50; 548.99 [3Pd-4CH3CN+2Cl-4PF6]2+; calcd: 548.99.
Synthesis of [Pd2(tpbz)(solvent)4](SbF6)4 (4Pd)
From 140 mg (0.41 mmol) of AgSbF6 and 116 mg (0.10 mmol) [Pd2Cl4(tpbz)] compound
4Pd was obtained as yellow solid in 78% yield (160 mg) (considering the isolation of
1
[Pd2(tpbz)(H2O)4](SbF6)4). H NMR (400 MHz, CD3CN): δ = 7.93 (br, 2H, C6H2P4),
7.70-7.65 (m, 24H, Ph), 7.52-7.50 (m, 16H, Ph). 31P{1H} NMR (161.9 MHz, CD3CN): δ
= 64.1 (s br, tpbz). F NMR (376 MHz, CD3CN): δ = -123.8 (six, J(121Sb-19F) = 1940
19
Hz; oct, J(123Sb-19F) = 1050 Hz, SbF6). IR (KBr disk):
!
ν
= 1482, 1438, 1100, 658. ESI(+)
LC/MSD-TOF (acetone) m/z: 257.006 [4Pd-4H2O-4SbF6]4+; calcd: 257.008. ESI(+)
Orbitrap (acetonitrile) m/z: 589.96 [4Pd-4H2O+2CH3CN+2Cl-4SbF6]2+; calcd: 590.01;
569.44 [4Pd-4H2O+CH3CN+2Cl-4SbF6]2+; calcd: 569.50; 548.93 [4Pd-4H2O+2Cl-
4SbF6]2+; calcd: 548.99; 395.32 [4Pd-4H2O+3CH3CN+Cl-4SbF6]3+; calcd: 395.36.
Synthesis of [Pt2(tpbz)(solvent)4](BF4)4 (2Pt)
From 80 mg (0.41 mmol) of AgBF4 and 135 mg (0.10 mmol) of [Pt2Cl4(tpbz)] compound
2Pt was obtained as white solid in 75% yield (125 mg) (considering the isolation of
1
[Pt2(tpbz)(CH3CN)2(H2O)2](BF4)4). H NMR (400 MHz, CD3CN): δ = 7.94 (tt, J(1H-31P)
= 69.7 Hz; J(1H-31P) = 8.9 Hz, 2H, H-tpbz), 7.70-7.30 (m, 40H, Ph). 31P{1H} NMR (161.9
2
MHz, CD3CN): δ = 40.0 (m(AA’XX’), Ptrans-N, J(31P-195Pt) = 3385 Hz, 33.7
(m(AA’XX’), Ptrans-O 2J(31P-195Pt) = 3810 Hz). F NMR (376 MHz, CD3CN): δ = -154.7
19
10 11
(s, BF4), -155.1 (s, BF4). IR (KBr disk):
!
ν
= 2327, 2300, 1482, 1437, 1084, 1063,
996. ESI(+) Orbitrap m/z: 454.36 [2Pt-2H2O+CH3CN+Cl-4BF4]3+; calcd: 454.40; 342.03
[2Pt-2H2O+2CH3CN-4BF4]4+; calcd: 342.06; 331.78 [2Pt-2H2O+CH3CN-4BF4]4+; calcd:
331.81.
Synthesis of [Pt2(tpbz)(solvent)4](PF6)4 (3Pt)
From 105 mg (0.41 mmol) of AgPF6 and 135 mg (0.10 mmol) of [Pt2Cl4(tpbz)]
compound 3Pt was obtained as white solid in 74% yield (140 mg) (considering the
isolation of [Pt2(tpbz)(CH3CN)2(H2O)2](PF6)4. 1H NMR (400 MHz, CD3CN): δ = 7.94 (tt,
26
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J(1H-31P) = 65.6 Hz; J(1H-31P) = 8.5 Hz, 2H, H-tpbz), 7.72-7.11 (m, 40H, Ph). P{1H}
31
NMR (161.9 MHz, CD3CN): δ = 40.0 (m(AA’XX’), Ptrans-N, 2J(31P-195Pt) = 3392 Hz, 33.7
(m(AA’XX’), Ptrans-O 2J(31P-195Pt) = 3811 Hz), -144.6 (sept, J(31P-19F) = 706 Hz, PF6). F
19
NMR (376 MHz, CD3CN): δ = -72.97 (d, J(31P-19F) = 706 Hz, PF6). IR (KBr disk):
!
ν
= 2333, 2305, 1483, 1439, 1104, 836.
Synthesis of [Pt2(tpbz)(solvent)4](SbF6)4 (4Pt)
From 140 mg (0.41 mmol) of AgPF6 and 135 mg (0.10 mmol) of [Pt2Cl4(tpbz)]
compound 4Pt was obtained as white solid in 66% yield (150 mg) (considering the
1
isolation of [Pt2(tpbz)(CH3CN)2(H2O)2](SbF6)4. H NMR (400 MHz, CD3CN): δ = 7.94
(tt, J(1H-31P) = 66.0 Hz; J(1H-31P) = 8.8 Hz, 2H, H-tpbz), 7.72-7.24 (m, 40H, Ph). 31P{1H}
NMR (161.9 MHz, CD3CN): δ = 40.0 (m(AA’XX’), Ptrans-N, 2J(31P-195Pt) = 3386 Hz, 33.7
(m(AA’XX’), Ptrans-O 2J(31P-195Pt) = 3809 Hz). F NMR (376 MHz, CD3CN): δ = -124.0
19
(six, J(121Sb-19F) = 1932 Hz; oct, J(123Sb-19F) = 1045 Hz, SbF6) IR (KBr disk):
!
ν
= 2337, 2310, 1483, 1439, 1104, 656. ESI(+) LC/MSD-TOF (acetone) m/z: 311.29 [4Pt-
2H2O-CH3CN-4SbF6]4+; calcd: 311.29; 301.04 [4Pt-2H2O-CH3CN-4SbF6]4+; calcd:
301.04. ESI(+) Orbitrap (acetonitrile) m/z: 678.51 [4Pt-2H2O+2Cl-4SbF6]2+; calcd:
678.57; 454.36 [4Pt-2H2O+CH3CN+Cl-4SbF6]3+; calcd: 454.40.
Synthesis of [Pt2(tpbz)(PF2O2)4](5Pt)
Solid AgPF2O2 (85 mg, 0.41 mmol) was added to a dichloromethane/acetonitrile
(20:20ml) suspension of [Pt2Cl4(tpbz)] (135 mg, 0.10 mmol) at room temperature. After
stirring in the dark overnight, the reaction mixture was filtered and the resulting solution
evaporated to dryness. The solid residue was extracted with nitromethane (2x10 mL). The
combined extracts were concentrated and after the addition of diethyl ether a white solid
1
was obtained in 59% yield (95 mg). H NMR (400 MHz, CD3NO2): δ = 8.16 (s br, 2H,
H-tpbz), 7.75-7.21 (m, 40H, Ph). P{1H} NMR (161.9 MHz, CD3NO2): δ = 30.6 (s,
31
2J(31P-195Pt) = 4099 Hz, tpbz), -15.9 (t, 1J(31P-19F) = 768 Hz, PF2O2-). 19F NMR (376 MHz,
1
CD3NO2): δ = - 81.3 (d, J(31P-19F) = 968 Hz). IR (KBr disk):
= 1483, 1437, 1297,
!
ν
1131, 1102, 843.
Synthesis of [{Pd(η3-2-Me-C3H4)}6(4-PPh2py)12{Pd2(tpbz)}3](CF3SO3)18 (1a61Pd3)
Method A: To a dichloromethane solution (20 ml) of [Pd(η3-2-Me-C3H4)(COD)] CF3SO3
(25 mg, 0.06 mmol) were added successively 32 mg (0.12 mmol) of 4-PPh2py and 53 mg
(0.03 mmol) [Pd2(CH3CN)4(tpbz)](CF3SO3)4 as a solids at room temperature. After 2h of
27
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stirring, the reaction mixture was filtered, concentrated to 5 ml under vacuum and
precipitated with diethyl ether. A pale yellow solid was obtained in 76% yield (75 mg).
Method B: To a dichloromethane solution (20 ml) of the previously synthesized [Pd(η3-2-
Me-C3H4)(4-PPh2py)2]CF3SO3
(1a)
(50
mg,
0.06
mmol)
solid
[Pd2(CH3CN)4(tpbz)](CF3SO3)4 (53 mg, 0.03 mmol) was added. After 2h of stirring, the
reaction mixture was filtered, concentrated to 5 ml under vacuum and precipitated with
1
diethyl ether. A pale yellow solid was obtained in 86% yield (85 mg). H NMR (400
MHz, CD2Cl2): δ = 8.88 (s br, 24H, Hα− ), 8.05-6.84 (m, 270H, Ph+Hβ− ), 3.51 (s, 12Hsyn,
py
py
Me-C3H4), 2.27 (s br, 12Hanti, Me-C3H4), 1.87 (s, 18H, Me-C3H4). P{1H} NMR (161.9
31
MHz, CD2Cl2): δ = 55.2 (s, tpbz), 25.6 (s, PPh2py). 19F NMR (376 MHz, CD2Cl2): δ = -
!
ν
= 1601, 1485, 1440, 1277, 1164, 1029. ESI(+) Q/TOF m/z:
78.6. IR (KBr disk):
2324.55 [1a61Pd3-4CF3SO3]4+; calcd: 2324.56; 2115.18 [1a61Pd3-1a-4CF3SO3]4+; calcd:
2115.29; 1830.80 [1a61Pd3-5CF3SO3]5+; calcd: 1829.85; 1662.21 [1a61Pd3-1a-
5CF3SO3]5+; calcd: 1662.24; 1499.88 [1a61Pd3-6CF3SO3]6+; calcd: 1499.89; 687.16 [1a-
CF3SO3]+; calcd: 687.19.
Metallamacrocycles na6nPd3 and na6nPt3 were synthesized following analogous
procedures to those described for compound 1a61Pd3.
Synthesis of [{Pd(η3-2-Me-C3H4)}6(4-PPh2py)12{Pt2(tpbz)}3](CF3SO3)18 (1a61Pt3)
Method A. From 25 mg (0.06 mmol) of [Pd(η3-2-Me-C3H4)(COD)]CF3SO3, 32 mg (0.12
mmol) of 4-PPh2py and 60 mg (0.03 mmol) of [Pt2(CH3CN)2(H2O)2(tpbz)](CF3SO3)4
compound (1a61Pt3) was obtained as a white solid in 77% yield (80 mg).
Method B: From 50 mg (0.06 mmol) of [Pd(η3-2-Me-C3H4)(4-PPh2py)2]CF3SO3 (1a) and
60 mg (0.03 mmol) of [Pt2(CH3CN)2(H2O)2(tpbz)](CF3SO3)4 compound (1a61Pt3) was
obtained as a white solid in 86% yield (90 mg). 1H NMR (400 MHz, CD2Cl2): δ = 8.89 (s
br, 24H, Hα− ), 8.13-6.14 (m, 270H, Ph+Hβ− ), 3.62 (s, 12Hsyn, Me-C3H4), 2.25 (m, 12Hanti,
py
py
Me-C3H4), 1.90 (s, 18H, Me-C3H4). P{1H} NMR (161.9 MHz, CD2Cl2): δ = 29.1 (s,
31
2J(31P-195Pt) = 3245 Hz, tpbz), 26.0 (s, PPh2py). 19F NMR (376 MHz, CD2Cl2): δ = -78.1.
!
ν
= 1595, 1485, 1440, 1277, 1166, 1030. ESI(+) Orbitrap m/z:
IR (KBr disk):
1936.1164 [1a61Pt3-5CF3SO3]5+; calcd: 1936.1267; 1588.6135 [1a61Pt3-6CF3SO3]6+;
calcd: 1936.6135; 1340.3662 [1a61Pt3-7CF3SO3]7+; calcd: 1340.3898; 687.1317 [1a-
CF3SO3]+; calcd: 687.1319.
Synthesis of [{Pd(η3-2-Me-C3H4)}6(4-PPh2py)12{Pd2(tpbz)}3](BF4)18 (2a62Pd3)
28
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Method A. From 22 mg (0.06 mmol) of [Pd(η3-2-Me-C3H4)(COD)]BF4, 32 mg (0.12
mmol) of 4-PPh2py and 45 mg (0.03 mmol) of [Pd2(tpbz)(CH3CN)4](BF4)4 (2Pd)
compound 2a62Pd3 was obtained as a white solid in 80% yield (70 mg).
Method B: From 45 mg (0.06 mmol) of [Pd(η3-2-Me-C3H4)(4-PPh2py)2]BF4 (2a) and 45
mg (0.03 mmol) of [Pd2(tpbz)(CH3CN)4](BF4)4 (2Pd) compound 2a62Pt3 was obtained as
1
a white solid in 91% yield (80 mg). H NMR (400 MHz, CD2Cl2): δ = 8.69 (s br, 24H,
Hα− ), 8.10-6.77 (m, 270H, Ph+Hβ− ), 3.66 (s, 12Hsyn, Me-C3H4), 2.13 (m, 12Hanti, Me-
py py
C3H4), 1.91 (s, 18H, Me-C3H4). P{1H} NMR (161.9 MHz, CD2Cl2): δ = 57.6 (s, tpbz),
31
25.0 (s, PPh2py). F NMR (376 MHz, CD2Cl2): δ = -146.7 (s br, BF4-)in, -150.7 (s,
19
!
ν
= 1597 , 1481, 1442, 1100, 1084, 1060, 995. ESI(+) Q/TOF
BF4)out. IR (KBr disk):
m/z: 2106.4661 [2a62Pd3-4BF4]4+; calcd: 2106.4874; 1667.7846 [2a62Pd3-5BF4]5+; calcd:
1667.7891; 1375.4906 [2a62Pd3-6BF4]6+; calcd: 1375.4902; 1166.5715 [2a62Pd3-7BF4]7+;
calcd: 1166.5624; 687.1283 [2a-BF4]+; calcd: 687.1319.
Synthesis of [{Pd(η3-2-Me-C3H4)}6(4-PPh2py)12{Pt2(tpbz)}3](BF4)18 (2a62Pt3)
Method A. From 22 mg (0.06 mmol) of [Pd(η3-2-Me-C3H4)(COD)]BF4, 32 mg (0.12
mmol) of 4-PPh2py and 50 mg (0.03 mmol) of [Pt2(tpbz)(CH3CN)2(H2O)2](BF4)4 (2Pt)
compound 2a62Pt3 was obtained as a white solid in 81% yield (75 mg).
Method B: From 45 mg (0.06 mmol) of [Pd(η3-2-Me-C3H4)(4-PPh2py)2]BF4 (2a) and 50
mg (0.03 mmol) of [Pt2(tpbz)(CH3CN)2(H2O)2](BF4)4 (2Pt) compound 2a62Pt3 was
obtained as a white solid in 86% yield (80 mg). 1H NMR (400 MHz, CD2Cl2): δ = 8.69 (s
br, 24H, Hα− ), 8.14-6.79 (m, 270H, Ph+Hβ− ), 3.75 (s, 12Hsyn, Me-C3H4), 2.10 (m, 12Hanti,
py
py
Me-C3H4), 1.92 (s, 18H, Me-C3H4). P{1H} NMR (161.9 MHz, CD2Cl2): δ = 30.6 (s,
31
2J(31P-195Pt) = 3270 Hz, tpbz), 25.9 (s, PPh2py). δ = 57.6 (s, tpbz), 25.0 (s, PPh2py). F
19
NMR (376 MHz, CD2Cl2): δ = -146.6 (s br, BF4-)in, -151.0 (s, BF4)out. IR (KBr disk):
!
ν
= 1601 , 1481, 1437, 1099, 1057, 996. ESI(+)Q/TOF m/z: 1464.0421 [2a62Pt3-6BF4]6+;
calcd: 1464.0503; 1242.4517 [2a62Pt3-7BF4]7+; calcd: 1242.4710; 1076.3908 [2a62Pt3-
8BF4]8+; calcd: 1076.4117; 687.1220 [2a-BF4]+; calcd: 687.1319. LC/MSD-TOF m/z:
3014.95 [2a62Pt3-3BF4]3+; calcd: 3015.10; 2239.66 [2a62Pt3-4BF4]4+; calcd: 2239.58;
1774.41 [2a62Pt3-5BF4]5+; calcd: 1774.26; 1464.18 [2a62Pt3-6BF4]6+; calcd: 1464.05;
1242.59 [2a62Pt3-7BF4]7+; calcd: 1242.47.
Synthesis of [{Pd(η3-2-Me-C3H4)}6(4-PPh2py)12{Pd2(tpbz)}3](PF6)18 (3a63Pd3)
29
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