Palladium fluoro complexes: Useful tools to access organometallic metallamacrocycles

DOI: 10.1002/anie.200703393

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Angewandte Chemie - International Edition p. 8674 - 8678 (2007)

Update date:2022-07-31

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Authors:

Steffen, Andreas

Braun, Thomas

Neumann, Beate

Stammler, Hans-Georg

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Article abstract of DOI:10.1002/anie.200703393

Fluorine's the key: Fluoropalladium complexes open up a new route to metallamacrocycles. Treatment of 1 with 1-trimethylsilylated derivatives of imidazole, 2-phenylimidazole, or purine (see scheme) gives neutral molecules such as the bowl-shaped compound 2 (see structure, iPr groups have been omitted for clarity). All compounds represent rare examples of neutral organometallic macrocycles and do not undergo reductive elimination of a C-N bond. (Chemical Equation Presented).

Full text of DOI:10.1002/anie.200703393

Communications

DOI: 10.1002/anie.200703393

Fluorinated Macrocycles

Palladium Fluoro Complexes: Useful Tools To Access Organometallic

Metallamacrocycles**

Andreas Steffen, Thomas Braun,* Beate Neumann, and Hans-Georg Stammler

The remarkable reactivity and exceptional properties of d⁸

transition-metal fluoro complexes account for their role in the

synthesis of highly fluorinated organic building blocks and

provide novel synthetic pathways to unique coordination

compounds.^[1,2]It has been demonstrated that fluoro com-

plexes can serve as fluorinating agents,^[1,3]but they also

appear as intermediates in catalytic conversions,^[1,2]for

instance in cross-coupling reactions. The fluoro ligand in an

intermediate fluoro species often exhibits higher reactivity

than a chloro or bromo ligand.^[2]One striking example

4,4’-bipyridine (4,4’-bpy) under dissociation of NO₃to give

the macrocyclic compound [{Pd(en)(m-4,4’-bpy)}₄][NO₃]₈.^[6a]

Comparable behavior of Pd F complexes has not yet been

reported.

Herein, we demonstrate the applicability of fluoride

exchange at palladium for the synthesis of organometallic

macrocycles; the latter comprise heteroaromatic rings as

spacer units between Pd centers. This approach provides new

opportunities for the synthesis of neutral macrocycles,

examples of which are scarce. We use this strategy to prepare

square and triangular molecules, which are stabilized by

tetrafluoropyridyl ligands. Comparable triangular compounds

have been referred to as “metallacalixarenes”.^[6a,7,8]

Treatment of a solution of palladium fluoro complex 1

(Scheme 1) in THF with 1-trimethylsilyl-imidazole at 203 K

led to the formation of the imidazole derivative trans-[Pd(1-

C₃N₂H₃)(4-C₅NF₄)(PiPr₃)₂] (2a), which is only stable below

283 K. Above this temperature, free phosphine and macro-

cycle 3a form. Palladacycle 3a was characterized by NMR

spectroscopy, mass spectrometry, elemental analysis, and X-

ray diffraction analysis. Single crystals of 3a were obtained

from a solution in benzene.^[9]Both enantiomers of the chiral

compound 3a were found in the unit cell; one is shown in

Figure 1.

The palladium centers exhibit square-planar coordination

geometry, thus leading to a square macrocycle with C₄

symmetry. The dihedral angle between the coordination

planes at the transition-metal centers is 31.18, whereas the

imidazole units are arranged almost perpendicular to the Pd

coordination planes. The diagonal Pd···Pd distance is 8.763 ,

and the separation of two Pd atoms on the same edge is

6.197 . The stacking of the molecules leads to a channel

arrangement in the solid state (see the Supporting

involves the activation of a C F bond of 2,4,6-trifluoro-5-

chloropyrimidine in the presence of a thermodynamically

weaker C Cl bond at {Ni(PPh₃)₂}.^[2a]Only the resulting nickel

fluoro complex shows catalytic activity towards C C coupling

reactions with aryl boronic acids, whereas the chloro analogue

does not. Comparable behavior has been found for a C Si

coupling reaction at a palladium center.^[2c]In this case, a

disilane is employed to replace the fluoro ligand through the

formation of a strong Si F bond. V. V. Grushin and co-

workers found that palladium halide complexes of the type

trans-[PdX(Ph)(PPh₃)₂] (X = Cl, Br, I) undergo CO insertion

into the M C bond, but no reductive elimination occurred.

When trans-[PdF(Ph)(PPh₃)₂] is used, trans-[PdF(PhCO)-

(PPh₃)₂] forms under CO atmosphere. This complex is only

stable up to 108C, and reductive elimination of benzoyl

fluoride is reported.^[4]Access to d⁸transition-metal fluoro

complexes is provided by reaction of an appropriate precursor

complex with a fluoride source, such as HF, AgF, XeF₂,

Me₃SnF, or ClF, or by activation of a carbon–fluorine bond at

a transition-metal center.^{[1a–e,2,4,5]}Pd complexes bearing

anionic ligands, such as chloro, nitrato, or triflato ligands,

have been found to undergo self-assembly in the presence of

ligands that can serve as bridging units.^[6]For example,

[Pd(en)(NO₃)₂] (en = ethylenediamine) readily reacts with

Information). The C N bond lengths of the imidazole units

are all in the same range. The equal N2 C17 and N3 C17

bond lengths and the angle N2-C17-N3 of 112.98, which is

widened compared to the free heterocycle, suggest that, to a

degree, electron density is delocalized through the ring.^[10]

Although the [{Pd}₄(1-C₃N₂H₃)₄] ({Pd} = Pd(4-C₅NF₄)(PiPr₃))

species 3a is stable in the solid state as well as in solution, it

undergoes fragmentation in MALDI-TOF experiments even

at low laser intensities, giving a signal at m/z 1868.1, which

corresponds to [3aÀC₃N₂H₃]⁺according to the isotope

pattern.^[11]Further fragments have been found at m/z 1384.6

[{Pd}₃(C₃N₂H₃)₂]⁺and m/z 900.4 [{Pd}₂(C₃N₂H₃)]⁺.

The same synthetic strategy as for the preparation of 2a

can be employed to obtain trans-[Pd(1-C₂N₃H₂)(4-C₅NF₄)-

(PiPr₃)₂] (2b) by addition of trimethylsilyltriazole to 1

(Scheme 1). Compound 2b shows a similar behavior as 2a,

and conversion to the tetrameric triazole species 3b and free

[*] A. Steffen, Prof. Dr. T. Braun

Institut für Chemie

Humboldt-Universität zu Berlin

Brook-Taylor-Strasse 2, 12489 Berlin (Germany)

Fax: (+49)30-2093-6939

E-mail: thomas.braun@chemie.hu-berlin.de

B. Neumann, Dr. H.-G. Stammler

Fakultät für Chemie

Universität Bielefeld

Postfach 100131, 33501 Bielefeld (Germany)

[**] We would like to acknowledge the Deutsche Forschungsgemein-

schaft and the Fonds der Chemischen Industrie for financial

support. We thank Ms. A. Penner and Dr. B. Ziemer for the help with

the crystal structure analysis of 3c.

Supporting information for this article is available on the WWW

under http://www.angewandte.org or from the author.

8674

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Angew. Chem. Int. Ed. 2007, 46, 8674 –8678

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Angewandte

Chemie

Encouraged by these results, we tried to extend

our reaction route to the preparation of macro-

cycles that exhibit bowl-like structures.^[7,12]Suitable

heterocyclic spacer units can be provided by

silylated compounds such as 1-trimethylsilylated

2-phenylimidazole, benzimidazole, or purine.

Addition of these heterocycles to a solution of 1

at room temperature led to the slow formation of

2c and 4a,b (Schemes 1 and 2).

We were not able to isolate 2c, 4a, or 4b,

because the subsequent reactions to the macro-

cyclic compounds with concomitant dissociation of

a phosphine ligand proceeded while the starting

compound 1 was still present. Upon heating a

solution of 2c, macrocycle 3c is formed

(Scheme 1). Single crystals suitable for X-ray

diffraction analysis^[9]were obtained from a solution

in fluorobenzene. The molecular structure shown in

Figure 3 clearly demonstrates the presence of a

tetranuclear macrocyclic compound in which the 2-

phenylimidazole units each connect two Pd atoms. The

phenylimidazole moieties are arranged in an alternating up

Scheme 1. Synthesis of 2a–c and formation of the macrocycles 3a–c.

Figure 1. Crystal structure of 3a. Thermal ellipsoids are set at the 50%

probability level. H atoms and iPr groups have been omitted for clarity.

Selected bond lengths [] and angles [8]: Pd1–N2 2.078(2), N2–C17

1.340(3), N3–C17 1.338(3); N2-C17-N3 112.9(2).

Figure 2. Crystal structure of 3b. Thermal ellipsoids are set at the 50%

probability level. H atoms and iPr groups have been omitted for clarity.

Selected bond lengths [] and angles [8]: Pd1–N4 2.057(6), N4–C29

1.341(11), N3–C29 1.347(10); N3-C29-N4 112.8(7).

phosphine has been observed. X-ray dif-

fraction analysis^[9]indicates an N1,N4

bridging mode for the triazole units

(Figure 2). Judging from the geometric

data, delocalization of electron density

seems to be feasible. The Pd···Pd separa-

tions of atoms located on the same edge

are 6.132and 6.305 , while the separa-

tions along the diagonals are 8.729 and

8.860 . Unlike the situation in 3a, the

1,2-alternating triazole moieties deviate

about 258 from a perpendicular confor-

mation relative to the metal coordination

plane. The identity of 3b was also con-

firmed by mass spectrometry with signals

in the MALDI-TOF mass spectrum at

m/z 1874.2([ 3bÀC₂N₃H₂]⁺) and 1792.3

([3bÀC₅NF₄]⁺).

Scheme 2. Formation of the metallamacrocycles 5a, 5b, and 6b.

Angew. Chem. Int. Ed. 2007, 46, 8674 –8678

ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.angewandte.org

8675

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Communications

unprecedented for an organometallic compound.^{[6,7,8e,12,14,15]}

The purine units in 5b exhibit a N1,N3 bridging mode and are

oriented to the same face of the Pd₃triangle, unlike in other

Pd^II-based macrocycles.^[8a,e,12e]The distance between a palla-

dium atom and the opposite heterocyclic spacer unit is about

5.9 . Lippert and co-workers have reported the synthesis of

cationic metallacalix[4]- and metallacalix[6]arenes of the type

[a₂PdL]_nⁿ⁺(a₂= 1,2-diaminocyclohexane, L = hydroxypyrimi-

dine derivatives, n = 4,6).^[12]Furthermore, 5b represents a

rare example of a coordination compound with a triangular

geometry with metal atoms at the vertices.^{[6a,8,13,15c,d]}

The transformations presented above can also be carried

out at elevated temperatures when non-silylated heterocycles

are employed together with the bases NEt₃and Cs₂CO₃to

give the macrocycles 3a–c, 5a,b, and 6b. However, under

these conditions no isolation or spectroscopic detection of

2a–c or 4a,b has been successful, and several unidentified

byproducts are formed (12–50%).

The fluoro ligand in trans-[PdF(4-C₅NF₄)(PiPr₃)₂] (1) is

evidently crucial for the formation of the monomeric building

blocks, because the corresponding chloro complex trans-

[PdCl(4-C₅NF₄)(PiPr₃)₂]^[2c]cannot be used for the transfor-

mations presented above, neither on employing silylated

heterocycles nor on using non-silylated heterocycles in the

presence of bases (e.g. NEt₃and Cs₂CO₃), even at elevated

temperatures.

Figure 3. Crystal structure of 3c. Thermal ellipsoids are set at the 50%

probability level. H atoms and iPr groups have been omitted for clarity.

Selected bond lengths [] and angles [8]: Pd1–N1 2.098(13), N1–C1

1.339(18), N2–C1 1.302(18); N1-C1-N2 116.28(16).

and down mode with respect to the square plane defined by

the four Pd atoms.^[12]A MALDI-TOF mass spectrum with

signals at m/z 2096.3 [3cÀC₉N₂H₇]⁺and 2046.5 [3cÀ

(C₃H₇)C₅NF₄]⁺confirms the identity of the tetramer 3c.^[11]

At 343 K, the transformation of the monomers 4a and 4b

into the metallacalix[3]arenes 5a and 5b is completed

(Scheme 2). With purine as the spacer unit, the generation

of a second macrocycle, 6b, was also observed (ratio 5b/6b

1:1, Scheme 2). On the basis of mass spectra, we believe that

the latter consists of a pentanuclear macrocycle. ³¹P NMR

spectroscopic investigations revealed that 5b and 6b do not

interconvert upon heating a solution of the two in toluene or

THF.^[6a,13]Signals at m/z 1601.6 and 1484.4 in the MALDI-

TOF spectra of 5a correspond to the parent ion [5a]⁺and to

[5aÀC₇N₂H₅]⁺. The palladacycles 5b and 6b give rise to

fragmentation signals at m/z = 1491.4 [5bÀC₅N₄H₃]⁺and

2561.1 [6bÀC₅N₄H₃]⁺, respectively. Single crystals of 5b

suitable for X-ray diffraction analysis^[9]were obtained. The

data reveal a bowl-shaped conformation with C₃symmetry

(Figure 4). To our knowledge, such an arrangement is

The metal atoms of Pt^II- and Pd^II-based macrocycles are

often stabilized by cis-coordinating chelating ligands to avoid

dissociation and scrambling of the monomers to cycles of

different sizes.^{[8,12d,e,14,15]}Complexes 3a–c and 5a,b are not

stabilized in such a way. Instead, it is more likely that a

stabilizing influence of the tetrafluoropyridyl ligands^[16]plays

a key role not only for the stability but also in the formation of

the tetrameric or trimeric species. Even at elevated temper-

atures, no reductive elimination of a 4-(N-heterocycle)tetra-

fluoropyridine compound is observed, neither from 2a–c, 3a–

c, nor from 4–6.^[2]

Some of the Pd macrocycles synthesized could potentially

be used for host–guest chemistry.^{[12,15d,17,18]}Most of the known

palladacycles are cationic with multiple charges^{[7,8,12–15]}and

thus restricted to the recognition of anions or electron-rich

systems. The fact that the metallamacrocycles 3a–c, 5a, 5b,

and 6b are neutral compounds is therefore of particular

interest. They might be capable of coordinating neutral,

anionic, and cationic guests through p interactions, depending

on the substitution pattern of the heterocyclic spacer

units.^[12,15d,17]

In conclusion, we presented a new strategy to access

organometallic macrocycles. In this approach, fluoro ligands

are replaced by heterocyclic building blocks, leading to

molecular squares and triangles. We believe that it will be

possible to expand this reaction route to other transition-

metal fluorides. Our work also reveals that other organome-

tallic macrocycles bearing electron-withdrawing anionic

carbon ligands such as C₅F₄N should be accessible.^[8e]

Figure 4. Crystal structure of 5b. Thermal ellipsoids are set at the 50%

probability level. H atoms and iPr groups have been omitted for clarity.

Selected bond lengths [] and angles [8]: Pd1–N2 2.091(3), N2–C19

1.344(5), N5–C19 1.331(5); N2-C19-N5 115.3(3).

Received: July 27, 2007

Published online: October 10, 2007

8676 www.angewandte.org

ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Angew. Chem. Int. Ed. 2007, 46, 8674 –8678

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Angewandte

Chemie

h) D. Noveski, T. Braun, S. Krückemeier, J. Fluorine Chem. 2004 ,

Keywords: fluorine · fluoro complexes · macrocycles ·

metallacycles · palladium

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[9] Data for the X-ray structure analyses. All structures were solved

by direct methods and refined with full-matrix least-square

methods on F²(SHELX-97).^[19,20]3a: C₆₈H₉₆F₁₆N₁₂P₄Pd₄, M_r=

1935.05, 0.28 0.20 0.10 mm³, tetragonal, space group P4/n, a =

17.4280(3), c = 14.8970(3) , Z = 2, V= 4524.74(14) ³, 1_calcd

1.420 gcm^À3, 2q_max= 54.948, Mo_Karadiation (l = 0.71073 ), T=

100(2) K, 55351 reflections collected, 5175 were unique (R_int

0.049), Nonius KappaCCD diffractometer, multiscan absorption

correction (min/max transmission 0.7813/0.9130), m =

0.927 mm^À1, final R₁= 0.0452, wR₂= 0.0879 (all data), R₁=

0.0352, wR₂= 0.0839 [4241 reflections I₀> 2s(I₀)], residual

electron density + 0.703/À0.908 e^À3. 3b: C₈₈H₁₁₆F₁₆N₁₆P₄Pd₄,

M_r= 2251.45, 0.17 0.14 0.10 mm , triclinic, space group P1,

a = 10.4617(7), b = 14.9170(12), c = 17.3570(8) , a = 67.107(4),

b = 80.368(4), g = 87.575(4)8, Z = 1, V= 2459.2(3) ³, 1_calcd

1.520 gcm^À3, 2q_max= 508, Mo_Karadiation (l = 0.71073 ), T=

100(2) K, 46456 reflections collected, 8567 were unique (R_int

0.1131), Nonius KappaCCD diffractometer, multiscan absorp-

tion correction (min/max transmission 0.8667/0.9184), m =

0.866 mm^À1, final R₁= 0.1331, wR₂= 0.1565 (all data), R₁=

0.0678, wR₂= 0.1281 [5089 reflections I₀> 2s(I₀)], residual

electron density + 0.842/À0.952e ^À3. 3c: C₁₁₆H₁₃₂F₂₀N₁₂P₄Pd₄,

M_r= 2623.82, 0.30 0.08 0.06 mm³, tetragonal, space group I4₁/

a, a = 33.001(2), c = 11.0402(6) , Z = 4, V= 12023.4(13) ³,

1_calcd= 1.449 gcm^À3

2q_max= 50.58, Mo_Karadiation (l =

0.71073 ), T= 100(2) K, 86185 reflections collected, 5412

were unique (R_int= 0.3991), STOE IPDS 2T diffractometer,

numerical absorption correction (min/max transmission 0.8121/

0.9578), m = 0.724 mm^À1, final R₁= 0.2689, wR₂= 0.2066 (all

data), R₁= 0.0857, wR₂= 0.1482[5412reflections with

2s(I₀)], residual electron density + 1.270/À0.473 e

I₀>

5b:

À3

C₆₄H₉₀F₁₂N₁₅OP₃Pd₃, M_r= 1725.62, 0.16 0.14 0.02 mm³, tri-

clinic, space group P1, a = 10.6090(2), b = 15.3420(3), c =

[4] a) S. L. Fraser, M. Y. Antipin, V. N. Khroustalyov, V. V. Grushin,

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24.7640(4) , a = 77.3280(11), b = 77.7970(10), g = 81.8330(9)8,

Z = 2, V= 3824.24(12) ³, 1_calcd= 1.499 gcm^À3, 2q_max= 508, Mo_Ka

radiation (l = 0.71073 ), T= 220(2) K, 75989 reflections col-

lected, 13450 were unique (R_int.= 0.058), Nonius KappaCCD

diffractometer, multiscan absorption correction (min/max trans-

mission 0.8774/0.9834), m = 0.839 mm^À1, final R₁= 0.0616, wR₂=

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CCDC-653977 (3a), CCDC-653978 (3b), CCDC-653716 (3c),

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ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.angewandte.org 8677

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Take advantage of blue reference links

&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&

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8678 www.angewandte.org

ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Angew. Chem. Int. Ed. 2007, 46, 8674 –8678

&&&&

&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&

&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&

&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&

Take advantage of blue reference links

&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&&

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