Metal-Containg and Metallosupramilecular Polymers and Materials

Chapter 17

Metallo Groups Linked to the Surface of Phosphorus-Containing Dendrimers *

*

Downloaded by UNIV OF SYDNEY on August 12, 2013 | http://pubs.acs.org Publication Date: March 23, 2006 | doi: 10.1021/bk-2006-0928.ch017

Jean-PierreMajoral ,Anne-MarieCaminade ,and Regis Laurent Laboratoire de Chimie de Coordination du C N R S , 205 route de Narbonne, 31077 Toulouse Cedex 4, France

This paper is a review concerning metallic derivatives linked to the surface of phosphorus-containing dendrimers, that are dendrimers possessing one phosphorus at each branching point. The synthetic aspects will be described first, concerning in particular the complexation of transition metals (Fe, W, Rh, Pt, Pd, Ru) by monophosphine or diphosphine end groups, the grafting of metallocene derivatives (zirconocene and ferrocene), and the interaction with various clusters (Au-Fe, Au, Ti). Some applications of these metallo phosphorus dendrimers will be described in the field of materials science (modification of the surface of existing materials or creation of new materials), and in the field of catalysis (Stille couplings, Knoevenagel condensations, Michael additions).

230

© 2006 American Chemical Society

In Metal-Containing and Metallosupramolecular Polymers and Materials; Schubert, U., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2006.

231

Introduction 1,2

The grafting of metallic derivatives to the surface of dendrimers is an area of current and constant interest, mainly driven by the catalytic properties of some of the resulting metallo-dendrimers. * In many cases, the complexation of metals has been conducted with organic dendrimers; however, many examples exist also concerning metallic derivatives linked to the surface of phosphoruscontaining dendrimers, that are dendrimers having one phosphorus atom at each branching point. " This paper is a review concerning phosphorus dendrimers in which metallic derivatives are linked to their periphery, mostly but not exclusively through phosphine end groups. In most cases, the internal structure of these dendrimers is constituted of OC H4CH=NNMeP(S) linkages, emanating from a afunctional (P=S) or hexafunctional (N3P3) core. In most cases, the complexing end groups are constituted either of phosphines or diphosphines. The structure of the first generation of three of the most widely used phosphorus dendrimers is shown in Figures 1 and 2; these compounds were synthesized up to the tenth generation for dendrimers 1-G„ (3072 phosphines), up to the fourth generation for dendrimers 2-G„ (48 diphosphines), and up to the fifth generation for dendrimers 3-G„ (192 phosphines). 3,4

5


9

8

10

6

11

12

11

Figure 1. Monophosphine and diphosphine end groups linked to the surface of first generation ofphosphorus dendrimers built from a afunctional core.


232 Ph P-CH Μβ-Ν. Η H î > 0 . ·? Me 2

H C-PPh -γ^Ν-Ν-Μ· Me\.0\J H

2

2

Ν5

2

u

H, M e

P" P-C 2

M e u

Ph P-C 2

Q

S"O-0.

,/>0

D

Ρ Ν Ν ί

Me

2

J»C0

-CK

X

2

u

^

'Me H, ,C-PPh

N*N ^

ν

H

0

^CH

2

*

¥·.0-0*8

δΟ-0-Ρ Ρ-0·Ο-0=Ν·ΝΡ. ^ ,CH^

2

H

2

H. 2

.L ^° - - -Me N

C

N


M, Me

N

.- ;g -PP^ Me N

1

2

Figure 2. Monophosphine end groups linked to the surface of the first generation of a phosphorus dendrimer built from a hexafunctional core.

Compounds 1-G„ and 3-G„ afforded the first examples of large phosphine complexes linked to the surface of any type o f dendrimers. In the first part of this review, the grafting of transition metals, metallocenes, and organometallic clusters using various types of end groups will be described; then, some properties o f these métallo dendrimers will be discussed, particularly in the fields of new materials and of catalysis. 11

Complexation of transition metals The advantage of phosphines as end groups is that a single type of dendrimer may serve as complexing agent for different types of metals, as illustrated in Scheme 1 for metals of groups 6, 8, and 9. In this Scheme, as well as in several other schemes throughout this review, Dendri indicates that the internal structure is constituted of OC H CH=NNMeP(S) linkages. First experiments were conducted with common M(0) derivatives [Fe(CO) and W(CO) ], then, with two types of Rh(I) derivatives. In most cases, experiments were carried out at least up to the fourth generation, and in some cases up to the fifth or sixth generation. For the largest compounds, 192 Rh(acac)(CO) groups have been linked to the surface of dendrimer ld-G for the 1-G series, whereas 96 RhCl(COD) have been complexed by dendrimer 3 c - G , which is the largest compound of series 3-G„. In all cases, the complexation goes easily to completion within a few hours at room temperature, as show by P N M R . 6

4

4

5

13

6

n

4

14

3 ,


233 Fe (CO) 2

Dendri-(0-^-C=N-NP-f O - ^ O N - N

9

/

e ( C 0 ) 4

1a-G„: core = P(S) up to G 3a-G|i core = N P 5

3

3

1b-G„: core = P(S) up to G Zb-G^: core = N P 4

1-G » 3 . G H

3

2/x

3

n

/

[RhCI(cod)l

2

Me /

u

Me

\>

Dendrt4o^C= -N-p/o-^C=N-N^^ N

J

1c-G : core = P(S) up to G 3c-G : core = N P up to G Me\ n


C , ( C O d )

4

n

3

3

4

Rh(acac)(CO)

2

\^JT

J t \ ^ H ^-PPh

2

1d-G : core = P(S) up to G n

Me>

6

Scheme L Complexation of transition metals by monophosphine end groups. Only the most external layers are shown in all cases.

The complexation properties of phosphino groups linked to another type of end groups were also tested with Fe(CO) and W(CO) (Scheme 2). This series of compounds possesses several types of functions at each end groups, besides the phosphine complexes: allyl groups, secondary amines, and tertiary amines, illustrating the concept of "multiplurifunctionalization '. 15

4

5

1

Fe (CO) 2

16

9

0C=N-N-|C -^ -P Ph 4a-G : up to generation 2 N

F e { C O ) 4 j

2

• / _ Η *? Dendri4oQ-C=N-N-pC β

H

V-

n

N

N

-PPh /x 4-G : core = P(S) up to generation 7 / Me HN-^ Me HN W(CO) THF Dendri|o-(]}-C=N-N-pC. '^ 2

n

5

N

ι

H

\

Se

4b-G : up to generation 2

W(CO)

5

V-p

ν

Ph

2

n

Scheme 2. Complexation of Fe and W derivatives by another type of monophosphine end groups.


234 In the previous examples, all end groups of the dendrimers are identical, whereever their locations are on the surface. However, some special dendrimers exist, in which part of the surface possesses one type of end groups, and another part possesses another type o f end groups. These special dendrimers, called "surface block", are generally built by association of two different dendrons (dendritic wedges) by their core or on a core. However, the diblock compound 5G\G was synthesized by the step-by-step growth on one side to graft ammonium groups, then on the other side to graft phosphino groups. Finally, iron is complexed by the phosphines, on one third of the end groups. 17

Q

18

MePh P=N /

Me/"


2

,

Me.

^

\Ph P-C

=

2

JJ

jζ

2

"

\\

5? 4 O H Q - C N - N . K ^ N H E I N

N

2

I Fe2(CO) ® NHEt I _ Η ""Η ;P O-Q-C N- -P-N^θ E

t

Ph Ph C=N-N-P10-4 >C=N Ν 2-G„ core = P(S)

2

\ \

}

I P»CI (cod) 2

Dendrlk)-Q-C=N-N-PÔ-Q-C=NN m Vpy

2a-G„:uptoG

3

P

h

c

IJ

î

Scheme 4. Complexation of platinum(Il) by diphosphine end groups.


235 The same type of experiment was carried out with PdCl . In this case, a real organometallic chemistry was developed on the surface of the dendrimer, as illustrated in Scheme 5 . A n easy halogen exchange occurs when 2b-Gt is reacted with K B r , whereas halogen exchange and alkylation of palladium occur simultaneously with the Grignard reagent MeMgBr. A monomethylation is also observed with Cp ZrCI , leading to complexes 2e-G„ (n < 3). The presence of Pd-Me bonds allowed to carry out C O insertion; a second insertion was observed using norbornene, which took place readily in the Pd-acetyl bond, leading to 2gG„. 2

12

2

2


S=P

/

—« H

ν \ PdBr (cod) 2

2 d

_

V* I G

5

' i

/

_

X

2c-Gi

Ô

H

.Me\\ MeMgBr

/κ

3

Ph Ph

2

2

^

/

e

_

Ph rP* .Br\\ 2

H

4

S

Ph

I

Ph

KBf

PdCI (cod) 2-G„ • Dendrl core « P(S)

2 / 3

2

2

2

2b.G 2b-G 1(

PdMeCI(cod)

jcp ZrMe

3

2

P h 2

2

/ /erv Η ψ Ι /κ .Me\\ • DendrHO-4>C=N-NP40-4>C N-N W s

2e-G :uptoG

%

|

p

&2 Ph Ο / /=v H >Me\\ DendrHO-^C=N-N-P40-Q-C=N-N ,Pd 1j n

3

1 ê / f

2f-e :up.oG n

/

|

3

H

»

[

2

r

N o r b 0 f n e n e

K

«*

_

Dendrl4o-Q-C=NN f \ o { > C N - N

>d

s

\

S

2g-G :uptoG n

^

H

Ph P n

2

2

Ο

J / 2

/

x

Scheme 5. Complexation of palladium derivatives by diphosphine end groups.

12

Dendrimers 2-G„ were also used to complex Rh(acac) and ruthenium hydride derivatives (Scheme 6). In the latter case, two different behaviors were observed for the resulting complexes, depending on the nature of the hydrido complex. In the case of 2i-G„, the complex is stable, whereas dendrimers 2k-G„ exist as a mixture of isomers, depending on the relative position of PCy3, both hydrides and H - H ligands. Furthermore, a fluxional behaviour is observed. However, in both cases addition of C O gives the analogous complexes 2 j - G and 21-G„ in which either one PPh or the dihydrogen is replaced by CO. 19

n

3


236 Rh(acac){cod)

JRuHjiPPhsiJ

/

H

Me/

/

Η

""β /

\

2J.6

S

\

f

"Dendrl4o^C=N-NP4o-Q-C:N-N^

\ Downloaded by UNIV OF SYDNEY on August 12, 2013 | http://pubs.acs.org Publication Date: March 23, 2006 | doi: 10.1021/bk-2006-0928.ch017

n

Η

2Μ5

η

S\

ρ

\

ΡΗ

2

Η

^ < ^

)

3

Ph H

7

2

Ph Η Η [RuH (H ) (PCy ) J / Η Me / Η ^ρ, | Ε » DendrHOC=N-N|^0e^ Ph H 2k-G 2

2

2 2

r

Γ

\

3 2

2

n

Core = P(S) up to G in all cases

Ph CO / _ H Me / _ H /-Ρ^Γ*.-^ \ Dendri40C=N-NP40^C.-"^^^ -P* H 2

3

Scheme 6. Complexation of rhodium and ruthenium derivatives by diphosphine end groups.

Other bidentate ligands have been grafted to the surface of phosphorus dendrimers, in particular P , N ligands, which are able to complex P d C l . These reactions have been applied both to a dendrimer leading to 6 a - G , , and a dendron leading to 7 a - G (Scheme 7). 2

20

21

2

Scheme 7. Complexation of PdCh by bidentate end groups.


237

Metallocene derivatives Besides phosphino complexes, metalloeene derivatives constitute another important way to graft organometallic derivatives on the surface of dendrimers. Concerning particularly phosphorus-containing dendrimers, two types of metallocenes have been used: zirconocenes and ferrocenes. The first example concerns the formal [3+2] cycloaddition of 2-phosphino-lzirconaindene 9 with various aldehydes, for example as when applied to the aldehyde-terminated dendrimers 8 - G and 8 - G (Scheme 8). These reactions lead to unusually stable anionic zirconocene complexes on the surface of dendrimers 8a-G and 8 a - G , which constitute the first polyzwitterionic métallo dendrimers. 22,23

4

8

24


4

8

Scheme 8. Grafting of zirconocene derivatives leading to polyzwitterions.

Ferrocene derivatives are the most popular metallocenes, mainly due to their high thermal stability and their well-behaved electrochemical properties. They are linked to the surface of phosphorus-containing dendrimers through a phenol linkage, which reacts in basic conditions with P(S)C1 end groups. First experiments were carried out with nonchiral ferrocenes, leading to dendrimers 10a-G„ (n < 9). The largest compound in this series (10a-G ) possesses theoretically 1536 ferrocenyl end groups (Scheme 9). Among numerous types of end groups, these ferrocenes afford one of the highest thermal stability to phosphorus-containing dendrimers (376 °C for 10a-G ). Several types of enantiomerically pure ferrocenyl compounds having a planar chirality were also grafted to the surface of phosphorus-containing dendrimers. In some cases, these ferrocenes bear another function, such as an aldehyde (10f-G„) or a phosphine protected by borane (10c-G„), which can be deprotected by D A B C O to afford 10d-G (Scheme 9). A l l these reactions have been carried out at least up to the ninth generation, and even up to the eleventh generation for 10e-Gu. Study of the chiroptical properties within each series 2

25

9

26

5

27

n


238 shows that the value of the molar rotation divided by the number of chiral end groups versus generation is a constant. Concerning electrochemical properties, in all cases dendrimers 10a-f-G exhibit a single oxidation wave, corresponding to a multielectronic transfer of equivalent and electrochemically independent ferrocenyl end groups; this fact confirms the absence o f steric hindrance, even for high generations. Furthermore, changes in solubility are observed in the oxidation state, leading to stable modified electrodes. Indeed, the multiferroceniums obtained upon exhaustive electrolysis at controlled potential deposit onto the Pt electrode surface, forming a blue conducting film.


n

Me DendrHO-^J-C=N-NPtOH "•o-O-g

"2

ft

N

^

n

n

DendrlÔ-^C=N-NPCI J — 2

10-G

H21

10a-6„R = H 10b-G R = Me 10c.G R = P h P B H 3 — j

x

/

2

_ H *? / e

P h

D A B C 0

2 *w' P

Dendri+O^C=N-Np(o-Q-C 7^ H S\ \ 10d-G x

2

n

n

NaO R* core = P(S) up to Gg

10e-G R = Me, core = P(S) up to G 10f-G R = CHO n

u

n

Scheme 9. Grafting offerrocene derivatives on the surface of dendrimers.

Clusters as end groups. Toward materials. Dendrimers, and in particular phosphorus-containing dendrimers, have been used in many cases in the field of materials science, either to modify the surface of existing materials, as illustrated above by the modified electrodes, or to create new materials. This latter field can be illustrated by the interaction of organometallic clusters with dendrimers. In a first attempt, the clusters were created on the surface of phosphorus dendrimers, starting from compounds l e G„ and 3e-G„ terminated by Au-CI end groups. These end groups were particularly useful for imaging dendrimers by transmission electron microscopy ( T E M ) , and were able to undergo a reaction of the Au-Cl linkages, as shown by 28

11


239 the reaction with C p Z r M e (Scheme 10). Thus, the reaction with the monoanionic complex 11, and the dianionic complex 12 leads to dendrimers IgG„ and l h - G , possessing neutral AuFe clusters or monoanionic AuFe clusters as end groups. 2

2

B

2

3


29

Scheme 10. Reactivity ofAu-Cl end groups, and characterization by electron microscopy. Synthesis of Gold-Iron clusters from these Au-Cl end groups.

The second type of interaction between clusters and phosphorus-containing dendrimers was carried out with the thiol terminated dendrimer 11-G„, in order to take profit of the known propensity of thiols to form strong bonds with gold. The result of the interaction gives microcrystals (Scheme 11), which were shown by T E M , small- and wide-angle X-ray diffraction ( S A X R D , W A X R D ) IR spectroscopy, and energy-dispersive X-ray spectroscopy (EDX) analyses to be constituted for the first time of naked A u clusters, which have lost both all the PPh and C l ligands. A thin amorphous shell, presumably made of dendrimers, protects the microcrystals and induces their growing, as shown in Scheme 11. These crystals of naked Au s clusters might be candidates for future nanoelectronic devices working with quantum dots. 5 5

3

5

30



240

Scheme IL Synthesis of nanocrystals of nakedAu . TEM image of a monocrystal ofAuss, enveloped by an amorphous layer of ll-G . 55

4

The third experiment concerning clusters led to hybrid organic-inorganic materials, obtained by the assembly of two nanobuilding blocks with welldefined structures, that are dendrimers 12a,b-Gi and the titanium oxo cluster Tii60i (OEt) (Scheme 12). The hybrid interface is obtained by transalcoholysis with 12a-G], and nucleophilic substitution affording bridging carboxylates with 12b-G,. In both cases, 0 M A S N M R , FTIR, and X-ray diffraction show that the integrity of the titanium oxo bricks is preserved, and that the dendrimers act like spacers in the array of clusters, to form a long range ordered structure. 6

32

, 7

31,32

Scheme 12. Synthesis of mesostructured solids via the interaction of dendrimers with titanium clusters.


241 Larger dendrimers 12b-G and 12b-G were used in sol-gel processes with titanium alkoxydes (Ti(OEt) , Ti(OiPr) , Ti(OBu) ), and Ce(OiPr) . The carboxylic acid functions of the dendrimers act as anchoring sites for the development of the inorganic network. Thermolysis of the hybrid solids at 450°C induces the decomposition of the organic constituent (the dendrimer), and affords sponge-like mesostructured materials. 5

7

4

4

4

4

33


Catalytic properties. Métallo dendrimers might be ideal catalysts that combine the advantages of both homogeneous and heterogeneous catalysis, because they are generally easily soluble, and their large size allows an easy recovery. Various phosphoruscontaining dendrimers have been used as catalysts, concerning metals linked to the surface o f these dendrimers, mainly three types o f catalytic reactions have been tested: i) Stille couplings using the palladium derivatives 2b-G„ and 6aG i , ii) Knoevenagel condensations using the ruthenium derivatives 2i-G„, and iii) Michael additions using also 2i-G„. In most cases the catalysts can be reused at least twice. Despite numerous data, no rule can be deduced concerning the efficiency of the catalysis using dendrimers compared to monomers. A s shown in Scheme 13 for various Stille couplings, the efficiency of the conversion using dendrimer 6a-G compared to the corresponding monomer is either worse (case a), identical (case b), or better (case c). 34

3S

2 0

35

3S

f

20

/

à

u

Me

H

Monomer CI Pdl£jO 2

F c6-I 3

r

rJ \ '

Ο

\ Dendrimer Sa-Gi

Catalyst

*: % of catalyst expressed in molar percent of metal

Rate of conversion ( H NMR) Rate of conversion ('H NMR) Rate of conversion ( H NMR) tsioo tnoo b ) i î î î « " I 80 J-60 5-60 * Monomer 40 g 40 * Monomer • Dendrimer 6a-Gi ICS * ο 20 • Dendrimer Ga-Gj 5 20 * 0 * 06 HoursO HoursO 2 4 6 8 10 12 14 16 HoursO 1

1

e l

l t e

w

Scheme 13. Various Stille couplings catalyzed by a monomer or dendrimer 6a~Gi, Rate of conversion measured by HNMR l


242

Conclusion Numerous examples concerning the presence of metallic derivatives as end groups of phosphorus-containing dendrimers have already been described. Depending on the type of these end groups, the metal induces particular properties such as an increased thermal stability, various uses in the field of materials science, or in catalysis. Concerning this latter point, work is in progress to develop enantioselective catalyses using métallo phosphorus dendrimers decorated with chiral ligands.


36

References 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

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Metal-Containg and Metallosupramilecular Polymers and Materials

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