Polymer and metal oxide supported alkali metal naphthalenides: Application in the generation of lithium and sodium reagents

Article abstract of DOI:10.1016/S0022-328X(97)00543-3

Highly coloured paramagnetic polymer supported lithium 5,5′ and sodium 6,6′ naphthalenide complexes have been prepared from the reaction of THF solutions of lithium and sodium biphenylide with polystyrene bearing -CH₂SiMe₂(C₁₀H₇) groups. Treating chloropropyl functionalised silica, alumina and titania surfaces with H₃Al · NMe₃ or H₃Ga · NMe₃ afford hydroxyl depleted surfaces. Successive treatment with lithium biphenylide, 1-(chlorodimethylsilyl)naphthalene and an alkali biphenylide affords supported alkali naphthalenide complexes which generate in high yield lithium and sodium reagents when treated with a range of organic halides, nitriles and phosphates, as found for 6,6′ and 7,7′.

Full text of DOI:10.1016/S0022-328X(97)00543-3

Journal of Organometallic Chemistry 550 Ž1998. 283–300
Polymer and metal oxide supported alkali metal naphthalenides:
1
application in the generation of lithium and sodium reagents
a
b,)
Tania R. van den Ancker , Colin L. Raston
a
Faculty of Science and Technology, Griffith UniÕersity, Nathan, Qld. 4111, Australia
b
Department of Chemistry, Monash UniÕersity, Clayton, Melbourne, Vic. 3168, Australia
Received 26 February 1997
Abstract
X
X
Highly coloured paramagnetic polymer supported lithium 5,5 and sodium 6,6 naphthalenide complexes have been prepared from the
reaction of THF solutions of lithium and sodium biphenylide with polystyrene bearing –CH SiMe ŽC H . groups. Treating
2
2
10
7
chloropropyl functionalised silica, alumina and titania surfaces with H AlPNMe3 or H GaPNMe afford hydroxyl depleted surfaces.
3
3
3
Successive treatment with lithium biphenylide, 1-Žchlorodimethylsilyl.naphthalene and an alkali biphenylide affords supported alkali
naphthalenide complexes which generate in high yield lithium and sodium reagents when treated with a range of organic halides, nitriles
X
X
and phosphates, as found for 6,6 and 7,7 . q 1998 Elsevier Science S.A.
Keywords: Polystyrene; Lithium reagent; Sodium reagent; Silica; Alumina; Titania; Alane; Gallane
1
. Introduction
have been studied, including naphthalene, biphenyl and
X
4
,4 -di-t-butylbiphenyl. In these reactions only small
The use of alkali metal arene radical anion com-
amounts of the by-product arene is present in the prod-
uct mixtures. Chromatography is still required, how-
ever, when pure compounds are needed. In this way,
reactions of several types of organic chlorides have
been investigated including chloroketals 9 , aryl chlo-
yP
q
plexes, ArH M , as soluble sources of metal in the
formation of organoalkali metal species from organic
halides is well established w1–5x with the early work
focusing on the use of lithium naphthalenide w1x. Many
radical anion derivatives of lithium have been prepared
in recent years which show potential in the synthesis of
w x
rides 10 , dichlorobutenes 11 and chloromethyl ethyl
ether 12 . The same approach has also been used in the
preparation of lithium complexes from trialkylphos-
phates w13x, nitrile complexes w14x alkyl phenyl sulfones
w x
w x
w x
X
alkyllithium reagents. Lithium 4,4 -di-t-butylbiphenyl
Ž
LiDBB
. w6x is particularly noteworthy in that while it
acts as a source of lithium, removal of the DBB by-
1
w x
5 , dialkyl sulfates 16 , and phenyl sulfides 15 . Such
w x w x
product is facilitated by its low volatility w3x.
reactions are usually carried out, under argon at low
temperatures at ca. y788C in a coordinating solvent,
whereby a solution of the organic reagent in THF for
example is added to a suspension of lithium in the same
solvent, to which a catalytic amount of arene has been
added. The mixture is then stirred for 0.5–12 h prior to
quenching with an electrophile. For reactions that are of
a Barbier-type, the electrophile is added to a lithium
arene slurry before addition of RX.
Another approach to overcoming the objection of
having solutions of the target organoalkali metal species
loaded with the arene by-product is the use of a cat-
alytic amount of the arene w7,8x. Here, the arene under-
goes electron transfer with bulk metal affording a radi-
cal anion complex which then reacts with RX with
regeneration of the arene to complete the catalytic cy-
cle. Various percentages 1–20% and types of arene
Ž .
A variety of new lithium complexes have been pre-
pared using arene catalysed reaction of organochlorides
)
Corresponding author.
1
with lithium, for example 2- 3-lithiopropyl -1,3-di-
Ž .
Dedicated to Professor Ken Wade on the occasion of his 65th
Birthday in recognition of his outstanding contribution to
organometallic and inorganic chemistry.
oxolane which offers a direct synthesis to g-lactones
when treated with carbonyl compounds w17x. Similarly,
0
022-328Xr98r$19.00 q 1998 Elsevier Science S.A. All rights reserved.

2
84
T.R. Õan den Ancker, C.L. RastonrJournal of Organometallic Chemistry 550 (1998) 283–300
a variety of alcohols, dienic alcohols, and cyanoxepanes
have been isolated from reactions of masked lithium
d-enolates w18x.
Another approach to overcome generating solutions
of organoalkali metal species loaded with arene is the
use of supported radical anion species. This is the theme
of the work described herein which investigates the
preparation of supported alkali metal naphthalenide
complexes and their utility in forming lithium and
sodium reagents. It is an extension of a preliminary
account of the synthesis of polymer supported alkali
metal naphthalenides and their reactivity with organic
complexes w1x and of our studies on polymer w19,20x and
silica w21x supported magnesium anthracene complexes
which afford arene free solutions of Grignard reagents
in high yield when treated with benzylic halides.
2
. Results and discussion
Scheme 1.
2
.1. Polymer supported alkali metal naphthalenides
Treatment of a THF slurry of the Grignard reagent of
X
ca. 1% crosslinked chloromethylated polystyrene 1,1
2.2. Metal oxide supported alkali metal naphthalenides
y1
Ž
1.20–1.34 and 4.11–4.15 mmol g Cl, respectively
with excess 1- chlorodimethylsilyl naphthalene, 2,
.
Ž
.
Reactions of ‘endcapped’ lithiopropyl silica
pared via reaction of ‘endcapped’ chloropropyl silica
and lithium biphenylide w21x
with the chlorosilane 2
afforded the silica supported naphthalene complexes as
Ž
pre-
X
yielded the naphthalene functionalised polymer 3,3 ,
Scheme 1, in greater than 95% yield based on weight
increase, IR studies and analysis for residual chlorine
content. Compound 2 was prepared by quenching 1-
lithionaphthalene with excess dichlorodimethylsilane
w22x.
.
X
X
pale cream powders 8, 9
with the corresponding metal biphenylide afforded the
8 , 9 . Subsequent reactions
Ž .
X
X
X
lithium 10, 11 10 , 11 or sodium 12 12 silica
Ž . Ž .
Reactions involving modification of the chlorometh-
supported silylnaphthalenide complexes, Scheme 2.
Loading of the naphthalene functionality was deter-
mined by the quantity of isolated LiCl by-product.
Analysis of silica supports 8, 9 showed the level of
ylated polystyrene were monitored by
i changes in
Ž .
nC – H bending mode of the methylene group w23x, dis-
yl
yl
placed from 1265 cm to 1254 cm on converting the
chloride to the silane, and ii the appearance of charac-
teristic absorption bands at 1253 and 847 cm
shoulder , assigned to Si–C stretching and Si–Me de-
y1
y1
Ž
.
loading was 0.85 mmol g
spectively.
and 1.19 mmol g , re-
yl
Ž
.
Silica supported aminonaphthalene 13 was prepared
by refluxing a mixture of silica, N-methyl amino-
propyl trimethoxysilane, 1-chloromethylnaphthalene and
formations, respectively w23x.
Ž
Lithium biphenylide 4 and sodium biphenylide 5
were chosen as the electron transfer reagents because of
.
triethylamine in a toluenermethanol mixture. ‘Endcap-
their low reduction potential
Ž
y2.70 V vs. SCE
.
rela-
ping’ was achieved by treating 13 with chlorotrimethyl-
tive to that of lithium naphthalenide
Ž
2.50 V vs. SCE
.
,
silane andror H AlPNMe , 14, 15 or H GaPNMe
Ž
3 3
X X
3
3
thus in principle facilitating transfer from the biphenyl
14 , 15
metal biphenylide afforded lithium 16, 17
.
. Subsequent reactions with the corresponding
X X
to naphthalene respectively w24x. Solutions of lithium
Ž
16 , 17
Ž .
sodium 18, 19 18 silica supported aminonaph-
.
or
X
biphenylide in THF were added to THF slurries of
X
polymers 3,3 resulting in the formation of red-brown
thalenide complexes, Scheme 3. Alumina and titania
supported aminonaphthalenide complexes were pre-
pared by methods similar to the silica supported mate-
rial, albeit with significantly lower loading levels, 0.38
paramagnetic mixtures
mer supported lithium naphthalenide 6,6 . Similarly,
g s2.0034, 2.0035 of poly-
Ž .
av
X
addition of a THF solution of sodium biphenylide to
X
y1
THF slurries of polymers 3,3 resulted in the formation
and 0.19 mmol g , respectively.
of red-brown paramagnetic solutions
Ž
g s2.0034,
For both the silyl and aminonaphthalene metal oxide
complexes uptake of the alkali metal depended on the
choice of ‘endcapping’. For metal oxide complexes that
av
2
7
.0035
.
of polymer supported sodium naphthalenide
X
,7 .

T.R. Õan den Ancker, C.L. RastonrJournal of Organometallic Chemistry 550 (1998) 283–300
285
Scheme 2.
were only ‘endcapped’ with trimethylsilyl groups, a
several fold excess of the corresponding biphenylide
was required to generated the metal complex, only then
in very low yield. Thus, these complexes are unsuitable
as reagents for generating organolithiumrsodium com-
plexes. In contrast, metal oxides ‘endcapped’ with alu-
arene complexes in approximately 75% yield, and these
were found to be suitable reagents for the generation of
organo alkali complexes on reaction with RX.
2.3. Preparation of lithium reagents
minium hydride, or
a
mixture of aluminium
Reactions of the organoalkali complexes were based
hydridertrimethylsilyl groups reacted with the corre-
on two different methods w1–5x. The first involved the
sponding biphenylide readily, generating the target metal
formation of the organoalkali, which was then quenched
Scheme 3.

2
86
T.R. Õan den Ancker, C.L. RastonrJournal of Organometallic Chemistry 550 (1998) 283–300
to give the target complex, Eq.
Ž
1
.
. The second reaction
Table 1
Comparison of the yield of lithium reagent using polymer supported
lithium naphthalenide 6,6 , with the use of lithium arene complexes
Žgenerated catalytically.
involved the quenching of the organoalkali complex in
Ž .
situ, a Barbier-type reaction, Eq. 2 .
X
RCl, THF
X
6
6
,6
,6
™
RLi
Ž
Ž
1
2
.
.
X
–
2LiCl, - 5,5
RCN or
Ž
RO.3PO, THF, Eq
X
™
RE
non Barbier-type
X
-
5,5
In a typical experiment
Ž
.
the or-
ganic halide in THF was slowly added over 20 min to a
THF slurry of the polymer or metal oxide supported
lithium naphthalenide at y788C. This resulted in the
dissipation of the red colour of the supported lithium
naphthalenide and the formation of an orange solution.
After stirring for a further 1–3 h the mixture was
filtered to give the arene free organoalkali species. In a
typical Barbier-type experiment a mixture of the organic
halide and source of electrophile in THF was slowly
added over 45 min to a THF slurry of the polymer or
metal oxide supported lithium naphthalenide at y308C
or 08C. The resulting pale yellow mixture was stirred
for 15 min, filtered, hydrolysed, then extracted into
Et O. Distillation afforded the corresponding quenched
2
complex, free of arene or other by-products. In all
cases, target concentrations of the resulting lithium
reagent were close to 0.1 M.
Examples of lithium reagents prepared using poly-
X
mers 6,6 and a comparison with the use of lithium
arene catalysed reactions are presented in Table 1. The
yield of derived lithium reagents are high and compara-
ble to those obtained in Refs. w7–18x. Each of the
a
Reaction with lithium powder with 5% 1-Žbenzyldimethylsilyl.naph-
thalene 28.
b
Reaction at y788C.
organic halides studied were quenched with
chlorotrimethylsilane, and the resulting product charac-
c
n
Treated with LiBu Ž1.1 molar ratio, y108C. prior to reaction with
the lithium polymer.
1
d
terised by H NMR and HPLCrMS.
Reaction at y308C, Barbier-type reaction, isolated yield of distilled
The chlorinated dioxolane, 20, was lithiated by the
reaction with 6 in THF at y788C. Subsequent quench-
ing with chlorotrimethylsilane afforded the correspond-
ing silylated complex in high yield. The lithium reagent
quenched product.
e
Ref. w7,8x.
f
Ref. w9x.
g
Ref. w10x.
h
Reaction with lithium powder with 5% naphthalene Žnot from
of the chlorohydrin, 21, was obtained in high yield after
literature..
n
i
Ref. w14x.
Ref. w13x.
2
1 was pretreated with LiBu in THF at y108C to
j
lithiate the alcohol residue, then treated with 6 at y788C.
Quenching with chlorotrimethylsilane gave the bis-sily-
lated complex in high yield. Alternatively, the chlorohy-
drin 21 can be di-lithiated directly using excess 6. In
this case the yield of the derived bis-silylated complex
is reduced to 60%. For complexes 20 and 21, an
increase in reaction temperature resulted in decreased
yields. This is presumably due to partial or total decom-
position of the intermediates via proton abstraction from
the solvent. However, when the reactions were carried
out under Barbier-type conditions, slightly higher tem-
peratures could be used with minimal effect on yields,
viz. 92% for 20, y788C, cf. 83%, y608C.
excellent yields, and quenching with chlorotrimethylsi-
lane gave pure silylated derivatives. Changes in temper-
ature had only slight effect on the yield of quenched
products, viz. 62% for 23, y408C cf. )95%, y788C.
For temperatures greater than y408C significant de-
creases in the yield were observed. Under Barbier-type
conditions reaction temperatures of up to y258C for 23
still gave moderate yields, 58%.
The reaction of the nitriles 24, 25 with 6 in THF at
y308C in the presence of chlorotrimethylsilane, gave
after hydrolysis tetramethylsilane and phenyltrimethylsi-
lane respectively, in moderate yields. Reducing the
The lithium reagents of the arylchlorides, chloroben-
zene 22 and 9-chloroanthracene 23 were obtained in

T.R. Õan den Ancker, C.L. RastonrJournal of Organometallic Chemistry 550 (1998) 283–300
287
reaction temperature did not improve yields. Increasing
the reaction temperatures on the other hand to 08C
reduced the yields slightly by ca. 2–5% . The lower
yield for 24 may be due to the high volatility of the
quenched complex. In the work by Guijarro and Yus
w14x, lower yields of the target compound were at-
Table 3
Yield of sodium reagent derived from the reaction of polymer and
metal oxide supported sodium naphthalene complexes and recycled
complexes
Ž
.
Ž
.
Supported sodium naphthalenide
% Yield of sodium reagenta
Cycle 1
Cycle 2
tributed to the formation of by-products arising from
preformed RLi deprotonating the unreacted nitrile. For
example, the reaction of acetonitrile with benzaldehyde
7
7
85–95
80–85
62–71
63–71
37–50
43–51
33–47
37–49
75–80
60–70
56–69
60–67
22–35
27–35
24–36
30–39
X
1
1
2
X
2
gave PhCH OH CH CN. Other by-products were also
Ž .
2
18X
18
isolated in these reactions including pinacol-type prod-
ucts w14x. Only the target complex and excess starting
19
X
1
9
materials
Ž
-5%
HPLCrMS
.
were isolated in the reactions in the
present study
Ž
.
.
a
Range over three separate runs.
Reaction of the trialkyl- 26 and triaryl- 27 phos-
phates with 6 in THF at y308C in the presence of
chlorotrimethylsilane, after hydrolysis led to the forma-
tion of ethyltrimethylsilane and phenyltrimethylsilane
respectively in high yields. These products are being
isolated upon distillation from reaction solvents. In these
reactions, only one of the alkyl or phenyl groups of the
starting phosphate is converted to the lithium reagent.
The yields represent isolated yields after flash chro-
matography based on starting material. Changes in the
reaction temperature such as an increase to 08C, or
decrease to y788C, did not change the yield of product
significantly. However, a decrease in the reaction tem-
perature required an increase in reaction time, e.g. 26
ded water . The lithium aminonaphthalenide complexes
.
gave lower yields of the lithium reagents. The alumina
and titania supported complexes in general gave lower
yields of the organolithium reagents.
2.4. Preparation of sodium reagents
The sodium supports were tested for their ability to
form natriobenzene, Table 3. The polymer supported
sodium naphthalenide is more effective than the corre-
sponding metal oxide complexes. Reactions of the
sodium polymer supports were carried out using the
same procedure as described for the lithium analogues
whereby a solution of the halide was added to a slurry
of the support in THF at the y788C. Addition of the
halide resulted in the dissipation of the red colour of the
supported complex and the formation of an orange
solution of the sodium reagent which could be separated
from the spent polymer by filtration.
reaction time at y788C 3.5 h
85% , 08C 1 h 75%
Metal oxide supported lithium naphthalenides were
80% , y308C 2.5 h
Ž .
Ž
.
Ž
.
.
also studied for their ability to form lithium reagents,
Table 2. ‘Endcapping’ using chlorotrimethylsilane is
inadequate whereas ‘endcapping’ using alane, as the
trimethylamine adduct, H AlPNMe , gave a supported
3
3
lithium complex effective in generating lithium reagents.
The alane is more effective in removing residual hy-
droxyl groups and water, thus, giving the complexes
more stability towards decomposition and loss of lithium
i.e., lithium reacts with the silica only to form the
radical species and not with residual silanols or embed-
The sodium supported complexes tend to be less
stable than the corresponding lithium complexes, and
not surprising they often decomposed during the addi-
tion of the reactant, resulting in reduced yields, or no
sodium reagent formation. Similarly, the generated
sodium reagent often decomposed prior to the reaction
with the source of electrophile. It was therefore more
successful to conduct these reactions under Barbier-type
conditions which resulted in yields only slightly lower
than those obtained from the lithium reagent. Decompo-
sition of the reaction products most likely arises from
proton abstraction from the solvent increasing with
increasing temperature.
Ž
Table 2
Yield of lithium reagent derived from the reaction of metal oxide
supported lithium naphthalene complexes, and recycled complexes
% Yield of lithium reagenta
Metal oxide supported
lithium naphthalenide
Cycle 1
Cycle 2
8
8
9
9
1
1
1
1
80–85
84–88
80–85
82–85
50–56
53–56
50–54
51–58
78–83
79–84
79–81
79–83
40–44
45–50
38–42
40–49
X
2
.5. Recycling of polymers and metal oxides
X
X
6
6
7
7
The spent polymers 3,3 were tested for recycling
X
X
potential. After quenching the polymers with chloroben-
zene, the resulting lithium complex was filtered from
the spent polymer. The polymer was then collected and
washed with THF and loaded with lithium biphenylide
a
Range over three separate runs.

2
88
T.R. Õan den Ancker, C.L. RastonrJournal of Organometallic Chemistry 550 (1998) 283–300
as before, yielding a deep red polymer, which was
treated with chlorobenzene and the procedure repeated,
Table 4. Overall, the uptake of 4 and the yield of
lithium reagent obtained only differed slightly over
successive cycles. The inability of the recovered poly-
mers to consume the same amount of 4 as polymers in
earlier cycles is due to ‘poisoning’ of the active sites
within the polymer matrix through the formation of
dihydroanaphthalene moieties. This could arise from
proton abstraction by the radical anion centres from the
solvent during washings to remove 4 see below .
Ž .
The spent metal oxide supports were tested for recy-
cling ability, Tables 2 and 3. After quenching the
polymers or metal oxide supported lithium or sodium
naphthalenides with chlorobenzene, solutions of the re-
sulting sodium complex were filtered from the macro-
molecule. The spent macromolecules were then reloaded
with lithium or sodium, treated with chlorobenzene and
the procedure repeated. Clearly metal oxide ‘en-
dcapped’ with alane is the preferred material for recy-
cling purposes.
Scheme 4.
2
.6. Model compounds
thalene complex 31 which has been characterised by
1
13
29
FTIR, HPLCrMS, and H, C, Si NMR. This reac-
In an attempt to model the reaction of the function-
tion models that of the polymer supported complexes,
X
X
alised polymers 3,3 and 4,4 , 1-
naphthalene 28 was prepared by treating benzyl magne-
sium chloride with 2 in Et O. Reaction of 28 with
lithium or sodium metal yielded a deep green paramag-
Ž
benzyldimethylsilyl
.
X
X
whereby treatment of the polymers 6,6 , 7,7 with water
in THF results in the formation of a new material
X
2
assigned as the dihydronaphthalene polymer 32,32 , Eq.
3 . Formation of dihydronaphthalene species is com-
Ž .
netic solution of Li
THF.n 29,
g s2.0028
silyl naphthalene
Ä
1-
Ž
benzyldimethylsilyl
and Na 1- benzyldimethyl-
30, g s2.0028 , respec-
naphthalene -
. 4
monplace when alkali naphthalenides are treated with
water or alcohols, or by proton abstraction from the
Ž
Ž
.
Ä Ž
av
4
.
Ž
THF
.
Ž
.
n
av
w x
Ž
.
reaction solvent 25 . Substituted mono- or bis- dihy-
dronaphthalene complexes can also be formed upon
reaction with alkyl halides w25x.
tively, Scheme 4. Complexes 29 and 30 were also
prepared by the reaction of 28 with THF solutions of 4
and 5 respectively. The reaction of 29 or 30 with
chlorobenzene or 9-chloroanthracene both yielded the
corresponding lithium or sodium complexes.
Treatment of the lithium or sodium naphthalenide
complexes 29 or 30 with a solution of water in THF,
Scheme 4, resulted in the formation of a dihydronaph-
3
Ž .
Table 4
Uptake of lithium biphenylide, 4, by naphthalene functionalised
X
polymers 3,3 and yield of the lithium reagent from the subsequent
reaction with chlorobenzene in THF at ca. y788C, entry 1, and
recycling of the recovered polymers, entry 2, and then repeating this
process and recycling the recovered polymer, entry 3, etc.
Cycle
Addition of 4
Ž% theoretical.
% Lithium reagent
formation
2.7. Characterisation
All supported complexes were analysed using CP
a
X
X
3
3
3
3
1
3
29
110b
110b
MAS NMR C and Si , XPS, ESR and FTIR. NMR
Ž .
1
2
3
4
93–97
91–95
89–94
88–92
93–95
89–95
87–93
87–92
29
100
100
95
95
95
90
The Si CP MAS NMR spectra of the naphthalene
functionalised polymers 5 and the recycled material
from the lithiation reaction are shown in Fig. 1. The
spectra of 5 exhibits a single resonance at d y3.9 ppm;
a second resonance at d q4.9 ppm is subsequently
a
Range over three separate runs.
b
)
100% added as a result of some hydrolysis.

T.R. Õan den Ancker, C.L. RastonrJournal of Organometallic Chemistry 550 (1998) 283–300
289
observed on recycling which can be compared to the
spectrum of 32. The compound derived from the prod-
uct of 6 and water and has a resonance at d q5.0 ppm
and a lower intensity resonance at d y3.9 ppm, Fig. 1.
The former is attributed to the silicon of the dihydron-
aphthalene, while the latter is attributed to unreacted
starting material. Thus, for the recycled polymer the
latter is indicative of the formation of dihydronaphtha-
corresponding to the methylene carbon centres w29,30x.
29
A
Si NMR resonance at d y45 to y70 ppm corre-
sponds to the silicon bearing the propyl group. Subse-
quent trimethylsilyl ‘endcapping’ generates a new reso-
nance at d 8.0 ppm, as well as a new resonance in the
1
3
C NMR spectrum at dy0.1 ppm w24x. Functionalisa-
tion with silylnaphthalene generates a broad aromatic
resonance at d 127.9 ppm with reduction in the reso-
lene moieties. Similarly, for the higher loading polymer
nance at d 46.0 ppm
groups , Fig. 2. A large resonance at d 17.3 ppm is
Ž
residual unreacted ClCH2–
X
5
a single resonance is observed at d y3.5 ppm, and a
.
second resonance at d q4.7 ppm in the spectra of the
assigned to the carbons attached to the silicon function-
ality, –CH SiMe . Similarly, a new small resonance in
2
9
X
recycled material. Si CP MAS of 32 shows two
resonances, a dominant one at d q4.7 ppm correspond-
ing to the dihydronaphthalene polymer and a lower
2
3
2
9
the Si NMR spectrum at d 10 ppm is due to this
silicon functionality. This resonance is not always seen,
the intensity depending on a variety of factors including
loading level, NMR collection time and signal to noise
ratio.
X
intensity resonance at d y3.4 ppm corresponding to 5 .
The analogous spectra for recycled and water quenched
X
polymers from the sodium complexes 7,7 are the same
as the lithium polymers, with differences in chemical
Similar results were obtained for the corresponding
alumina and titania silylnaphthalene supports. Reso-
nances assigned to the functionalities on the support in
shift of F0.1 ppm.
2
9
Si CP MAS NMR has been used to identify the
1
3
average structure of the surfaces by studying the shifts
the C CP MAS NMR for the alumina and titania
complexes did not shift significantly compared to the
silica derivatives. For many of the complexes, however,
the signal corresponding to the trimethylsilyl ‘endcap-
ping’ was either very small, or could not be detected.
Similarly, the resonances assigned to the aromatic car-
bons of the naphthalene functionality were very weak
for the titania complexes. Shifts corresponding to the
of the various substituents on surfaces w26–29x. Succes-
sive step in the preparation of metal oxide silylnaphtha-
lene complexes, the reaction products were charac-
1
3
29
terised by C and Si CP MAS NMR spectroscopy.
Successive reactions are characterised by new reso-
1
3
29
nances in both the C and Si CP MAS spectra as
expected by the attached functional groups.
2
9
Chloropropyl functionalised silica has three distinct
C NMR resonances at d 10.0, 26.5, and 46.0 ppm
functionality in the Si CP MAS NMR for the alumina
and titania complexes did not shift significantly com-
pared to the silica derivatives.
1
3
Aminonaphthalene silica has four different carbons
corresponding to the silylating agent w31x, which were
1
3
easily identified in the C NMR spectrum at d 10.3,
2
0.7, 34.3, 52.6 ppm, with a broad resonance at d 130.9
29
representing the aromatic functionality. Si NMR reso-
1
3
nances were at d y50 to y75 ppm. A separate
C
NMR resonance for the methylene group attached to
naphthalene was not evident, and most likely coincides
with the N–Me resonance at d 34.3 ppm. Subsequent
trimethylsilyl ‘endcapping’ generated new resonances at
1
3
29
d 0.2 ppm
C NMR and d 10.2 ppm Si NMR .
Ž . Ž .
These signals are often very small or absent in the
spectrum, especially for the alumina and titania com-
plexes.
2
.8. XPS
Selective information could be obtained from the
data, including elemental percentages, chemical binding
onto the metal oxide and mode of adsorption of alane
and gallane species. More detailed analysis of peak
shape and atomic concentration ratios led to information
about the position and number of different types of
atoms within the molecule. The binding energies of
2
9
Fig. 1. Si CP MAS NMR spectra of Ži. naphthalene functionalised
polymer 3, Žii. polymer 3 after being recycled two times, Žiii.
dihydronaphthalene polymer 32.

2
90
T.R. Õan den Ancker, C.L. RastonrJournal of Organometallic Chemistry 550 (1998) 283–300
1
3
Fig. 2. C CP MAS NMR spectra of Ži. chloropropyl silica, Žii. trimethylsilyl ‘endcapped’ chloropropyl silica, Žiii. trimethylsilyl ‘endcapped’
silylnaphthalene silica.
each of the elements change only slightly irrespective of
the synthetic step applied to the metal oxides. Similar
results have been obtained by other groups w32–36x.
in the ratios of elemental atomic concentrations is in the
expected range and is in agreement with the desired
change in functionalisation at each step in the synthetic
pathways described. Fig. 3 shows the principal photo-
Elemental analyses were calculated using experimen-
tally determined sensitivity factors w37x. In all cases the
elemental analyses were normalised to 100%. The trends
electron peaks
1s for trimethylsilyl and trimethylamine alane ‘en-
Ž
C 1s, O 2p, Si 1s, Cl 2p, Al 2p and N
.

T.R. Õan den Ancker, C.L. RastonrJournal of Organometallic Chemistry 550 (1998) 283–300
291
dcapped’ chloropropyl silica. The O 1s and Si 2p
photoelectron peaks are symmetric and occur at E s
B
5
33.0 and 103.8 eV, respectively and are characteristic
of SiO . The Al 2p photoelectron peak is broad and
2
symmetric and occurs at E s75.7 eV, and is consis-
B
III
tent with Al or Al–O species w32,33x. The C 1s and N
s show multi species character. Multiple species are
1
expected from the carbon, as it is made up of the propyl
carbons, trimethylamine carbons and adventitious car-
bon on the silica surface. Curve fitting of the N 1s peak
indicated that at least two different nitrogen species are
present on the surface, at E s399.2 and 401.5 eV,
B
Fig. 4.
Surface adsorption characteristics of H AlPNMe
3
3
Fig. 3. Curve-fitted N 1s photoelectron peak for trimethylsilyl and
alane ‘endcapped’ chloropropyl silica.
on a SiO substrate have been investigated using X-ray
2
photoelectron spectroscopy XPS and static secondary
Ž .
Fig. 4. X-ray Photoelectron spectra of trimethylsilyl and alane ‘endcapped’ chloropropyl silica powder Ži. C 1s, Žii. O1s, Žiii. Si 2p, Živ. Cl 2p, Žv.
N 1s, Žvi. Al 2p.

2
92
T.R. Õan den Ancker, C.L. RastonrJournal of Organometallic Chemistry 550 (1998) 283–300
to the type and number of nitrogen species present; a
broad peak ranging from E s399.5 to 404 eV was
B
obtained. This is possibly made up of two peaks at
E s401 and 402 eV. Only slight changes in the
B
binding energies of the surface species was expected,
making interpretation difficult. The peaks could possi-
bly be attributed to the nitrogens of –OAlH NMe and
2
3
–
O AlNMe respectively. The N 1s photoelectron peak
Fig. 5. Ži. Molecularly adsorbed trimethylamine alane Žgallane.,
Si OMH NMe Ž5-coordinate.. Žii. Chemisorbed trimethylamine
3 3
of aluminium foil dosed with trimethylamine occurs at
E s402 eV, and is assigned to trimethylamine molec-
2
3
3
alane Žgallane., –OMH NMe Ž4-coordinate.. Žiii. Chemisorbed
2
3
B
trimethylamine alane Žgallane., –O MHNMe3 Ž4-coordinate.. Živ.
2
ularly adsorbed 41 . Similarly, the peak at 402 eV for
the alumina complex can be assigned to the nitrogen of
molecularly adsorbed trimethylamine. As only weak
signals were obtained for the N 1s photoelectron peak
analysis of trimethyl amine alane ‘endcapped’ titania
species is inconclusive to the type and number of
nitrogen species present.
w x
Chemisorbed trimethylamine alane Žgallane., –O MNMe Ž4-coordi-
3
3
nate..
ion mass spectrometry SSIMS
Ž . w38,39x. In this study,
the N 1s peak was deconvoluted into two component
peaks E s399.2 and 402 eV
w38,39x. The higher
binding energy component was attributed to nitrogen
from molecularly adsorbed trimethylamine alane for-
ming a 5-coordinate aluminium centre
.., and the
Ž
.
Similar analysis of the principal photoelectron peaks
B
Ž
C 1s, O 2p, Si 1s, Cl 2p, Ga 2p3r2 and N 1s for
.
Ž
trimethylsilyl and trimethylamine gallane ‘endcapped’
chloropropyl silica were investigated. The O 1s and Si
2p photoelectron peaks are symmetric and occur at
Ž
i
lower binding energy to the adsorption of free
trimethylamine w38,39x. These assignments were con-
E s533.0 and 103.8 eV, respectively and are charac-
B
firmed by analysis of SSIMS data, and by the dosing of
aluminium and oxidised silicon substrates with
trimethylamine w38,39x. Fig. 5 represents the possible
teristic of SiO . The Ga 2p
photoelectron peak is
2
3r2
broad and symmetric and occurs at E s1119.8 eV,
B
III
and is consistent with Ga or Ga–O species w32x. The
bonding modes of trimethylamine alane
gallane M5Ga
Ž
M5Al
.
or
C 1s and N 1s show multi species character. Analysis of
the N 1s peak for trimethylamine gallane ‘endcapped’
species suggested that the trimethylamine is molecularly
adsorbed onto the metal oxide surface and is also
molecularly bound to the gallium metal centres. The N
Ž
.
.
In the present study, the lower binding energy at 399
eV can be attributed to molecularly bound trimethyl-
amine. The second component at 401.5 eV can be
attributed to the nitrogen from chemically bound
trimethylamine alane in the form of partially oxidised
1s peak is broad and centred around E s401.7 eV.
B
Peak shape analysis reveals two possible component
aluminium hydrides
Ž
ii
.
Ä
Ž
iii
.
or
Ž
iv
.
4
, –OAlH NMe . In
peaks at approximately E s395.5 and 402.3 eV, which
2
3
B
this case, the aluminium in now in a 4-coordinate
environment, and a slight shift in the binding energy
would be expected. Preliminary investigations into the
analysis of the surface species by secondary ion mass
spectrometry showed that a large population of AlHq2
species existed, as indicated by a large peak at 29 amu.
Further evidence for the existence of this 4-coordinate
species is achieved by the analysis of the FTIR spectra.
In an attempt to further identify –OAlH NMe and
can be assigned to the nitrogens of molecularly ad-
sorbed trimethyl amine, and chemically adsorbed
trimethylamine gallane. Alumina and titania N 1s
photoelectron peaks were too small and noisy to be
deconvoluted in the similar manner.
The surface adsorption characteristics of H GaP
3
NMe on an SiO substrate has been investigated using
3
2
XPS and SSIMS by Butz et al. w42x. The N 1s peak is
axially symmetric and low in intensity
w42x. The intensity of the peak decreased with time in
E s400 eV
Ž .
2
3
B
5
OAlH NMe species on the silica surface, trimethyl-
3
3
amine alane was physisorbed on silica. Silica powder
and trimethylamine alane were stirred together for 3 h
under vacuum, in an attempt to mimic dosing experi-
ments of Elms et al. w38,39x and Simmonds et al. w40x.
the vacuum chamber, indicating that the adsorbed nitro-
gen species readily desorbs from the surface. The peak
was assigned to the nitrogen from the adsorption of
trimethylamine onto the substrate surface. SSIMS data
were also consistent with this assignment w42x. Molecu-
The surface adsorption characteristics of the resultant
substrate were investigated using XPS and SSIMS. As
expected, similar results to these earlier studies were
obtained, such that molecularly adsorbed trimethyl-
amine and trimethylamine alane were present as surface
species w38–40x.
lar adsorption of trimethylamine gallane would require
the formation of a 5-coordinate gallium species, which
are highly unstable
in a 4-coordinate environment. Low temperature dosing
of trimethylamine gallane onto a SiO wafer
see below , as gallium prefers to be
Ž .
Ž
y1908C
.
2
Analysis of the N 1s photoelectron peak of trimethyl-
amine alane ‘endcapped’ alumina were inconclusive as
was also investigated w42x. The N 1s peak in this case
deconvoluted into two component peaks at E s402.4
B

T.R. Õan den Ancker, C.L. RastonrJournal of Organometallic Chemistry 550 (1998) 283–300
293
Fig. 6. Curved fitted X-ray Photoelectron spectrum of Li 1s of trimethylsilyl ‘endcapped’ lithiopropyl silica.
and 400 eV, attributed to molecularly adsorbed H GaP
metal hydride, suggesting the formation of mono- and
di-hydridometal species.
3
NMe and NMe , respectively.
3
3
In the present study the N 1s peak was deconvoluted
Simmonds et al. w40x have studied the absorption of
into two component peaks E s402.3 and 395.5 eV,
dimethylethylamine alane onto an oxidised silicon sur-
face, and characterised the surface species by FTIR
spectroscopy. In their study, a change in the IR absorp-
tion band for Al–H was observed from 1780 to 1850
B
assigned to the nitrogens of chemisorbed H GaPNMe
3
3
and molecularly adsorbed NMe . The gallium species is
3
expected to be 4-coordinate. Five-coordinate gallium
y1
y1
species are in general unstable, for example H GaP
cm
attributed to the hydrides of physisorbed
bound dimethylethylamine alane. Partially oxidised
upon adsorption. The peak at 1780 cm
is
3
Ž
NMe3.2 decomposes -y268C to H GaPNMe w43x.
Ž
molecularly
3
3
FTIR is in agreement with these findings
Ž
see below
.
.
.
Analysis of the Li 1s photoelectron peak of
trimethylsilyl lithiopropyl silica shows multi species
character, Fig. 6. Asymmetry of the Li 1s peak arising a
high binding energy tail is due to the presence of Li–C
species. The low binding energy component is not a Li
aluminium hydrides, formed from the chemisorption of
dimethylethylamine alane on the silica surface generates
a new peak at 1850 cm . Heating to 1458C during
dosing on the surface resulted in even higher values of
the hydride shift. This is expected to be due to the
decomposition of dihydrido species and the subsequent
formation of mono-hydride species of aluminium oxide.
The higher value of the Al–H absorbances is consistent
with the formation of a 4-coordinate aluminium oxide
y1
1
s species, but a C 1s ghost peak from stray Al–Ka
radiation 233 eV lower than C 1s from the X-ray
Ž
.
source, Fig. 6ii. This is therefore in agreement with the
suggested formation of ‘OLi’ species on the surface of
the silica, during the reaction of lithium biphenylide
with the chloropropyl supported complexes.
sp ecies, e.g ., H 2 A l
HAl
N M e 3 O S iO 3 an d
Ž .
Ž
NMe3.ŽOSiO3.2 type species.
In the present study, physisorbed H AlPNMe has
3
3
2
.9. FTIR
Table 5
M–H stretching frequencies
At each successive step in the preparation of the
metal oxide complexes, the reaction products and start-
ing materials were characterised by FTIR as a method
of determining if residual hydroxyl groups were present.
For alane and gallane ‘endcapped’ complexes, ab-
sorbances attributable to residual Al–H and Ga–H
groups were present at 1870 and 1970 cmy1 respec-
tively. As expected the values of these complexes are at
a higher wavelength than the corresponding free metal
trihydride. A comparison of free metal hydride ph-
ysisorbed and chemisorbed metal hydride is given in
Table 5, and there is a change in the environment of the
Compoundrmaterial
nŽM–H.
y1
Žcm
.
H AlNMe
1760
1790
1890
1890
1875
1855
1860
1980
1985
3
3
physisorbed alane on silica
chemisorbed alane on silica
chemisorbed alane on alumina
chemisorbed alane on titania
H GaNMe
3
3
physisorbed gallane on silica
chemisorbed gallane on silica
chemisorbed gallane on alumina

2
94
T.R. Õan den Ancker, C.L. RastonrJournal of Organometallic Chemistry 550 (1998) 283–300
an absorbance assigned to the Al–H frequency at 1790
cm , and the chemisorbed species at 1870 cmy1. The
absorbance value of the chemisorbed species would
suggest the formation of a dihydro–aluminium oxides
surface species, when compared to values observed by
Simmonds et al. w40x. Absorbances of aluminium hy-
dride alkoxide species supports this theory w44–47x. A
y1
number of alkoxide aluminium hydrides have been pre-
pared, each having slight different absorbances at-
tributed to the Al–H of the complex. The complexes
Ž
i-C H OAlH . 2
,
Ž
t-C H O. 2 AlH and
Ž
t-
4
9
2
4
9
C H O
.
AlH have hydride absorbances at 1842, 1859
4
9
2
y1
and 1842 cm , respectively. Similarly, a variety of
amine alkoxide aluminium hydrides also have different
Fig. 8. FTIR spectra of the Ga–H and Si–H stretching regions of Ži.
physisorbed gallane Ž---., Žii. chemisorbed gallane Ž ..
absorbances attributed to the Al–H, including
y 1
A lH 2
Ž
O R . Ž N M e 3
.
1 8 0 0 – 1 9 0 0 c m
,
,
t
y1
wAlH
Ž
OR.ŽNMe3 x AlH2ŽOR. ŽNH Bu
.
.
.
1867 cm
Analysis of changes in the spectra of trimethylamine
alane and gallane when exposed to air indicate the
stability of the surface protecting groups. The gallane
species proved to be more stable with respect to oxida-
tion in air. Decomposition of the alane complexes re-
sults in the loss of a band attributable to the Al–H, and
the formation of an absorbance attributable to a hy-
droxyl group. This process was complete within a 10
min air exposure, compared with a 40 min exposure for
the gallane complex.
2
Ž
2
2
2
y1
t
AlH
OR. ŽOEt2
1896 cm , for RsC H Bu -2,6-
2
2
6
2
2
t
Me-4 w46–48x, and w
Ä
H Al
Ä
m-OC
Ž
H
.
Bu
4
AlH
Ž
m-H
.4 x
2
2
2
2
y1
1
868 cm w49x.
Similarly, higher shifts in the Ga–H species can also
be attributed to the formation of partially oxidised
species. In fact, as discussed in the XPS section the
gallium is most likely in a 4-coordinate environment.
Gallium hydride shifts for alkoxide complexes have
higher values for the Ga–H stretch. For example
t
y1
m-OC H
wH GaÄ Ž .Bu24x 1918 cm w49x.
2
2
Another important feature of the IR spectra of the
metal oxides ‘endcapped’ with aluminium hydride is the
formation of a new absorbance band at 2000 cm
2.10. EPR
y1
The EPR spectra of the polymer supported alkali
naphthalenides 6 and 7 were obtained at room tempera-
ture in THF. The EPR spectrum of 6 and a simulated
spectrum are given in the preliminary account of this
which can be attributed to Si–H, Fig. 7. The Si–H
species is either formed from the decomposition of
Al–H and the subsequent reaction with siloxanes gener-
ating a Si–H species, as suggested by Simmonds et al.
w40x, or the hydrides may be formed in situ with a
work w1x. The spectrum appears as a multiplet
Ž
g s
av
2.00275 with hyperfine coupling. Simulation using
.
dihydroaluminium oxide species. Similar species were
not detected in the gallium ‘endcapped’ samples, Fig. 8.
This is likely to be due to the high stability of the
gallium surface species, and this is evident by its stabil-
SOPHE w50x indicated the multiplet was generated from
7
the coupling of two equivalent lithiums
2.489"0.004 G , four equivalent hydrogens
1.401"0.002 G
Ž
A
A
Ž
Li
H
.
.
s
s
.
.
Ž
Ž1
and two other equivalent hydrogens
ity in air see below .
Ž .
Fig. 7. FTIR spectra of the Al–H and Si–H stretching regions of Ži.
physisorbed alane Ž---., Žii. chemisorbed alane Ž ..
Fig. 9. EPR spectra of polymer supported sodium naphthalenide 7.

T.R. Õan den Ancker, C.L. RastonrJournal of Organometallic Chemistry 550 (1998) 283–300
295
Ž
A
Ž1
H
.
s2.593"0.004 G
.
. Several simulation experi-
in vacuo and the resulting brown oil was distilled
affording a colourless liquid of the title compound 11.5
250 MHz,
ments were carried out for various couplings, including
Li–Li, Li–H, of varying combinations of atoms, and
numbers of equivalent atoms
Li, and 4=Li with 4=H . The best fit was obtained
for the system described above.
The EPR spectrum of polymer supported sodium
naphthalenide also gave a multiplet with hyperfine cou-
pling
signals making simulation difficult. The broadening may
arise from dipole–dipole interaction of the sodium atoms
which has been seen in sodium zeolite systems w51,52x.
Ž
1
g, 66%
CDCl3
7.53–7.74
62.8 MHz, CDCl3
C7 , 126.7 C3
4., 134.2
C2 , 134.3
59.61 MHz
Si–C 850 cm
.
, b.p. 1208C
, d 0.6 s, SiMe2
3H, m, H4,5,8 , 8.33
Ž
0.5 mmHg
.
. H NMR:
Ž
Ž
for example 6=Li, 4=
.
Ž
.
, 7.10–7.35
Ž
3H, m, H3,6,7.
,
1
3
.
Ž
.
Ž
1H, m, H2
.
;
C NMR:
Ž
.
, d 3.5 ppm
, 128.1 C8
C4a , 136.5
, d y26.3 ppm
Ž
SiMe2
, 129.7
C1a , 139.1
s, SiMe2
.
.
, 125.3
C5 , 131.8
C1
. IR
C6 ,
Ž .
126.1
Ž
.
Ž
.
Ž
.
Ž
.
Ž
C
Ž
.
Ž
.
Ž
.
Ž
.
;
2
9
Ž
Fig. 9
.
. In this case there is a broadening of the
Si NMR
thin film
Ž
n
.
Ž
y1
Ž
.
Ž
.
.
3.2. Synthesis of naphthalene functionalised polymers
X
,3
3
3
. Experimental section
A solution of 1-
1.67 g, 7.57 mmol;
50 ml was added to an ice-cold slurry of the Grignard
Ž
chlorodimethylsilyl
.
naphthalene, 2
w
Ž
a
.
b
Ž .
3.5 g, 15.8 mmolx in THF
Silica gel, Keisegel 60, 230 mesh was purchased
Ž
.
from Fluka. Alumina used was laboratory grade for
column chromatography, activity grade 1, basic, and
reagent of chloromethylated polystyrene w
Ž
a
.
7.0 g, 1.34
y1
y1
mmol g , 7.57 mmol;
Ž
b
.
6.52 g, 4.11 mmol g , 15.8
. The reaction mixture was
stirred for 12 h at room temperature. The modified
polymer was filtered, washed with THF 3=75 ml and
dried in vacuo for 6 h at 608C to afford compound 3,3
as a white solid w
. 6.8 g, 99%; . 6.2 g, 100% based
on weight gainx.
Found for 3 C, 89.2; H, 8.4; Cl,
-0.3%, 3 requires C and H 96.87, Cl 0% Found for
was obtained from Sigma
0446 was obtained from BDH Chemicals.
Chloromethylated polystyrene 1.20–1.34, and 4.11–
was purchased from BIO-RAD.
LiBu was obtained from Metallgesellschaft Germany
Ž
A-8878
.
. Titania
Ž
GPR
100 ml
mmolx in THF Ž .
3
.
Ž
Ž
.
y1
X
4
.15 mmol g
Cl
.
n
Ž
.
Ž
a
.
b
Ž .
as a hexane solution, typically 1.60 M, and was stan-
dardised before use. Benzonitrile, 1-bromo-naphthalene,
Ž
.
. Ž
X
X
9
-chloroanthracene, 1-chloromethylnaphthalene, 5-
chloro-2-pentanone, 3-chloro-1-phenyl-1-propanol, 3-
chloropropyl trimethoxysilane, triethylphosphate and
triphenylphosphate were obtained from Aldrich. N-
Methyl 3-aminopropyl trimethoxysilane was purchased
from Petrach chemicals. 1- Chlorodimethylsilyl naph-
3 C, 88.1; H, 7.9; Cl 0.2%, 3 requires C and H 92.86;
2
9
Cl, 0%
.
.
Si NMR
nujol : n
Ž .
79.45 MHz, CP MAS : d y3.9,
y1
Ž
.
y3.5. IR
Ž
.
Ž
C–H
.
1251, 1253 cm
n Si–C
Ž .
y1
844, 839 cm
.
Ž
.
Ž
.
3.3. Synthesis of polymer supported lithium naph-
X
thalene w22x, H AlPNMe w53x, H GaPNMe w54x,
Mg
biphenylide w56x were prepared following literature pro-
cedures. Lithium powder dispersed in paraffin, was
washed in hexane and dried prior to use. 2-
propyl
chloro-2-pentanone following standard literature proce-
dures w57x.
thalenide 6,6
3
3
3
3
Ž
anthracene.ŽTHF
.
w55x, lithium and sodium
3
X
A slurry of silylnaphthalene polymer 3,3 w
Ž
a
.
2.8 g,
was
stirred for 12 h at room temperature. A solution of
2.2 ml, 3.3 mmol;
3.13 mmol;
Ž
b
.
2.0 g, 5.09 mmolx in THF
50 ml
Ž .
X
Ž
3 -Chloro-
.
-2-methyl-1,3-dioxalane was prepared from 5-
lithium biphenylide 4 w1.5 M,
Ž
a
.
b
Ž .
3.6 ml, 5.4 mmolx in THF was added slowly to the
swollen polymer affording a deep blue mixture. This
was stirred for 12 h resulting in a reddish-brown solid.
The filtrate was removed, the polymer was washed with
3
.1. Synthesis of 1-(chlorodimethylsilyl)naphthalene 2
22]
[
THF 3=50 ml and dried in vacuo for 6 h to afford
Ž .
X
a 2.8 g; b 2.0
compound 6,6 as a redrbrown solid wŽ . Ž .
n
A hexane solution of LiBu
added to an ice-cooled solution of 1-bromonaphthalene
16.5 g, 80 mmol in Et O 100 ml over 10 min. The
Ž
55 ml, 84 mmol
.
was
gx. EPR g s2.0029, 2.0026.
av
Ž
.
Ž
.
3.4. Synthesis of polymer supported sodium naph-
2
X
resulting orange solution was stirred for 1 h at room
temperature during which time an orange precipitate
formed. The mixture was then added dropwise to a
thalenide 7,7
X
A slurry of silylnaphthalene polymer 3,3 w
Ž
a
.
3.7 g,
was
stirred for 12 h at room temperature. A solution of
2.9 ml, 4.4 mmol;
solution of dichlorodimethylsilane
Et O 50 ml
mixture stirred overnight, warming to room tempera-
ture. Volatiles were then removed in vacuo, the residue
taken up in hexane
remove lithium chloride. Volatiles were then removed
Ž
15 ml, 123 mmol
.
in
4.1 mmol; b 50 ml
Ž . 1.5 g, 3.8 mmolx in THF Ž .
Ž
.
, over 15 min at y788C, and the reaction
2
sodium biphenylide 5 w1.5 M,
Ž
a
.
b
Ž .
3.5 ml, 4.7 mmolx in THF was added slowly to the
swollen polymer affording a deep blue mixture. This
was stirred for 12 h resulting in a reddish-brown solid.
100 ml , and the solution filtered to
Ž .

2
96
T.R. Õan den Ancker, C.L. RastonrJournal of Organometallic Chemistry 550 (1998) 283–300
The filtrate was removed and the polymer was washed
with THF 3=50 ml and dried in vacuo for 6 h to
3.6 g;
lected and washed with THF then dried in vacuo at
0.6 g . IR nujol
Ž
.
358C for 10 h as a redrbrown powder
Ž
.
Ž
.
X
y1
afford compound 7,7 as a redrbrown solid w
Ž
a
.
n
Ž
Al–H
.
1878 cm
.
Ž
b
. 1.5 gx. EPR g s2.0033, 2.0100.
av
3
.8. Synthesis of alane ‘endcapped’ silica supported
3
.5. Synthesis of alane and trimethylsilyl ‘endcapped’
lithium naphthalenide 11
silica supported silylnaphthalene 8
Powder 9
Ž
0.9 g
.
was dispersed in THF
1.2 ml, 1.8 mmol added slowly
25 ml and
Ž .
To a suspension of lithiopropyl trimethylsilyl and
lithium biphenylide
Ž
.
alane ‘endcapped’ silica
lithium biphenylide with chloropropyl trimethylsilyl and
alane ‘endcapped’ silica 1.2 g was added 1- chlorodi-
methylsilyl naphthalene 0.5 g and the pale yellow
Ž
derived from the reaction of
yielding a deep blue mixture. The mixture was stirred
overnight affording a red slurry. Powder 11 was col-
lected and washed with THF then dried in vacuo at
Ž .
358C for 10 h as a redrbrown powder 0.9 g .
Ž
Ž
.
.
Ž
.
mixture stirred overnight. Powder 8 was filtered and
washed with THF then dried in vacuo at 608C for 6 h
3.9. Synthesis of alane and trimethylsilyl ‘endcapped’
silica supported sodium naphthalenide 12
2
9
Ž
1.2 g
y120
Si
CH . ., 0.0
CP MAS
CH SiCH3., 26.0
.
.
Si NMR
lattice silicon
Si
CH . .
: d 2.3
Ž
79.45 MHz, CP MAS
.
d y100 to
Ž
.
, y50 toy75
Ž
OSiCH , 10.5
.
2
1
3
Ž
Ž
Ž
Ž
;
C NMR
Ž
Ž
100.56 MHz,
CH Si , 17.2
small peak,
Powder 8
Ž
1.3 g
.
was dispersed in THF
1.5 ml, 2.3 mmol added slowly
25 ml and
Ž .
3
3
3 2
.
Ž
Si
Ž
CH3. ., 11.8
.
sodium biphenylide
Ž
.
3
2
Ž
Ž
CH CH CH
.
, 47.8
Ž
yielding a deep blue mixture. The mixture was stirred
overnight affording a bright red slurry. Powder 12 was
collected and washed with THF then dried in vacuo at
2
2
2
2
n
y1
CH Cl
.
, 127.2
Ž
Carom
.
. IR
Ž
nujol
.
Ž
Al–H
dy90 to y120
, 9.5 Si
CH . .
100.56 MHz CP
CH Si , 17.1
small peak,
.
1879 cm
.
2
X 29
w8 Si NMR
Ž
79.45 MHz, CP MAS
.
Ž
Ž
lattice silicon, y40 toy653ŽOSiCH2
.
Ž
Ž
Ž
,
3
358C for 10 h as a brown powder 1.3 g . IR nujol :
Ž . Ž .
3
1
y1
Si
Ž
CH . . Žnot detected
.
;
C NMR
n
Ž
Al–H
.
1881 cm
.
3
2
MAS
Ž
CH Cl
.
d
2.0
Ž
Si
Ž
Carom
Ž
CH3. ., 11.3
Ž
.
3
2
CH SiCH3., 27.0
CH CH CH
.
Ž
, 47.8
Ž
.
3.10. Synthesis of N–Me aminopropyl naphthalene sil-
ica 13
2
2
2
2
y1
.
, 128.0
Ž
.
. IR
Ž
nujol
.
: n
Ga–H
1980 cm
.
2
3
.6. Synthesis of alane ‘endcapped’ silica supported
A mixture of silica
methoxy silane 1.3 g
and triethylamine 0.5 ml
Ž
1.9 g
.
, N-Me
Ž
3-aminopropyl
0.7 g
.
.
tri-
silylnaphthalene 9
Ž
.
, chloromethylnaphthalene
Ž
Ž
.
in a toluenermethanol solu-
To a suspension of lithiopropyl alane ‘endcapped’
tion was refluxed for 24 h. Volatiles were removed in
vacuo and the resulting powder was washed in toluene
. Ž . Ž .
2=30 ml , water 2=50 ml CHCl3 2=30 ml and
methanol. The product was dried in vacuo at 608C for 6
silica
with chloropropyl alane ‘endcapped’ silica
added 1- chlorodimethyl silylnaphthalene
the pale yellow mixture stirred overnight. Powder 9 was
filtered and washed with THF then dried in vacuo at
Ž
derived from the reaction of lithium biphenylide
0.5 g.. was
0.2 g and
Ž
Ž
Ž
Ž
.
.
2
9
h
Ž
2.2 g
.
.
Si NMR
lattice silicon
100.56 MHz, CP MAS
, 34.3 CH N
Ž
79.45 MHz, CP MAS
, y45 to y75 OSiCH
d 10.3
, 52.6
.
d y90 to
13
y115
Ž
.
Ž
.
;
C
2
.
2
9
6
08C for 6 h
d y100 to y125
OSiCH , 1.0 Si
CH3. .
11.5
CH CH CH , 48.0
Ž
0.5 g
.
.
Si NMR
Ž
79.45 MHz, CP MAS
, y50 to y80
100.56 MHz, CP
CH SiCH3., 28.0
.
NMR
Ž
.
.
Ž
CH Si
, 20.7
Ž .
CH N , 130.9
2
2
Ž
lattice silicon
.
Ž
Ž
Ž
CH CH CH
.
Ž
2
2
2
3
1
3
Ž
.
d
Ž
Ž
Ž
;
C NMR
, 18.0
small peak, CH Cl
Carom .
.
2
2
MAS
.
CH Si
.
Ž
2
2
Ž
Ž
Ž
.
Ž
.
, 128.8
3.11. Synthesis of trimethylsilyl and alane ‘endcapped’
N–Me aminopropyl naphthalene silica 14
2
2
2
2
y1
X 29
Carom
79.45 MHz, CP MAS
OSiCH2
100.56 MHz, CP MAS
.
. IR
Ž
nujol
.
: n
Ž
Al–H
d y90 to y125
, 0.7 Si
CH . .
d 11.5
, 47.9
.
1876 cm . w9 Si NMR
.
Ž
lattice silicon,
1
3
y40 to y80
Ž
.
Ž
Ž
;
C NMR
CH Si , 17.8
small peak,
To a suspension of 13 2.5 g , was added 10 ml of
Ž .
3
2
Ž
Ž
.
Ž
.
chlorotrimethylsilane and the mixture refluxed for 6 h
under nitrogen and then allowed to stir overnight at
room temperature. The excess reactant was removed by
distillation, and washed with water, followed by ethanol
to remove traces of HCl. The silica was dried in vacuo
2
CH SiCH3., 26.9
Ž
CH CH CH
.
.
Ž
2
2
2
2
y1
CH Cl
.
, 128.2
Ž
Carom
. IR
Ž
nujol
.
n
Ž
Ga–H
.
1979 cm
.
2
3
.7. Synthesis of alane and trimethylsilyl ‘endcapped’
silica supported lithium naphthalenide 10
at 608C for 4 h, then suspended in THF
and H AlNMe 0.6 g was slowly added. After gas
15 ml at 08C
Ž .
Ž
3
.
3
Powder 8
Ž
0.6 g
.
was dispersed in THF
Ž
25 ml
.
and
evolution ceased the mixture was stirred overnight at ca.
208C whereupon the solid was collected, washed with
THF then dried in vacuo at 608C for 2 h as a white
lithium biphenylide
yielding a deep blue mixture. The mixture was stirred
overnight affording a red slurry. Powder 10 was col-
Ž
1.2 ml, 1.8 mmol added slowly
.
2
9
powder
Ž
2.5 g
.
.
Si NMR 79.45 MHz, CP MAS d
Ž .

T.R. Õan den Ancker, C.L. RastonrJournal of Organometallic Chemistry 550 (1998) 283–300
297
y90 to y120
0.2 very smallrbroad Si
MHz, CP MAS d 0.24
CH CH CH
Ž
lattice silicon
.
, y45 to y75
Ž
OSiCH2
C NMR 100.56
CH3.3., 10.4
CH N , 52.1
79.45 MHz, CP
.
, y45 to y70
3
.
,
3.16. Synthesis of alane ‘endcapped’ N–Me amino-
propyl sodium naphthalenide silica 19
1
3
1
Ž
Ž
CH . .
;
Ž
3
3
.
Ž
Ž
very small, Si
, 34.0
Ž
Ž
Ž
Ž
CH Si
.
.
, 20.3
, 127.1
d y90 to y120
OSiCH2 , 9.9 very small Si
MHz, CP MAS d 0.6 very small, Si
CH CH CH , 34.0
.
.
Powder 15
Ž
0.3 g
.
was dispersed in THF
1.5 ml, 2.3 mmol added slowly
25 ml and
Ž .
2
2
2
2
3
X 29
CH N
MAS
Ž
Carom
.
. w14 Si NMR
Ž
sodium biphenylide
Ž
.
2
.
Ž
lattice silicon
yielding a deep greenrblue mixture. Powder 18 was
1
Ž
.
Ž
Ž
CH3. .; C NMR
Ž
100.56
CH3. ., 10.5
collected and washed with THF then dried in vacuo at
3
.
Ž
Ž
Ž
358C for 1 h as a redrbrown powder
0.3 g .
Ž .
3
.
Ž
Ž
CH Si
.
, 21.2
, 127.9
.
.
Ž
CH N
, 52.4
2
2
2
2
3
y1
CH N
.
Ž
Carom
.
. IR
Ž
nujol
: n
Ž
Ga–H
.
1983 cm
x
3.17. Synthesis of benzyl-1-(dimethylsilyl)naphthalene
2
2
8
3
.12. Synthesis of alane ‘endcapped’ N–Me amino-
propyl naphthalene silica 15
1-
mmol
magnesium chloride
Ž
Chlorodimethylsilyl
was added to a THF
0.153 M, 33.7 mmol, 220 ml
.
.
-naphthalene
50 ml solution of benzyl
and
Ž
4.15 g, 18.2
.
Ž
.
To a suspension of 13
Ž
0.4 g
.
in THF
0.6 g
lution ceased the mixture was stirred overnight at ca.
08C, whereupon the solid was collected, washed with
THF then dried in vacuo at 608C for 2 h as powder 33
Ž
15 ml
.
at 08C
Ž
was slowly added H AlPNMe3
Ž
.
. After gas evo-
the reaction mixture was stirred overnight at room
temperature. Volatile materials were removed in vacuo
Ž .
and the residue taken up in hexane 70 ml , filtered to
remove magnesium chloride and the solvent removed in
vacuo to afford a brown oil. Distillation yielded a
colourless oil 28
3
2
2
9
Ž
0.4 g
.
.
Si NMR
lattice silicon
100.56 MHz, CP MAS
, 34.3 CH N , 52.4
Ž
79.45 MHz, CP MAS
, y40 to y60 OSiCH2
d 9.5 CH Si
.
d y90 to
13
y120
Ž
.
Ž
.
;
C
3.42 g, 66% b.p. 1378C 0.5 mmHg .
Ž . Ž .
NMR
Ž
.
Ž
.
, 20.7
.
, 132.9
X 29
Ž
Found for 28 C, 82.46; H, 7.51%, 28 requires C, 82.53;
2
1
Ž
Ž
Ž
CH CH CH
Carom
79.45 MHz, CP MAS
.
Ž
.
Ž
CH N
H, 7.31. H NMR
Si 2H, s, SiCH2
CH3. ., 2.2
H2,3,5– 8,arom C NMR 50.3 MHz, CDCl3
CH3. .; 14.8
SiCH2
, 125.7
C4 , 132
Si NMR
CH3.2 .
Ž
200 MHz, CDCl3
d 0.0 6H, s,
. Ž
2
2
2
3
2
y1
.
. IR
Ž
nujol
.
n
Ž
Al–H
.
1879 cm . w15 Si NMR
lattice sili-
100.56 MHz,
Ž
Ž
3
.
, 6.5–7.8
Ž
12H, m,
d_y1.7
2
1
.
d y90 to y120
Ž
.
;
Ž
.
.
1
3
con
CP MAS
CH N , 52.1
.
, y40 to y70
Ž
OSiCH2
.
;
C NMR
Ž
Ž
Ž
Si
Carom
Ž
Ž
C6
, 117.45, 124.5, 124.6, 128.7
2
.
d 9.8
Ž
CH Si
CH N
.
, 21.0
, 130.7
Ž
CH CH CH
.
n
, 34.3
.
Ž
, 125.5
C5 , 130.5
, 140
1.8 ppm
Ž
.
Ž
C7
.
Ž
, 126.1
Ž
C3
.
, 128.5
C4a , 136.5
d_y
C8 ,
Ž .
2
2
2
2
.
Ž
H
.
Ž
x
.
Ž
Carom
.
. IR
Ž
nujol
Ž
Ga–
129.7
C1a
.
Ž
.
C2 , 134.4
.
Ž
.
3
2
y1
29
.
1981 cm
Ž
.
Ž
C1
s, Si
.
;
Ž
79.45 MHz, C H
.
6
6
2
Ž
Ž
.
3
.13. Synthesis of trimethylsilyl and alane ‘endcapped’
N–Me aminopropyl lithium naphthalenide silica 16
3.18. Synthesis of benzyl-1-(dimethylsilyl) lithium naph-
thalenide 29
Powder 14
Ž
0.4 g
.
was dispersed in THF
1.5 ml, 2.3 mmol added slowly
25 ml and
Ž .
lithium biphenylide
Ž
.
Lithium
of benzyl-1-
mmol in THF
Ž
0.02 g, 2.88 mmol
dimethylsilyl naphthalene 28
100 ml . The reaction mixture was
.
was added to a solution
yielding a deep greenrblue mixture. Powder 16 was
Ž
.
.
Ž
0.8 g, 2.88
collected and washed with THF then dried in vacuo at
.
Ž
3
58C for 1 h as a brown powder
Ž
0.4 g
.
.
stirred overnight to give deep blue solutions. EPR gav
s2.0028.
3
.14. Synthesis of alane ‘endcapped’ N–Me amino-
propyl lithium naphthalenide silica 17
3.19. Synthesis of benzyl-1-(dimethylsilyl) sodium naph-
thalenide 30
Powder 15
Ž
0.3 g
.
was dispersed in THF
1.5 ml, 2.3 mmol added slowly
25 ml and
Ž .
lithium biphenylide
Ž
.
Sodium
of benzyl-1-
mmol in THF
Ž
0.07 g, 3.04 mmol
dimethyl-silyl naphthalene 28
100 ml . The reaction mixture was
.
was added to a solution
yielding a deep greenrblue mixture. Powder 17 was
Ž
.
Ž
0.8 g, 2.88
collected and washed with THF then dried in vacuo at
.
Ž
.
3
58C for 1 h as a brown powder
Ž
0.3 g
.
stirred overnight to give deep blue solutions. EPR gav
s2.0028.
3
.15. Synthesis of trimethylsilyl and alane ‘endcapped’
N–Me aminopropyl sodium naphthalenide silica 18
3.20. Synthesis of benzyl-1-(dimethylsilyl)dihydronaph-
thalene 31
Powder 14
Ž
0.4 g
.
was dispersed in THF
1.5 ml, 2.3 mmol added slowly
25 ml and
Ž .
sodium biphenylide
Ž
.
To a stirred solution of lithium benzyl-1-
silyl
naphthalenide 29 wprepared from the reaction of 28
2 g, 7.25 mmol and lithium powder 0.5 g, 7.25
mmol 100 ml was added a moist solution of
x in THF
Ž
dimethyl-
yielding a deep greenrblue mixture. Powder 18 was
.
collected and washed with THF then dried in vacuo at
Ž
.
Ž
3
58C for 1 h as a redrbrown powder
Ž
0.4 g
.
.
.
Ž
.

2
98
T.R. Õan den Ancker, C.L. RastonrJournal of Organometallic Chemistry 550 (1998) 283–300
2
9
THF
resulting in the dissipation of the blue solution to a clear
solution. The solution was diluted in hexane 100 ml
washed with water 2=25 ml and the organic layer
Ž
25 ml
.
and the mixture was stirred for 1 h,
THF then dried in vacuo at 608C for 2 h
NMR 79.45 MHz, CP MAS d y90 to y120
silicon . IR nujol Ga–H 1976 cm
Ž
1.9 g
.
.
Si
Ž
.
.
Ž
lattice
y1
Ž
.
,
Ž
.
n
Ž
.
.
Ž
.
separated and dried over anhydrous magnesium sul-
phate. Removal of the solvent afforded a pale yellow
oil. Analysis by H NMR indicated a mixture of 31 and
unreacted 28, in a ratio of 95:5. H NMR
CDCl3
3.25. Synthesis of gallane ‘endcapped’ silica (physi-
sorbed)
1
1
Ž
200 MHz,
A mixture of silica
was stirred in vacuo at 608C for 4 h
79.45 MHz, CP MAS d y90 to y115
con . IR nujol : n Ga–H
Ž
1.0 g
.
and H GaNMe
Ž
0.2 g
Si NMR
lattice sili-
.
3
3
2
9
.
: d 0.2
3H, m, 6.7–7.4,
50.3 MHz, CDCl3
, 62.6 CH2 , 67.9
Carom , 125.7 C6
C2 , 139.3 C4a , 139.7
Ž
6H, s, Si
Ž
CH3. ., 1.8
Ž
2H, s, SiCH
.
,
2
Ž
1.0 g
.
.
Ž
2
1
3
3
.4–3.7
Ž
Ž
11H, m, H2,3,5– 8,arom
: d y2.5 Si
CH3. .; 25.7
CHSi , 124.0, 124.1, 128.0,
, 126.3
C1a
.
;
C
Ž
.
y1
NMR
Ž
.
Ž
Ž
.
Ž
.
Ž
.
1860 cm
.
2
Ž
SiCH2
.
Ž
Ž
.
Ž
.
.
1
1
28.3
29.1
.
Ž
Ž
.
C7
.
, 126.7
, 142.6
Ž
;
C
3.
Si
,
3.26. Reaction of chlorobenzene and polymer 6
2
9
Ž
Ž
.
Ž
.
Ž
Ž
C1
.
NMR
79.45 MHz, C H6.: d y4.8 ppm
Ž
s, Si
Ž
CH3. .
.
THF
Ž
75 ml
.
was added to polymer 6 derived from
with lithium biphenylide
.1 ml, 1.7 mmol and the reaction mixture stirred for 4
h at room temperature. A THF solution of chloroben-
zene 0.15 M was added to the resulting red slurry,
yielding a colourless solution and pale yellow solid after
the addition of 6 ml of the halide solution. Quenching
of aliquots with excess HCl, followed by back titration
with NaOH indicated 95% lithium reagent formation.
The filtrate was removed via a cannular and the poly-
Ž .
mer washed with THF 2=50 ml . Chlorotrimethylsi-
lane 1 ml, 8 mmol was added to the combined filtrate
and washings, after stirring for 2 h at room temperature
the resulting solution was extracted into hexane and
filtered. The solvent was distilled from the mixture to
6
2
reaction of 3
Ž
1.4 g, 1.6 mmol
.
X
3
.21. Synthesis of dihydronaphthalene polymer 32,32
Ž
.
1
To a stirred solution of polymer supported lithium
Ž
.
X
X
naphthalenide 6,6 wderived from, the reaction of 3,3 :
1.5 g, 1.5 mmol; 1.1 g, 2.8 mmol with lithium
biphenylide and 50
2.2 ml, 3.3 mmolx in THF
ml was added a moist solution of THF 25 ml and the
Ž
a
.
b
Ž .
b
Ž
.
Ž
a
.
Ž
.
Ž
.
Ž
.
mixture was stirred for 1 h, resulting in the dissipation
of the blue solution. The polymer was filtered, washed
with THF
afford a mixture of 32 and 3
3=50 ml dried in vacuo for 6 h at 608C to
Ž .
Ž
.
X X
Ž
32 and 3
solid, in a ratio of 90:10. Si NMR 79.45 MHz, CP
MAS nujol C–H
.
as a white
2
9
Ž
.
d 5.0, y3.9; 4.7, y3.4. IR
Ž
.
n
Ž
.
y1
y1
1
1
253, 1255 cm , n
Ž
Si–C
.
842, 841 cm
.
afford a colourless liquid, which was shown by H
NMR and HPLCrMS analysis to be pure
phenyltrimethylsilane. The recovered polymer was dried
in vacuo for 12 h at 408C to afford compound 3 and 31
3
.22. Synthesis of alane ‘endcapped’ silica (chemiso-
rbed)
in a ratio of 90:10
recovery
Ž1st cycle. Ž1.4 g, 100% total
To a suspension of silica
Ž
3.0 g
.
in THF
4.0 g . After gas
evolution ceased the mixture was stirred overnight at ca.
40 ml at
Ž .
.
.
0
8C was slowly added H AlNMe3
Ž
.
3
A full set of the yields are given in Table 1. For
Barbier-type reactions the products were distilled from
2
08C, whereupon the solid was collected, washed with
1
13
2
9
the reaction solvent then analysed by H and C NMR.
Distillation temperatures at ambient pressure for
quenched reaction product from the reaction of lithiated
complexes of 24–27 with chlorotrimethylsilane was
THF then dried in vacuo at 608C for 2 h
Ž
3.1 g
.
.
Si
. Ž
d y95 to y120 lattice
y1
NMR
silicon
Ž
79.45 MHz, CP MAS
. IR nujol Al–H 1880 cm
.
Ž
.
n
Ž
.
.
0
8C, 1708C and 698C, respectively, these values com-
3
.23. Synthesis of alane ‘endcapped’ silica (physi-
sorbed)
pare well with literature values w58x.
3
.27. Reaction of chlorobenzene and metal oxide sup-
A mixture of silica
was stirred in vacuo at 608C for 4 h
79.45 MHz, CP MAS : d y90 to y120
silicon . IR nujol Al–H
2.0 g and H AlNMe 0.5 g
Ž . Ž .
3 3
29
ported lithium naphthalenides
Ž
2.1 g
.
.
Si NMR
lattice
Ž
.
Ž
y1
Reactions were carried out similarly to the above,
and yields were determined in the same manner. The
results of this study are represented in Table 5.
.
Ž
.
n
Ž
.
1790 cm
.
3
.24. Synthesis of gallane ‘endcapped’ silica (chemiso-
rbed)
3
.28. Synthesis of 3-trimethylsilyl-1-phenyl-1-trimethyl-
To a suspension of silica
Ž
2.0 g
.
in THF
Ž
25 ml
.
at
siloxy-propane
0
8C was slowly added H GaNMe
Ž
2.2 g . After gas
.
3
3
evolution ceased the mixture was stirred overnight at ca.
08C, whereupon the solid was collected, washed with
To a solution of 3-chloro-1-phenyl-1-propanol
Ž
0.75
n
2
g, 0.44 mmol
.
was added LiBu
Ž
0.3 ml, 0.47 mmol
.

T.R. Õan den Ancker, C.L. RastonrJournal of Organometallic Chemistry 550 (1998) 283–300
299
1
13
affording an orange solution. The resulting solution was
added to a slurry of polymer 6 derived from reaction of
in a solution of 28 in hexane
NMR consistent with literature values w58x. Method C.
A solution of 9-chloroanthracene 0.34 g, 1.6 mmol in
THF 40 ml was added slowly over 20 min to a
suspension of lithium powder 0.024 g, 3.4 mmol and
28 0.022 g, 0.08 mmol in THF 40 ml at y788C.
Ž
0.39 g, 96%
.
. H and
C
5
1
Ž
0.9 g, 1.0 mmol
.
with lithium biphenylide
Ž
0.7 ml,
Ž
.
.1 mmol . This resulted in the dissipation of the red
.
Ž
.
colour yielding a colourless solution and pale yellow
solid. The filtrate was removed via a cannular and the
Ž
.
Ž
.
Ž
.
polymer washed with THF
Chlorotrimethylsilane 1.3 ml, 10 mmol
the combined filtrate and washings and after stirring for
h at room temperature. Volatiles were removed in
Ž
12 = 50 ml
.
.
This resulted in the dissipation of the green colour, and
the consumption of some of lithium powder yielding a
pale yellow solution containing excess lithium powder.
The solution was stirred for a further 2 h.
Ž
.
was added to
2
vacuo, and the resulting orange solid was taken up in
hexane, and filtered. Concentration and cooling to
Chlorotrimethylsilane 0.40 ml, 3.1 mmol was added
Ž .
and the resultant solution stirred for 1 h at room temper-
ature. Volatiles were removed in vacuo, and the result-
ing yellow oil was taken up in hexane and filtered.
y308C afforded the bis-silylated compound as a pale
1
orange solid
d y0.1
.7–2.0
2H, m, CH2
Ž
0.8 g, 80%
.
. H NMR
Ž
Ž
200 MHz, CDCl
.
,
3
Ž
Ž
9H, s, Si
Ž
CH3. ., y0.5
9H, s, Si
Ž
CH3. .
Concentration and cooling to y308C afforded 9-
methylsilyl anthracene, with a small amount of 52 0.40
. H and C NMR data agree with literature
values w58x. Method D. A solution of 9-chloroanthra-
cene 0.20 g, 0.94 mmol in THF 40 ml was added
slowly over 20 min to a suspension of lithium powder
0.024 g, 3.4 mmol and naphthalene 0.022 g, 0.02
mmol in THF 40 ml . This resulted in the dissipation
Ž
tri-
3
3
1
3H, m, CH SiMe , CHOSiMe3., 3.68–3.81
.
Ž
2
3
1
3
1
13
Ž
.
, 6.92–7.30
Ž
5H, m, Harom
SiCH3 , y1.7
COSiMe3., 40.7
CH
.
;
C NMR
SiCH3
.
, 124.0,
2
g, 98%
.
Ž
50.3 MHz, CDCl3
.
d y1.5
Ž
.
Ž
.
,
1
1
Ž
6.6
Ž
CH Si
.
, 23.5
Ž
Ž
Ž
.
Ž
.
2
q
27.8, 128.0, 143.8
OSiMe qSiMe3..
Ž
Cph
.
; MS mre 118
Ž
54%, M
–
.
Ž
.
Ž
3
.
Ž
.
of the green colour, and the consumption of some of
lithium powder yielding a pale yellow solution contain-
ing excess lithium powder. The solution was stirred for
3
.29. Synthesis of 9-trimethylsilyl(anthracene)
X
Method A. THF
derived from reaction of 3
lithium biphenylide 1.9 ml, 2.8 mmol
Ž
75 ml.X was added to polymer 6
1.0 g, 2.5 mmol
a further 2 h. Chlorotrimethylsilane 0.40 ml, 3.1 mmol
Ž .
Ž
.
with
.x and the mixture
was added and the resultant solution stirred for 1 h at
room temperature. Volatiles were removed in vacuo,
and the resulting yellow oil was taken up in hexane and
filtered. Concentration and cooling to y308C afforded
Ž
stirred for 4 h at room temperature, then stirred at
y788C for 1 h. A THF solution of 9-chloroanthracene
Ž
0.15 M
.
was added to the resulting red slurry at
9-
Ž
trimethylsilyl
.
anthracene, with a small amount of
1
13
y788C, yielding a colourless solution and pale yellow
solid after the addition of 13 ml, 1.95 mmol of the
halide solution. Quenching of aliquots with HCl showed
5% lithium reagent formation. The filtrate was re-
moved via a cannular and the polymer washed with
naphthalene
with literature values w58x.
Ž
0.22 g, 95%
.
. H and C NMR consistent
Ž
.
9
3
.30. Reaction of chlorobenzene and polymer 7
THF
mmol
Ž
.
2=50 ml . Chlorotrimethylsilane 1.3 ml, 10
. Ž
was added to the combined filtrate and washings
THF
reaction of 3
0.9 ml, 1.3 mmol
h at room temperature. A THF solution of chloroben-
zene 0.15 M was added to the resulting red slurry,
yielding a colourless solution and pale yellow solid after
the addition of 3.2 ml, 0.48 mmol of the halide
Ž
75 ml
1.0 g, 1.1 mmol
and the reaction mixture stirred for 2
.
was added to polymer 7 derived from
and after stirring for 2 h at room temperature the
volatiles were removed in vacuo and the resulting
residue extracted into hexane, concentration and cooling
Ž
.
with sodium biphenylide
Ž
.
to y308C afforded pale yellow crystals of 9-
Ž
trimethyl-
. H and C NMR con-
sistent with literature values w58x. Method B. A solution
of 9-chloroanthracene 0.34 g, 1.6 mmol in THF 40
ml was added slowly over 30 min to a solution of 29
wderived from reaction of 28
0.47 g, 1.7 mmol with
lithium powder 0.012 g, 1.7 mmol 40 ml at
x in THF
Ž
.
1
13
silyl anthracene 0.46 g, 94%
. Ž .
Ž
.
Ž
.
Ž
solution. Quenching of aliquots as above indicated 88%
sodium reagent formation. The filtrate was removed via
.
Ž
.
a cannular and the polymer washed with THF
ml . Chlorotrimethylsilane 0.9 ml, 7.0 mmol was added
Ž
2=50
Ž
.
Ž
.
.
Ž
.
y788C. This resulted in the dissipation of the blue
to the combined filtrate and washings and after stirring
for 2 h at room temperature the resulting solution was
extracted in the usual manner to afford a colourless
colour yielding a pale yellow solution, stirring was
continued for a further 3 h. Chlorotrimethylsilane
ml, 3.1 mmol was added and the resultant solution
Ž
0.40
l
.
liquid which was shown by H NMR and HPLCrMS
stirred for 1 h at room temperature. Volatiles were
removed in vacuo, and the resulting yellow oil was
taken up in hexane and filtered. Concentration and
analysis to be pure phenyltrimethylsilane 0.06 g, 82% .
Ž .
The recovered polymer was dried in vacuo for 12 h at
408C to afford compound 3 and 32 in a ratio of 85:15
Ž1st cycle. Ž1.03 g, 103% total recovery.
.
cooling to y308C afforded 9-
Ž
trimethylsilyl
.
anthracene

3
00
T.R. Õan den Ancker, C.L. RastonrJournal of Organometallic Chemistry 550 (1998) 283–300
w27x C.A. Fyfe, Y. Zhang, P. Aroca, J. Am. Chem. Soc. 114 Ž1992.
252.
3
.31. Reaction of chlorobenzene and metal oxide sup-
3
ported sodium naphthalenides
w28x J.W. De Haan, H.M. van den Bogaert, J.J. Ponjee, L.J.M. van
de Ven, J. Coll. Interface Sci. 110 Ž1986. 591.
Reactions were carried out similarly to the above,
and yields determined in the same manner. The results
of this study are represented in Table 3.
w29x F. Garbassi, L. Balducci, P. Chiurlo, L. Deiana, Appl. Surf. Sci.
8
4 Ž1995. 145.
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w31x D.E. Leyden, D.S. Kendall, T.G. Waddell, Anal. Chim. Acta.
Acknowledgements
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26 Ž1881. 207.
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of New South Wales, for helpful discussions, and Barry
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